Journal of Cleaner Production xxx (2016) 1e10

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Journal of Cleaner Production

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A cleaner and greener fuel: Biofuel blend formulation and emission

assessment
Haslenda Hashim a, b, *, Menaka Narayanasamy a, b, Nor Alaza Yunus a, b,
Lim Jeng Shiun a, b, Zarina Ab Muis a, b, Wai Shin Ho a, b
a
Process Systems Engineering Centre (PROSPECT), Research Institute for Sustainable Environment, Universiti Teknologi Malaysia (UTM), 81310, UTM Johor
Bahru, Johor, Malaysia
b
Faculty of Chemical and Energy Engineering, Universiti Teknologi Malaysia (UTM), 81310, UTM Johor Bahru, Johor, Malaysia

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 15 May 2016
Received in revised form
3 June 2016
Accepted 3 June 2016
Available online xxx

Biofuel is an attractive vehicular fuel option for the transportation sector. Diverse biofuel blends can be
produced from biomass. Complexity arises when optimum biofuel blends need to be designed to comply
with fuel regulation standards as well as generate less emission. This paper discusses an integrated
computational and experimental technique to design economically viable and environmentally friendly
tailor-made biofuel blends from palm biomass that is abundant in Malaysia. An experimental based trialand-error method is time consuming and uses up resources. Computational approaches adopt a systematic blend formulation methodology that assists focused experimental work. The biofuel design
problem has been formulated as a Non-Linear Program to satisfy specied target properties such as
density, kinematic viscosity, cetane number, gross caloric value, distillation temperature, and sulphur
content. Target properties predicted through mixture property models were experimentally validated
according to ASTM standard test methods. Five optimum tailor-made biofuel blend formulations were
generated based on cost, gross caloric value and emission limitations. The result indicates that biofuel
blends with butyl levulinate could increase the price of biofuel up to 80% from the retail price of B5
diesel. However, cleaner biofuel with less cost and highest caloric value can be achieved for biofuel
blends that contain B5 diesel, butanol and ethanol. The application of this model yields about 26% CO2
emission reduction and about 22% less sulphur content as well as comply with the EN590 fuel regulation
standard.
2016 Elsevier Ltd. All rights reserved.

Keywords:
Biofuel
Fuel standard
Computational method
Experimental
Emission assessment

1. Introduction
Government regulations, stringent laws on greenhouse gas reductions, and unstable fuel prices have prompted the search for an
alternative source of energy for the transportation sector. Biofuel is
an environmentally friendly and renewable source that has been
globally adopted in many countries with the support of government policies. The International Energy Agency, IEA (2013) predicted that around 27% of transportation fuel would be completely
replaced by biofuels before the year 2050.
Malaysia is now part of a long list of countries that implement
biofuel through the introduction of B5 diesel, which has a 5% blend

* Corresponding author. Faculty of Chemical and Energy Engineering, Universiti

Teknologi Malaysia (UTM), 81310, UTM Johor Bahru, Johor, Malaysia.
E-mail address: haslenda@utm.my (H. Hashim).

of fatty acid methyl ester obtained from palm biomass. Generally,

no modication is required on existing diesel engines and fuel
systems that run on small amounts of biofuel blends. However, fuel
blends need to adhere to the specied standards of conventional
diesel.
Palm biodiesels are known to be highly viscous (Knothe, 2010)
and emit increased levels of NOx gases (Hamdan and Khalil, 2010)
due to their fuel properties. Many effort aims to improve the
properties of palm biodiesel through the combination of multiple
biofuel sources. Iqbal et al. (2015) investigated the effects of
blending palm biodiesel with coconut and jatropha biodiesel. It was
found improved fuel blend properties and competitive engine
performance with emission characteristics were observed in 20%
jatropha-palm-coconut blend compared to conventional diesel.
Sanjid et al. (2014) evaluated performance and emission characteristics of palm and jatropha blends. However, tests conducted at 5
vol% and 10 vol% blends recorded high fuel consumption and

http://dx.doi.org/10.1016/j.jclepro.2016.06.021
0959-6526/ 2016 Elsevier Ltd. All rights reserved.

Please cite this article in press as: Hashim, H., et al., A cleaner and greener fuel: Biofuel blend formulation and emission assessment, Journal of
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nitrogen oxide emissions. Bio-alcohols are particularly useful when

dealing with viscosity issues (Hussan et al., 2013). However, the low
cetane number and caloric value of bio-alcohols require a combination of additives for better performance (Oguz et al., 2010).
The experimental based trial-and-error method is time
consuming and uses up resources. A more efcient way is to use a
model-based systematic methodology that employs computational
approaches to narrow down the search region, followed with
focused experimental work. The biofuel blends can be tailored to
meet specic attributes, so as to be sustainable, economically
sound, and environmentally friendly.
Systematic product design methodologies have recently
expanded to include biofuel blend design. Hada et al. (2011)
implemented chemometric techniques through a systematic
method to identify molecular structures of biodiesel additives. The
approach enabled the combination of property clustering techniques and group contribution methods in enhancing the design of
molecular fragments that meet target properties. Simasatitkul et al.
(2013) proposed systematic methodology to design, synthesis, and
analysed an integration of market dynamics of biodiesel integrated
with fatty alcohol and waste edible oil via an economical and
operationally feasible process. Voll et al. (2012) combined a spatial
partial equilibrium model of the wood market to predict price and
demand for methyltetrahydrofuran protability. Hechinger et al.
(2012) proposed a framework that combined rigorous generation
of molecular structures with stepwise reduction to simplify the
screening and selection of potential biofuel candidates based on
fuel properties. Phoon et al. (2015) implemented a decompositionbased computer-aided approach to identify feasible green diesel
blend candidates that meet property constraints. Ulonska et al.
(2015) presented a methodology to systematically screen fermentation products and processes that serve as a platform for biofuel
production from lignocellulosic biomass. Manuel and Wolfgang
(2016) developed a framework for model-based fuel design for
the identication of biofuel components for use in spark-ignition
and compression-ignition engines. Yunus et al. (2012) developed
a computer-aided methodology to design gasoline with different
types of blending agents. This work was later expanded upon to
cover formulations of blended liquid mixtures with verication
using rigorous models (Yunus et al., 2014). Kashinath et al. (2012)
focused on the design an economical and environmental benign
of tailor-made green diesel blends. However SO2 emission has been
neglected in the emission assessment. In addition, all the computational results obtained from related researches have not been
validated by experimental work. This study aims to develop a new
framework to design tailor-made biofuel blends via a computeraided model-based approach with experimental validation.
Experimental validation ensures the reliability of the designed
biofuels, but has been frequently neglected except in a handful of
studies. Fuel target properties were established according to the
European Standard of fuel quality i.e. EN 590. The predicted biofuel
properties were then validated through laboratory tests. The carbon dioxide emissions and fuel sulphur content of these biofuel
blends are also discussed in this paper.
2. Methodology
Most studies on fuel blend design employs a forward approach
that relies on property prediction from a set of fuel blend compositions. The model-based systematic methodology approach is
based on the reverse of this concept. Systematic methodology in
the design of the proposed fuel blend for this study follows the
fundamental concept introduced by Gani (2004). The methodology
is divided into four main tasks i.e. problem denition, identication
of property models, generation of fuel blend formulation, and

experimental validation of the formulated blend properties. Fig. 1

illustrates the tasks involved in designing tailor-made biofuel
blends.
2.1. Task 1: problem denition
2.1.1. Dening attributes of interest
Dening the problem is key in constructing a systematic
methodology for product design. Pertinent information could then
deducted from problem denition. Attributes of interest in terms of
designing tailor-made biofuel blends include cost, environmental
impact, safety factor, and product performance. Generally, traits of
product design encompass criteria such as economical viability and
environmental friendliness without forsaking product quality.
Nonetheless, the safety attribute is equally important, especially in
the design of fuel blends. These attributes are then translated into
target properties and target values. Table 1 summarises the list of
target properties based on attributes of interest for the design of
the tailor-made biofuel blends in this study.
2.1.2. Dening target properties
Important physiochemical properties that inuence the fuel
blends fraction include density (Benjumea et al., 2008), kinematic
viscosity (Demirbas, 2008), cetane number (Varatharajan and
Cheralathan, 2012), caloric value (Silitonga et al., 2013), and
distillation temperature (Pandey et al., 2012). Fuel density and
viscosity are important parameters that directly inuence fuel
atomisation (Jayed et al., 2011) and spray pattern (Al-Hamamre and
Al-Salaymeh, 2014), which affects engine performance.
Cetane number characterises the tendency of fuel to combust
under certain pressure and temperature on its own volition. Fuel
with higher cetane number is more preferable as it ensures smooth
engine operation and reduces exhaust emissions (Jayed et al., 2011).
The caloric value of fuel is associated with the amount of power
the fuel produces during combustion. Fuel with higher energy
content will increase engine power output with less fuel consumption (Channiwala and Parikh, 2002). Distillation temperature
represents the volatility of diesel, the readiness of liquid diesel
change into vapor (Sajjad et al., 2014).
Denoga and Quiros (2004) observed a weak correlation between
distillation temperature of fuels and engine performance parameters. However, fuel economy was shown to improve with lower
distillation temperatures. Since distillation temperature signies
the volatility of fuel, this fuel property is markedly important as a
safety measure. Maximum values for distillation temperature are
commonly specied in fuel standards. The fuel sulphur content
(Tan et al., 2009) is another property that is of great concern, as it
greatly affects emissions from diesel engines and is a controlled
factor in fuel standards (Tan et al., 2013).
2.1.3. Dening constraints
Novel biofuel blends need to adhere to consistent fuel properties
to ensure suitability in engine testing and evaluation. In the
absence of a standard for biofuel blends, both the American Society
for Testing and Materials (ASTM) D975 and EN590 standards for
conventional diesel fuels in the United States and Europe can be
used as the baseline for biofuel blends containing up to 20% biodiesel (Geng et al., 2009).
In this study, the EN590 standard was employed as the baseline
standard. Table 2 shows key fuel properties and their limits, as per
the EN590 standard for fuels. Limits for caloric value are seldom
specied in fuel standards. However, gauging the ability of power
generation in alternative fuels is an important criterion. Thus, extra
constraint in terms of fuel caloric value was set to design the
tailor-made biofuel blends in this study. A 10% reduction from

Please cite this article in press as: Hashim, H., et al., A cleaner and greener fuel: Biofuel blend formulation and emission assessment, Journal of
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TASK 1.1: Defining attributes of interest

TASK 1: Problem definition

TASK 1.2: Defining target properties

TASK 2: Identification of
property models

TASK 1.3: Defining constraints

TASK 1.4: Selection of fuel blending
components

TASK 3: Generation of blend

formulation

TASK 3.1: Defining and declaring parameters,

variables and equaons
TASK 3.2: Solving the model for two different
scenario

Maximum fuel calorific

Minimum raw material

TASK 3.3: Screening alternatives based on

feasible cost and minimum sulphur content

TASK 4: Experimental validation of formulated blend properties

Fig. 1. The systematic methodology for the design of tailor-made biofuel blends.

Table 1
Attributes of interest and target properties for fuel blending design.
Attributes of interest

Target properties

Product performance

Density
Kinematic viscosity
Cetane number
Caloric value
Distillation temperature
Fuel sulphur content
Raw material cost

Safety factor
Environmental impact
Cost

Table 2
Fuel properties and limits as per the EN590 standard for diesel fuels.
Fuel property

Units

Density at 15
C
Kinematic viscosity at 40
C
Cetane number
Caloric value
Distillation temperature
Sulphur content

kg/m3
mm2/s
e
MJ/kg


C
ppm

a
b

Limits
Min

Max

820.0
2.0
46a
40b
e
e

845.0
4.5
e
e
360.0
10.0

Cetane index.
Estimated value.

caloric value of B5 diesel was specied as the lower limit.

2.1.4. Selection of biofuel blend components
Extensive research work has given rise to a long list of promising

candidates for biofuel blending. Biodiesel, bio-alcohols, and levulinate ester are three of the most attractive candidates. Among
these, alcohols are the most widely investigated component.
Incorporating alcohols in biofuel blends reduce viscosity (Yasin
et al., 2013) and density of blends (Hussan et al., 2013). Therefore,
ethanol is generally preferred as it is easily attainable. Although it
contributes to emission reductions, ethanol has low energy content
and cetane number (Hansen et al., 2005). Furthermore, ethanol is
poorly miscible with diesel, especially in high ratios.
The drawback of ethanol as a sole blend component is that it
requires different chemical groups to act as additives or cosolvents. In this study, besides ethanol, butanol and butyl levulinate were also chosen as biofuel blend components. Butanol, an
attractive alcohol candidate, has a relatively higher cetane number
(Dogan, 2011) and energy content (Rakopoulos et al., 2010). Butanol
is easily miscible with diesel without any evident phase separation,
even in high blending ratios and does not require engine modication or compromises in safety (Atmanli et al., 2014).
A few studies have been conducted on butyl levulinate as a fuel
blend component. Being an oxygenated fuel, butyl levulinate was
discovered as a promising candidate for the reduction of particulate
matter (Chuck and Donnelly, 2014) and smoke emissions (Janssen
et al., 2010). Butyl levulinate can be produced through esterication of levulinic acid with butanol and is miscible with diesel, unlike its counterpart ethyl levulinate (Harwardt et al., 2011).
However, its high oxygen content results in lower caloric value
and cetane number (Jenkins et al., 2013), so it must be blended with
a suitable fuel component or added with cetane improvers
(Christensen et al., 2011). Therefore, butyl levulinate was

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investigated as a fuel blend component in diesel (Kashinath et al.,

2012) and gasoline fuels (Yunus et al., 2014) in relation to its
properties.
The biofuel blend in this study comprises of B5 diesel, butanol,
ethanol, and butyl levulinate. Petroliam Nasional Berhad (PETRONAS) supplied the B5 diesel for this study with property values
obtained from Enffue Carotino (2007). Butanol and ethanol were
purchased from I-Chem Solution Sdn. Bhd. (2013) with a purity of
99% and 99.9%, while SigmaeAldrich (M) Sdn. Bhd. (2013) supplied
butyl levulinate of 98% purity. The fuel properties of ethanol and
butanol were obtained from Giakoumis et al. (2013) whereas the
property values of butyl levulinate were obtained based on the
thorough study of Christensen et al. (2011). Table 3 shows the
physiochemical properties and raw material costs of these fuel
blend components.

2.2. Task 2: identication of property models

To design the optimum blend, consistent fuel blend properties
need to be obtained. Physiochemical properties of a fuel blend
component can either be measured experimentally or estimated
through pure component property models based on group contribution or atom connectivity models (Gani, 2004). These are then
incorporated into the design in the form of mixture property
models. Each set of property model is exclusive to the design
problem.
In contrast to pure component properties, mixture properties
are more difcult to obtain through measurement. Data from
experimental tests do not cover the entire blend fraction range at
different test conditions. The variability in components makes this
process even harder. Thus, prediction of mixture properties will
have to rely on thermodynamic insights like mixing rules and
correlations.
Linear mixing rules are employed with the principle that the
volume of components becomes an additive when blended. The
mixture properties will be a function of blend fraction and pure
component properties. Although not all fuel properties are additive,
the linear mixing rule helps simplify the blend design methodology. Eqs. (1) and (2) represent the general mixing rule for the target
properties (Garcia et al., 2010) and correlation with kinematic viscosity (Weirong and Lempe, 2006), both of which were originally
proposed by Kay and Arrhenius and then applied in this study.

ymix

n
X

2.3. Task 3: generation of blend formulation

The tailor-made biofuel blend design problem is formulated
using Non-Linear Programming (NLP) via a model-based approach.
In this study, a Generalised Algebraic Modelling System (GAMS)
was used to generate a set of tailor-made biofuel blends that are
optimised in terms of product performance, cost, safety, and environmental effect. The mixture property models, constraints, and
target values were coded into the GAMS. The model was then
applied in two different scenarios in order to generate more potential biofuel blend candidates.
The rst scenario involved minimising the total fuel blend cost
to ensure that the formulated tailor-made biofuel blends are
economically viable. The model was then solved for the maximum
fuel blend caloric value in the second scenario to improve engine
performance. Next, the formulated biofuel blends were screened
based on fuel cost and minimum sulphur content. In the last stage,
experimental tests were conducted to validate formulated biofuel
blend properties.

2.3.1. Declaring and dening data

Table 4 indicates the fuel mixture properties model that will be
coded into the GAMS. The subscript i represents individual biofuel
blend components whereas the subscript j represents the biofuel
blend mixture. The mathematical model is further subjected to the
following constraints, as shown in Eqs. (3) to (10):
I. Target property
1. Density

820  rj  845

(3)

2. Kinematic viscosity

Table 4
Mixture property models implemented in this study.
Fuel property

vi yi

(1)

ln mmix

the biofuel blend, n is the number of components in the biofuel

blend, ymix is the mixture property for dened target properties,
and m signies kinematic viscosity in mm2/s.

Density at 15
C (kg/m3)
Kinematic viscosity at 40
C (mm2/s)

n
X

Cetane number

vi ln mi

(2)

Caloric value (MJ/kg)

Distillation temperature (
C)

where vi is the fraction (in volume or mass based on properties

unit) of each blend component, i refers to individual components in

Sulphur content (ppm)

Cost (MYR/L)

Mixture property model

P
rj yi  ri
i
P
lnmj  yi  ln mi
Pi
CNj yi  CNi
i
P
CVj mi  CVi
i
P
DTj yi  DTi
P i
SCj mi  SCi
i
P
zj yi  Ci
i

Table 3
Property values of fuel blend components.
Fuel property

B5 diesel

Butanol

Ethanol

Butyl levulinate

Density at 15
C (kg/m3)
Kinematic viscosity at 40
C (mm2/s)
Cetane number
Caloric value (MJ/kg)
Distillation temperature (
C)
Sulphur content (ppm)
Cost (MYR/L)

854.70
4.57
56.10
45.14
364.70
0.26
2.76

810.00
2.50
25.00
33.00
118.00
0.00
42.00

789.00
1.20
8.00
26.80
78.00
0.00
44.00

974.00
1.99
14.00
27.44
232.00
0.80
400.00

Note e cost of B5diesel, butanol, ethanol and butyl levulinate is of June 2014.

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2:0  mj  4:5

(4)

3. Caloric value

CVj  40

(5)

4. Distillation temperature

DTj  360

(6)

5. Fuel sulphur content

SCj  10

(8)

(9)

8. Blend fraction of butyl levulinate

0  blj  1

(10)

where vi and mi represents the volume and mass fraction of each

biofuel blend component; rj is density of the biofuel blend in kg/
m3; mj refers to kinematic viscosity of biofuel blend in units of mm2/
s; CVj is caloric value of the biofuel blend in MJ/kg; DTj is distillation temperature of the biofuel blend in
C; and SCj corresponds
to sulphur content of biofuel blend in units of ppm while elj represents the ethanol fraction in blend and blj is butyl levulinate
fraction in each biofuel blend.
The ethanol fraction in the biofuel blends is limited to a
maximum allowable limit of 10 vol% (Shahir et al., 2014). Ethanol is
known to have poor miscibility with diesel but phase separation is
not expected in lower ethanol content fuel blends (Hussan et al.,
2013). Hajba et al. (2011) proved that the presence of more than
10 vol% ethanol could adversely affect fuel blend properties like
cetane number, caloric value, and viscosity. A study by Li et al.
(2005) reported that the engine power of fuel blends with 10 vol
% ethanol was only slightly affected, with no decrease in thermal
efciency. Research ndings by Al-Hassan et al. (2012) also supported this study. A constraint was also imposed on butyl levulinate
to enable its selection as a tailor-made biofuel blend component
despite its high raw material cost.

2.3.2. Solving model and screening alternatives

The Non-linear model for designing tailor-made biofuel blends
was solved for two different scenarios, minimising the total cost of
tailor-made biofuel blends and maximising the caloric value. The
rst scenario is minimising the total fuel blend cost as written in Eq.
(11) where only the raw material cost of the fuel blend components
were taken into account.

fmin mincost

The potential candidates from each scenario, which satisfy the

imposed constraints, are then subjected to a screening process. The
screening criteria are based on attributes of interest for the biofuel
design. The total cost of tailor-made biofuel blends cannot exceed
MYR 20/L. This assumption was vaguely based on general social
acceptance towards alternative vehicular fuel prices. Fuel blends
were also screened for sulphur content of less than 10 ppm to
comply with the EN590 fuel regulation standard. Subsequently, the
screened tailor-made biofuel blend candidate properties were
validated with experimental tests.
2.4. Task 4: experimental validation of formulated blend properties

7. Blend fraction of ethanol

elj  0:1

(12)

(7)

6. Fraction balance for volume and mass

vi f0  vi  1g or mi f0  mi  1g

fmax max CVj

(11)

While the second scenario is maximising the gross caloric

value (CVj) of blends as formulated in Eq. (12)

Tailor-made biofuel blends in this study were formulated via a

model-based approach, through the use of mixture property
models. Mixture property models follow linear mixing rules to
predict all biofuel blend properties except for kinematic viscosity.
Although linear models are good estimates for ideal mixtures,
experimental validation is essential to verify the appropriateness of
the models employed in this study.
Samples of tailor-made biofuel blends were prepared according
to their formulation. The tailor-made biofuel blends were labelled
as Blend 1, Blend 2, Blend 3, Blend 4, and Blend 5. The biofuel blends
were prepared using a splash-blending method 48 h prior to testing
and then stored tightly at room temperature to observe possible
phase separation. Medium speed mechanical stirrers were used to
ensure proper blending. Experimental testing was performed by
Lotus Laboratory Services (M) Sdn. Bhd. Test methods conformed to
the strict ASTM procedures, which recommend that testing of fuel
properties be repeated at least twice for each sample. Note that the
experimental data presents in this paper is represents the average
experimental value.
3. Results and discussions
This section presents the results obtained from the proposed
model with experimental validation.
3.1. Biofuel blends and the impact on cost, caloric value and
emission
The tailor-made biofuel blend design problem was formulated
as a NLP model and solved through the GAMS solver (version 24.2)
for two different scenarios, minimise cost and maximise caloric
value. Table 5 illustrates the optimum tailor-made biofuel blends
for both scenarios. The emissions analysis from the formulated
tailor-made biofuel blends are also computed and presented.
The tabulated results clearly show butanol as the more favoured
alcohol blend candidate and present in all optimised biofuel blends.
Favourable physiochemical properties of butanol in fuel blends
evidently support these ndings (Yoshimoto et al., 2013). Despite
the high raw material cost, three of the formulated blends consisted
of butyl levulinate blend have lower caloric value which means
that more amount of biofuel is required in order to generate the
same amount of energy. Fraction of butyl levulinate in biofuel
blends was found as dominant factor in affecting the total cost of
tailor-made biofuel blends. Blend 1, Blend 3 and Blend 4 are
considered non-competitive biofuel blends as compared to B2 and
B5 diesel.
The blending of different biofuel components leads to various
sulphur content in the tailor-made biofuel blends. The fuel sulphur
content of B5 diesel at 0.216 ppm is undoubtedly higher than the

Please cite this article in press as: Hashim, H., et al., A cleaner and greener fuel: Biofuel blend formulation and emission assessment, Journal of
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H. Hashim et al. / Journal of Cleaner Production xxx (2016) 1e10

Table 5
Results of the optimum tailor-made biofuel blends.

Blend
Blend
Blend
Blend
Blend

1
2
3
4
5

Fuel blend components (vol%)

B5 diesel

Butanol

Ethanol

Butyl levulinate

74.6
78.3
75.7
79.3
83.0

24.4
21.7
12.3
9.77
7.0

0
0
10.0
10.0
10.0

1.0
0
2.0
1.0
0

tailor-made biofuel blends. However, Blend 5 was found to have the

lowest cost among all the formulated blends i.e. MYR 9.63/L and
considered among the highest caloric value. On the other hand,
Blend 1 has the lowest sulphur content at 0.202 ppm. However, this
blend also costs MYR 16.30/L, which is more expensive than the
MYR 2.76/L B5 diesel (retail price in June 2014) and has lower
caloric value as compared to Blend 2 and Blend 5. Hence, it is
important to consider the trade-off between biofuel blends total
cost and caloric value for the selection of the optimum biofuel
blends.
Table 6 summarises the predicted and tested properties of the
formulated biofuel blends for validation against the property
models. Note that the experimental data in this table represents the
average experimental value. The Absolute Percentage Error (APE)
between both results was computed using Eq. (13). Among the
biofuel properties, the kinematic viscosity and distillation temperature recorded the highest APE, while the other properties
recorded less than 10% APE, which is deemed acceptable.



Approximate  Actual
  100%
Absolute % error 

Actual

Total fuel cost (MYR/L)

Caloric value (MJ/kg)

Fuel sulphur content (ppm)

16.30
11.28
19.67
14.65
9.63

42
42.5
41.5
42
42.4

0.202
0.204
0.213
0.214
0.216

error at 26%. The linear mixing model shows the best agreement
with prediction viscosities of ideal mixtures, as originally proposed
by Arrhenius, and is not suitable for implementation in this study.
However, these ndings are contradictory to the ndings of
Gautam and Agarwal (2014). Investigating kinematic viscosity of
biodiesel blends through Arrhenius's linear mixing model, reported
APE less than 10%. Krisnangkura et al. (2006) also reported similar
ndings.
Predicted and experimentally tested viscosities of tailor-made
biofuel blends in this study comply with the EN590 standard,
ranging between 2.0 and 4.5 mm2/s. Thus, the mixture property
models are deemed acceptable. Several other correlations from
various studies were implemented to observe the best agreement
with the predicted kinematic viscosities. Fig. 2 illustrates the differences between the experimentally tested viscosities of tailormade biofuel blends with the predicted values using ve different
correlations including the one through GAMS.
It can clearly be observed from Fig. 2 that the kinematic viscosity

4.5

(13)

where Approximate depicts predicted biofuel properties via GAMS

and Actual represents results from experimental testing.
Kay's mixing rule for estimation of distillation temperature was
found as not appropriate for this study. The prediction of distillation temperature reported errors of more than 10% for all the tailormade biofuel blends except for Blend 5, which reported a minimum
APE of exactly 10%. Blend 1 had the maximum APE of 14%. However,
the reported values were less than the distillation temperature of
B5 diesel and the maximum allowable limit imposed by the EN590
fuel reference standard.
The predicted kinematic viscosity recorded the highest APE with
a maximum value of 38% (Blend 2). Blend 3 reported minimum

4.0
Kinematic viscosity (mm2/s)

Tailor made biofuel blends

3.5
Tesfa et al.

3.0

GAMS Predicon

2.5

Gautam&Agarwal

2.0

Krisnangkura et al.

1.5

Experimental Test

1.0

Edreder&Mezughi

0.5
0.0
0

2
3
4
Tailor made biofuel blends

Fig. 2. Comparison of correlations between the kinematic viscosities of tailor-made

biofuel blends from various studies and the experimental values.

Table 6
Comparison between predicted and tested tailor-made biofuel blend properties.
Fuel blend properties

Calculation method

Tailor made biofuel blends

Blend 1

Blend 2

Blend 3

Blend 4

Blend 5

Density at 15
C (kg/m3)

GAMS prediction
Experimental test
APE (%)
GAMS prediction
Experimental test
APE (%)
GAMS prediction
Experimental test
APE (%)
GAMS prediction
Experimental test
APE (%)
GAMS prediction
Experimental test
APE (%)

845.00
843.10
0.23
3.91
2.90
34.93
48.10
50.00
3.80
42.00
41.00
2.44
303.30
352.00
13.85

845.00
842.80
0.26
4.01
2.90
38.24
49.40
49.00
0.72
42.50
41.00
3.66
311.20
350.00
11.10

845.00
843.10
0.23
3.65
2.90
25.86
46.60
50.00
6.78
41.50
41.00
1.10
302.90
354.00
14.43

845.00
842.80
0.26
3.74
2.90
29.00
47.90
49.00
2.33
42.00
40.00
4.88
310.80
350.00
11.19

845.00
842.60
0.29
3.83
3.00
27.77
49.10
50.00
1.78
42.40
40.00
6.13
318.80
354.00
9.96

Kinematic viscosity at 40
C (mm2/s)

Cetane number

Caloric value (MJ/kg)

Distillation temperature (
C)

Please cite this article in press as: Hashim, H., et al., A cleaner and greener fuel: Biofuel blend formulation and emission assessment, Journal of
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H. Hashim et al. / Journal of Cleaner Production xxx (2016) 1e10

values predicted using the correlation developed by Tesfa et al.

(2010) had the best agreement with the experimentally tested
values, with APE of less than 10%. The correlation relates kinematic
viscosity to the function of density and can be applied at any given
temperature as long as the units correlate. Kinematic viscosities of
tailor-made biofuel blends predicted through correlations proposed by Krisnangkura et al. (2006) and Gautam and Agarwal
(2014) showed similar results with the GAMS-predicted values.
The correlation developed by Edreder and Mezughi (2014) had the
highest prediction deviation compared to the experimental values.
In future, the correlation developed by Tesfa et al. (2010) will be
integrated into this model to substitute Arrhenius's linear mixing
model and predict tailor-made biofuel blend viscosities.
3.2. Biofuel blend properties testing
Formulated tailor-made biofuel blends comply with the EN590
fuel regulation standard, as all tested biofuel blend properties are
within the stipulated range. Fig. 3 and 4 graphically display the
range of density and kinematic viscosity of tailor-made biofuel
blend properties predicted using GAMS and experimental tests.
Density was tested using the ASTM D4052 test method at 15
C
whereas kinematic viscosity followed the ASTM D445 test method
at 40
C.
The density of the biofuel blends complied with the minimum
and maximum limits of 820 kg/m3 and 845 kg/m3 as specied in
the EN590 fuel reference standard. Deviation in density values was
quite small, with APE ranging between 0.23% and 0.29%. However,
considerable discrepancy occurred in the prediction of kinematic
viscosity for the biofuel blends due to incompatibility of the linear
model used in the GAMS prediction. Since the predicted and tested
values fall within the stipulated range of 2.0e4.5 mm2/s, the
applied mixture property model is still applicable for this study.
Fig. 5 exhibits the validated results from the GAMS prediction
for cetane number of the tailor-made biofuel blends. The ASTM
D976 test method was used to compute the cetane number. The
predicted and tested values were greater than the minimum limit
of 46 set by the EN590 fuel reference standard. Substantial difference only occurred in Blend 3 with APE reported as 6.78%, which
could be attributed to high blend fraction of butyl levulinate in the
biofuel blend. Nonetheless, experimental values contradict with
this assumption.
Fig. 6 displays the caloric value from the GAMS prediction with
experimental validation for the tailor-made biofuel blends. The
ASTM D4868 test method was conducted following experimental
testing. Both caloric values comply with the imposed minimum
limit of 40.0, as graphically depicted. The APE for the biofuel blends

Fig. 4. The predicted and experimentally tested kinematic viscosity of the tailor-made
biofuel blends.

Fig. 5. The predicted and experimentally tested cetane number of the tailor-made
biofuel blends.

Fig. 6. The predicted and experimentally tested caloric value of the tailor-made
biofuel blends.

was recorded to vary from 1% to 7%. Fig. 7 shows the comparison

between distillation temperature values. Experimental tests were
conducted using the ASTM D86 test method. Although the APE
values were reported to be above 10%, it still complied with EN590
fuel reference standard with the maximum limit of 360
C.

3.3. Biofuel blend emission results

Fig. 3. The predicted and experimentally tested density of the tailor-made biofuel
blends.

The CO2 emissions of the tailor-made biofuel blends were

computed via Eq. (14), as described in the study by Kashinath et al.
(2012).

Please cite this article in press as: Hashim, H., et al., A cleaner and greener fuel: Biofuel blend formulation and emission assessment, Journal of
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H. Hashim et al. / Journal of Cleaner Production xxx (2016) 1e10

diesel.
4. Conclusions and further recommendations

Fig. 7. The predicted and experimentally tested distillation temperature of the tailormade biofuel blends.

Fig. 8. CO2 emission of the tailor-made biofuel blends and B5 diesel.


CO2

3:11  rj  vdj
1000


(14)

where rj represents density of the biofuel blends in kg/m3; vdj

represents volume fraction of the B5 diesel in the biofuel blends;
and CO2 is expressed in terms of kg/L. Fig. 8 shows the CO2 emitted
by the tailor-made biofuel blends in comparison with the baseline
B5 diesel. It was found that the tailor-made biofuel blends recorded
a signicant reduction in CO2 emission levels with Blend 1 generating the least amount of CO2 i.e. 26% less than the B5 diesel. Fig. 9
illustrates the fuel sulphur content of the biofuel blends in comparison with B5 diesel. It was found that Blend 1 had the least
amount of sulphur content with a 22% difference compared to B5

In this study, a systematic methodology for designing tailormade biofuel blends was developed and further validated with
experimental work. A decomposition-based method was applied to
solve the blending problem, where the objective was to quickly
screen-out optimal biofuel blends that satisfy the properties set by
the EN590 fuel standard at minimum cost, maximum caloric value
and less environmental impacts. The linear mixing model for
density, kinematic viscosity, cetane number, caloric value and
distillation temperature were validated using an average value of
experimental data in order to examine its accuracy. It can be seen
that there is a very good agreement between the predicted using
model and measured values except for kinematic viscosity and
distillation temperature. Average deviation of the predicted values
from the measured ones for each data generates absolute % error
less than 10%. For kinematic viscosity, the results of Tesfa et al.
(2010) had the best agreement with the experimentally tested
values, with APE of less than 10%. Though signicant errors existed
for distillation temperature, all investigated fuel properties complied with the limits imposed by EN590 fuel reference standard.
The results show that signicant CO2 reductions and less
sulphur content could be attained for Blend 1 that contains B5
diesel, butanol, and butyl levulinate. Achieving maximum CO2 reductions (26%) and less sulphur content (22%) however, results in
an average 83% rise in biofuel cost and also has lower caloric value.
In contrast Blend 5 was found to have the lowest cost among all the
formulated blends with the cost MYR 9.63/L and having among the
highest gross caloric value. The results featured in this paper
showcase the ability of the decomposition-based method to minimize the cost of tailor-made biofuel blends and produce cleaner
biofuel. An integrated study that includes engine performance
testing using formulated tailor-made biofuel blends will be further
discussed in another publication.
Acknowledgements
The authors would like to thank the Malaysian Ministry of
Higher Education (MoE) and Universiti Teknologi Malaysia (UTM)
for funding this project under the vote Q.J130000.2544.10H67.
Nomenclature

Abbreviation
ASTM
American Society for Testing and Materials; EN European
Standard
FAME
Fatty Acid Methyl Ester
GAMS
Generalised Algebraic Modelling System
NLP
Non-Linear Programming
Subscripts
i
individual fuel blend component
j
fuel blend mixture
n
number of components in the fuel blend

Fig. 9. The fuel sulphur content of the tailor-made biofuel blends and B5 diesel.

Parameters and variables

blj
volume fraction of butyl levulinate in fuel blend mixture
elj
volume fraction of ethanol in fuel blend mixture
fmax
maximising function
fmin
minimising function
ri
density of individual fuel blend fraction in kg/m3
rj
density of fuel blend mixture in kg/m3

Please cite this article in press as: Hashim, H., et al., A cleaner and greener fuel: Biofuel blend formulation and emission assessment, Journal of
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H. Hashim et al. / Journal of Cleaner Production xxx (2016) 1e10

mi
mj
vdj
vi
mi
yi
ymix
zj
cost
Ci
CNi
CNj
CVi
CVj
DTi
DTj
SCi
SCj

kinematic viscosity of individual fuel blend fraction in

mm2/s
kinematic viscosity of fuel blend mixture in mm2/s
volume fraction of B5 diesel in biofuel blend
blend fraction by volume
blend fraction by mass
individual fuel properties
mixture properties
total fuel blend cost in MYR/L
objective function to minimize cost of fuel blend mixture
raw material cost of each fuel blend fraction in MYR/L
cetane number of individual fuel blend fraction
cetane number of fuel blend mixture
gross caloric value of individual fuel blend fraction in
MJ/kg
gross caloric value of fuel blends in MJ/kg
distillation temperature of individual fuel blend fraction
in
C
distillation temperature of fuel blend mixture in
C
sulphur content of individual fuel blend fraction in ppm
sulphur content of fuel blend mixture in ppm

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