Fuel 241 (2019) 155–163

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Fuel
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Full Length Article

Ultrasonic parameter measurement as a means of assessing the quality of T

biodiesel production
Raphaela M. Baêssoa,b, , Rodrigo P.B. Costa-Felixa, Piero Milorob, Bajram Zeqirib
⁎

a
Laboratory of Ultrasound, National Institute of Metrology, Quality, and Technology (Inmetro), Duque de Caxias, RJ, Brazil
b
Ultrasound and Underwater Acoustics Group, Centre for Chemical, Environmental and Medical Science, National Physical Laboratory, Teddington, United Kingdom

GRAPHICAL ABSTRACT

ARTICLE INFO ABSTRACT

Keywords: Whilst fossil fuels have been an industrial driver for many decades, environmental concerns related to global
Metrology warming have driven the development of alternative energy sources, such as the generation of biodiesel from
Speed of sound vegetable oils. For a biodiesel to be commercialised, it must meets property and quality requirements from
Ultrasound attenuation International Standards. Most of these checks must be performed off-line, with significant costs in terms of
Biodiesel
shutdown time and testing. On the other hand, ultrasound measurement can provide an in-line monitoring tool
Conformity assessment
to assess the advance of transesterification. Although this was highlighted in previous works, hitherto this has
not been the subject of a detailed metrological approach to define the uncertainty associated with ultrasound
techniques applied to biodiesel and related liquids. This paper presents such research and addresses measure-
ment of two ultrasound parameters, Speed of Sound (SoS) and attenuation coefficient (Att), and their capability
of assessing macroscopic characteristics of the biodiesel. The liquids tested were pure edible oils (vegetable,
corn, and sunflower), castor oil, pure biodiesel (B100), as well as blends of biodiesel with common contaminants
or by-products related to biodiesel transesterification. Details of the biodiesel manufactured were varied, using
different stirring speeds of rotation (200 rpm and 550 rpm), temperatures (40 °C and 50 °C), and KOH catalyst
concentrations (0.2% and 1.5%). Contaminants added to pure biodiesel were methanol (0.10% and 0.20%),
glycerol (0.10% and 0.15%) and triglyceride (2%). The acoustic characteristics of these liquids were determined
relative to water using a broadband through-transmission substitution method covering the frequency range
1–20 MHz. Normalized error analysis has been applied to assess the equivalence of experimental results, as well
as to discriminate the detection sensitivity of the technique. From the measurements, all edible oils showed
equivalent experimental values for SoS and Att over the usable frequency band 2 MHz to 18 MHz. In contrast,
biodiesel produced from sunflower and different reaction routes led to SoS and Att which were statistically
different over the same frequency range, reflecting the ability of ultrasound to monitor low-level contamination
of different blends. Finally, the paper concludes that ultrasound shows promise as a means of assessing biodiesel

⁎
Corresponding author at: Laboratory of Ultrasound, National Institute of Metrology, Quality, and Technology (Inmetro), Duque de Caxias, RJ, Brazil.
E-mail address: raphaelabaesso@gmail.com (R.M. Baêsso).

https://doi.org/10.1016/j.fuel.2018.12.032
Received 18 May 2018; Received in revised form 11 September 2018; Accepted 8 December 2018
Available online 12 December 2018
0016-2361/ © 2018 Elsevier Ltd. All rights reserved.
R.M. Baêsso et al. Fuel 241 (2019) 155–163

quality and purity with sensitivity sufficient to discern contaminants in a proportion as low as 0.1% in mass for
Att measurements.

1. Introduction parameters of interest, speed of sound and attenuation coefficient (Att).

The results for SoS and Att were carefully studied for a range of targeted
Fossil fuels have driven technological developments, economic liquids and are presented alongside complete uncertainty budgets. The
growth and human prosperity in the past and will continue to play a possibility to ultimately applying this method “in-line” whilst main-
major role in the future. However, the environmental impact and finite taining a good sensitivity establishes the ability of ultrasound in dis-
global reserves have spurred research on other sources of energy. criminate between different qualities of biodiesel blends.
Technological advances have enabled fossil fuels to be increasingly
replaced with alternatives that are less environmentally damaging.
Wind or hydropower, for instance, generate renewable energy with far 2. Material and methods
smaller environmental footprints than conventional coal or gas fired
power plants [1]. The vision of sustainable diesel production has led to Two acoustic parameters were assessed in this research: SoS and Att.
biodiesel being one of the most studied fuels in the last decade [2]. The setup for these measurements and the biofuels preparation proce-
Biodiesel, also known as fatty acid methyl ester (FAME), can be pro- dures will now be described.
duced from animal fat, vegetable oil and waste oil by a transester-
ification process [3]. Europe, USA, China and Brazil are expected to
2.1. Biofuels
drive global legislative processes to implement minimum blend ratios
and have already implemented local mandatory minimum biodiesel
2.1.1. Transesterification reactions
ratios to be added to commercialised diesel [2,4]. The classification of
The transesterification reactions were carried out at one atmo-
biodiesel blends is often demonstrated by BX, where X corresponds to
spheric pressure using a magnetic stirring hot plate (model 11-102-
the percentage value of biodiesel in the sample. For example, calling a
50SH, Fisher Scientific, Pittsburgh, PA, USA). Sunflower oil, obtained
mixture of B10 implies in that the mixture is composed of 10% biodiesel
from a local grocery store, was the source of triglyceride (TAG), whilst
and 90% diesel [5]. In the case of Brazil, for instance, the 10%-bio-
methanol (99.8% of purity from Sigma-Aldrich, St Louis, MO, USA)
diesel-ratio requirement initially scheduled to come into force in March
provided the short chain alcohol. According to the literature, to achieve
2019 was brought forward by 12 months and is already in place [3,6].
good conversion rates the oil to alcohol ratio should be 1:6 [25–29].
Due to similar physicochemical properties to diesel fuel, it is un-
Potassium hydroxide (85% of purity from Alfa Aesar Haverhill, MA,
surprising to find biodiesel as the principal recommended substitute,
USA), chemical formula KOH, was used as the basic catalyst. KOH
because of its renewability, higher combustion efficiency, lower exhaust
concentration (either 0.2% or 1.5%), the speed of magnetic stirring
emissions, and absence of sulphur and aromatics by-products. However,
(either 200 rpm or 550 rpm) and temperature of the reaction (40 °C and
it is essential that the physical properties do not change during its life-
50 °C) were varied in order to produce different quality biodiesels, as
cycle in order to guarantee the efficiency of the engine’s injection timing
summarized in Table 1.
and combustion rate [7–9]. For this purpose, and to homogenise and
The FAME manufacture conditions in this study as catalyst con-
establish a reference in specifying a biodiesel, it is necessary that the fuel
centration and stirrer rotation speed (Table 1) are well understood and
meets the property and quality requirements of the American Society for
presented previously in [3].
Testing and Materials (ASTM) D6751 standard in USA or the European
Standard (EN) 14,214 in Europe [10]. SoS in pure liquids such as oils has
already been well studied [11–15], and has been shown to be an im- 2.1.2. Biodiesel blends
portant tool to monitor chemical reactions [3,16–18]. The SoS (c) can be A commercial pure biodiesel (B100) was purchased from a local
related to the bulk modulus (β) through the following equation: = c 2 . biofuel company (Uptown Oil, London, UK). The company website [30]
In principle therefore, to predict bulk modulus (β) it would be necessary discloses all the biodiesel parameters required in order for it to be a
either measure the density of the liquid (ρ) or calculate ρ through commercially available product. All these parameters are in accordance
equations that consider the liquid composition, temperature and pres- to standardized European specifications and the specifications are de-
sure. It is beyond the scope of this research to investigate that relation. scribed in a table as a Supplementary Material. Blends were calculated
Nevertheless, it is a promising research to be developed further [8]. in weight percent. A weighing scale with 0.01 g accuracy (Pioneer
Many studies report the measurement of SoS in biodiesel made from PA2202, Ohaus, Parsippany, NJ, USA) was used. Table 2 summarises all
dissimilar fat and oil sources [9–10,19–22]. To the authors knowledge, of the blends used in this work.
none of these have presented a comprehensive assessment of the asso-
ciated uncertainties. A good understanding of the contributions to mea- Table 1
surement uncertainty is critical whenever a decision is based on the Preparation matrix for the biodiesel produced in-house from sunflower,
magnitude of the quantity of interest [3,23]. Furthermore, a proper showing variations in catalyst concentration, stirrer rotation speed and tem-
analysis of the factors affecting the uncertainty of the measurement, can perature.
lead to the optimization of the measurement procedure. Benefits of ac- Reaction Catalyst concentration Stirrer rotation speed Temperature
curate measurement have both quantitative and qualitative impacts,
underpinning improvements in emerging technologies, for environ- 0.2% (w/w) 1.5% (w/w) 200 rpm 550 rpm 40 °C 50 °C
mental aspects and quality of life [24].
I X X X
Currently, the majority of analytical procedures for biodiesel quality IA X X X
control are based on chromatographic methods, mostly gas chromato- II X X X
graphy, due to the high sensitivity and lower limit detection provided IIA X X X
[17]. Whilst the method is accurate, it is an offline technique involving III X X X
IIIA X X X
time-consuming procedures.
IV X X X
The aim of this paper is to study an ultrasound method capable of IVA X X X
assessing the quality of biodiesel through the variation of two specific

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Table 2
Biodiesel and biodiesel blends analysed as part of this research study.
Sample Biodiesel Methanol Glycerol Tag

A 100% – – –
B 99.9% 0.1% – –
C 99.8% 0.2% – –
D 99.9% – 0.1% –
E 97.85% – 0.15% 2%

2.2. Pure liquids

The liquids studied are relevant to the transesterification process.

Four different pure oils (castor, vegetable, corn, and sunflower) along
with methanol and glycerol were measured. Table 3 presents the fatty
acid composition and physical properties for the pure oils.

2.3. Facility measuring speed of sound and attenuation

SoS and Att of the liquids were determined at the National Physical
Laboratory (NPL, UK) employing the ultrasound materials character-
Fig. 1. Measurement system employed to determine the speed of sound and
ization facility. This is a broadband measurement based on through-
attenuation (a) transmitter/receiver transducer, (b) reference cell with the li-
transmission substitution technique covering the frequency range from
quid under test and (c) membrane hydrophone used to detect the ultrasound
1 MHz to 20 MHz, with reference to de-ionised water. The set-up, transmitted through the reference cell.
shown schematically in Fig. 1, and the method is an adaptation of the
one described by Zeqiri [40].
Liquids were poured into custom-build sealed acoustic cells of dif-
ferent thicknesses (path lengths) varying from 5 mm to 30 mm. Two
12 μm Mylar membranes (Goodfellow, Huntingdon, UK) are used as
acoustic windows, with an aperture of 50 mm diameter, large enough
such that there are no acoustic reflections from the acoustic beam
generated by the transmitting transducer. The speed of sound and
density of Mylar are 2400 m s−1 and 1380 kg m−3 respectively [41].
Fig. 2 shows a schematic of the reference cell structure, with the two
acoustic windows stretched taut across two o-rings (not shown in the
figure) to define specified thicknesses of fluid under test.
For the measurement protocol, the acoustic transmitter and acoustic
receiver were aligned in a tank filled with de-ionised water, using two

Table 3
Fatty acid composition physical properties for vegetable oils tested in this work.
Vegetable Oils (% w/w)

Fatty acid Castor Corn Rapeseed Sunflower [35]

[31] [32,33] [30,34]

__ __ __
8:0 4
__ __
10:0 7 0.01
__ __
14:0 0.6 0.1
__ __ __
15:0 0.02
16:0 1.38 10 4.6 6.4
__ __ __
17:0 0.04
18:0 1.39 3.5 1.7 2.3
__
20:0 0.06 0.2 0.3
__ __ __ __
22:0
Saturated total (%) 2.83 25.3 6.37 9.1
__ __ __ __
14:1
__ __ __
16:1 0.21
18:1 4.24 26.8 63.44 11.6
18:1 - OH 85.75 __ __ __ Fig. 2. Exploded view of a typical reference cell prepared for the acoustic
18:2 6.05 47.1 19.6 79.3 characterisation of liquids, with the following components: (a) fixing screws;
18:3 0.65 0.8 1.2 __ (b) plastic frame; (c) 12 µm Mylar membrane; (d) stainless steel chamber.
__ __ __
20:1 9.1
__ __ __
22:1 0.08
22:4 0.48 __ __ __ five degrees-of-freedom moving stages. An additional stage allows the
Unsaturated total (%) 97.17 74.7 93.67 90.9 rapid positioning and alignment of the test cell between the transmitter
Dynamic viscosity 921.0 64.4 [38] 67.8 [38] 67.3 [38] and receiver. Two different combinations of transmitter and receiver
(mPa s) 20 °C [36,37] were used. The first employed a single element broadband transmitting
Speed of Sound (m 1505 [39] 1467.8 1468.1 [12] 1472.4 [12]
s−1) 20 °C [12]
transducer manufactured by Force Technology (Brøndby, Denmark) of
active element of diameter 10 mm and a 25 μm bilaminar membrane

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hydrophone (receiver) manufactured by GEC-Marconi (Essex, UK) of Table 4

sensitive element of 30 mm diameter. The second deployed a pair of Uncertainty sources and their contribution.
nominally identical ultrasonic transducers (Olympus Panametrics-NDT Source of uncertainty 5 MHz 10 MHz Description
V313, 15 MHz centre frequency, 6.35 mm active element diameter).
The former combination maximized measurement bandwidth, the latter Uncertainty Contribution
Speed of sound (m s−1)
was used specifically to enhance signal-to-noise ratio at high fre-
Type A 0.19 0.19 Random/repetitions
quencies. Both configurations include a receiver sufficiently large to Oscilloscope Time base < 0.01 < 0.01 From oscilloscope
reduce the effect of diffraction on measurements. The devices were specifications
connected to an Olympus 5073PR pulser–receiver (Olympus NDT, Oscilloscope Resolution 0.26 0.26 Measured using 1 ns
Waltham, MA, USA). The acoustic signals were digitized using a Speed of sound in water 0.17 0.17 Calculated from [41]
Thickness 1.67 1.68 Calculated from
Tektronix DPO7254 Digital Phosphor Oscilloscope (Tektronix UK,
uncertainty in the
Bracknell, UK) and stored and analysed using a custom-developed thickness
LabView (National Instruments, Austin, TX, USA) application installed Temperature 1.03 1.04 Calculated for ± 0.5 °C
on a desktop PC. Diffraction errors on 0.05 0.02 Calculated from [45]
reflected pulses
To derive the required acoustic properties, four different acoustic
Diffraction errors on 0.01 0.02 Calculated from [46]
pulses were acquired in rapid succession in the following steps: (i) the transmitted pulses
through-water signal was acquired; (ii) the sample was then positioned Acoustic window 0.51 0.52 Calculated for 12 µm Mylar
in the acoustic path and aligned by maximizing the magnitude of the Attenuation coefficient (dB cm−1)
reflection from the reference cell front interface; (iii) the acoustic Type A 0.068 0.177 Random/repetitions
Oscilloscope Linearity 0.004 0.003 Measured in-house [44,47]
echoes from the front and rear reference cell interfaces were acquired
Oscilloscope range to range 0.062 0.090 Measured in-house [47]
and (iv) the signal transmitted through the sample to the membrane corrections
hydrophone was acquired. This set of four measurements allows the Oscilloscope Temperature 0.004 0.003 From oscilloscope
simultaneous evaluation of transmission loss, speed of sound and dependence specifications
thickness of the test sample, as described by Rajagopal et al. [41]. An Receiver Signal-to-noise ratio < 0.001 < 0.001 Measured in-house
Receiver Linearity 0.001 0.001 Measured in-house [44,47]
important feature of the analysis method employed is the use of Fourier Amplifier Linearity 0.021 0.028 Measured in-house [44,47]
techniques to derive the frequency dependent properties of the liquid: Temperature dependence 0.002 0.001 From internal data
this allows the determination of the phase velocity (SoS) and how this Non-linear propagation 0.002 0.003 Measured from [47,48]
varies with frequency. Absorption of water < 0.001 < 0.001 Calculated from [49]
Diffraction < 0.001 0.001 Calculated from [46]
For each combination of temperature, stirring and catalyst con-
centration, described in Table 1, 150 ml of FAME were produced and
poured into at least 3 different cell thicknesses that were used to derive
of the frequencies of interest. Expanded measurement uncertainty was
the attenuation from the transmission loss [42]. Some combination
evaluated accordingly.
were repeated to ensure the reproducibility of the process and the re-
Type B uncertainties arises from several sources, which were in-
sults were always within the uncertainty limits. Typical oscilloscope
dependently evaluated at different frequencies, as briefly described in
settings were: 1 GSamples/second and 5000 averages. Typical pulser
Table 4. Typical values for oils, at 20 °C, are 1470 m s−1 for SoS and
settings were: gain +33 dB, pulse repetition frequency 1 kHz, energy 2,
2 dB cm−1 and 6 dB cm−1 for Att at 5 MHz and 10 MHz, respectively.
damping 4. At least four independent sets of measurement were ac-
Table 4 describes an example of each uncertainty source contributions.
quired for each test cell, at four different transmitter-receiver separa-
tions. For each liquid a set of 12 repetitions was performed (3 different
cell thickness and 4 measurements at different distances each). Typical 2.5. Statistical analysis
separations used were in the range 120 mm and 250 mm, whilst the
distance between transmitter and the front window of the reference cell To evaluate the equivalence of the results, a statistical analysis was
was in the order of 60 mm. made assessing the normalised error (En) as described in [50]. The
Throughout the measurements, water temperature was monitored formula used for calculating En is shown below:
using a calibrated thermometer (IP 39C, G. H. Zeal, London, UK). The
experiments were carried out in a range of 19.5 °C – 20.0 °C. Once (x2 x1)
En =
immersed in water, the sample was allowed to reach thermal equili- (U22 + U12 ) (1)
brium before the data acquisition and the temperature was kept
within ± 0.1 °C during the acquisition of the four sets of measurement where xi are the quantities to be compared (e.g. the speed of sound
which constituted a measurement run. in two different liquids) and Ui the corresponding uncertainties
(p = 0.95). En was calculated over the frequency range 1–20 MHz
2.4. Uncertainties range. This analysis was used to establish the significance of the dif-
ference observed between two sets of measurement data. For normal-
Measurement uncertainty was evaluated following the guide to the ised errors lower than and equal one, the samples compared one to
expression of uncertainty in measurement [34]. The values quoted in another are considered statistically equivalent with respect to the
the results section are the standard uncertainty multiplied by a cov- parameter under consideration.
erage factor, k = 2, providing a coverage probability of approximately
95%, according to the method recommended by [43,44]. 3. Results and discussion
The expanded measurement uncertainty was determined using both
Type A (random) and Type B (systematic) uncertainty evaluations. 3.1. Pure liquids
For the SoS measurements, Type A uncertainty on each cell was
assessed from at least four repeat measurements. Results derived for the The SoS and Att for pure liquids related to the transesterification
same liquid using different cell thicknesses were combined using the process were determined in a range of 1 – 20 MHz.
weighted mean. For the attenuation coefficient, values of transmission Fig. 3 shows the variation of SoS and Att as function of frequency for
loss for the different thicknesses were subtracted and divided by the the pure liquids listed in Table 3. Att in oils shows a power law relation
difference in cell thicknesses to yield the attenuation coefficient at each with the frequency whose coefficients can be easily determined [12].

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R.M. Baêsso et al. Fuel 241 (2019) 155–163

Fig. 3. (a) SoS for pure liquids. (b) SoS for edible oils. Error bars represents the expanded uncertainty (p = 0.95). (c) Attenuation for pure liquids. (d) Attenuation for
edible oils. Error bars represent the expanded uncertainty (p = 0.95) and are visible for 10 – 20 MHz range.

For edible oils SoS and Att are statistically equivalent, as shown in 100% biodiesel commercialised in United Kingdom was employed as
Table 5. The chemical similarity can justify the proximity in the the reference biofuel.
acoustic parameters. There is no chemical formula representing fats and From the literature, it is well established that the SoS of oils is
oils as they are highly complex mixtures of triglycerides, and despite higher than it is in biodiesel made from that oil [3,17–18], and ac-
the available data establishing a relation of chemical composition and cording to [3] there is a qualitative relation between free glycerine
speed of sound [11–13], the experimental results associated to their concentration and SoS in biofuels. Fig. 4 shows that both biodiesel types
respective uncertainties makes the vegetable oils undistinguishable to produced in the laboratory did not have the same acoustic properties of
each other. the reference biodiesel. The biodiesel with lower catalyst concentration
For the three edible oils listed in Table 3, the En calculated from has acoustic properties closer to pure oil, indicating lower conversion in
experimental SoS and Att data show that they can be considered sta- FAMEs and higher TAG concentration [3] (See Figs. 5, 6, 7).
tistically equivalent over the frequency range 1 to 20 MHz. For the The FAMEs are considered a biodiesel when they are in accordance
calculation, specific frequencies were chosen in Table 3 to illustrate the with requirements and specifications in proper technical standards
results. Given that the deteriorating signal-to-noise at frequencies af- specifications. Those specifications can be found in (ASTM) D6751
fects the quality of the attenuation coefficient measurements, En values (standard in USA) and also in (EN) 14,214 (standard in Europe). Many
were considered only up to 18 MHz. The difference between oleic acid literature studies of the SoS of FAMEs do not show the specifications of
(main component of vegetable oil) and ricinoleic acid (main component the fuel that is measured. This makes the SoS range very large and
of castor oil) is the presence of a hydroxyl. Its presence does not only might lead to the wrong conclusion that the results reported are from a
modify the viscosity of the oil, which increases about 13 times pure biodiesel and not just from a FAME. With this caveat, values found
(67.3 mPa s−1 for vegetable/rapeseed oil and 921.0 mPa s−1 for castor in literature for SoS at 20 °C in sunflower biodiesel [10,52] are sig-
oil) [36–38], but also the values of SoS and Att, Fig. 3 The Att of the nificantly lower than the ones found for the FAMEs produced from
castor oil is close to that one found for the glycerol, which has a visc- 0.2% (w/w) KOH in the current study (1403–1412 m s−1 in literature
osity 1.6 times greater than that oil, 1499 mPa s−1 [51]. Thus, it is
observed that, despite being an important property, viscosity together
with the chemical composition is not enough to predict the values of Table 5
SoS and Att. However, a metrological study can add value to the results Normalised error for edible oils measured in this study.
obtained. Therefore, despite many studies suggesting the establishment Frequency En Vegetable/Corn En Vegetable/ En Corn/Sunflower
of relations between chemical compositions and SoS e Att, predicting [MHz] Sunflower
values of SoS and Att becomes unfeasible for edible oils with proximity
Att SoS Att SoS Att SoS
in their composition.
3 0.12 0.55 0.66 0.05 0.54 0.60
5 0.00 0.56 0.71 0.10 0.71 0.66
3.2. Fames and biodiesel 10 0.98 0.52 0.10 0.18 0.88 0.70
13 0.04 0.47 0.31 0.25 0.36 0.73
15 0.28 0.45 0.39 0.25 0.12 0.70
Considering that the concentration of a catalyst can directly influ- 17 0.50 0.43 0.34 0.32 0.16 0.75
ence the properties and composition of the produced biodiesel [18], a

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Fig. 4. Experimental results for different biodiesel production: (a) SoS and (b) Att as function of the frequency for pure oil, FAMEs produced in-house (Reactions II
and IV), and the commercial pure biodiesel at 20.0 °C.

Fig. 5. (a) Speed of sound and (b) attenuation for FAMEs synthetized with 0.2% (w/w) of KOH at 20.0 °C, using the various protocols identified in Table 1.

Fig. 6. (a) Speed of sound and (b) attenuation for biodiesel synthetized with 1.5% (w/w) of KOH at 20.0 °C.

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Fig. 7. (a) Speed of sound and (b) attenuation at 20 °C for blends described in Table 2.

for pure sunflower methyl ester depending of their final composition).
This was expected because FAME production through transesterifica-
tion is an endothermic reaction. A concentration of 0.2% of catalyst was
not enough to reduce the activation energy and make 40 min suffi-
ciently long to produce lead to a FAME with the same acoustics char-
acteristics of those ones produced with 1.5% of KOH.
Table 6 brings the results of En for the reactions cited in Table 1.
The mathematical analysis of En shown in Table 6 shows statistical
equivalence for the produced FAMEs. The equivalence is based on the
calculated En over the 2–18 MHz range.
Increasing the temperature of the transesterification process by
10 °C decreases the SoS for reactions I and IA (7.5 m s−1), as well as for
reactions II and IIA (11.8 m s−1). This difference can be up to 17 m s−1
for reactions with KOH at 0.2% (w/w) and different stirrer rotation and
temperature, I and IIA. On the other hand, for reactions with higher
catalyst concentration (III, IIIA, IV, and IVA), the increase of 10 °C
during the reaction process or the increase of stirring velocity produces
FAMEs with similar acoustic properties, suggesting that this con-
centration is enough to generate the highest quality achievable in our
laboratories. Considering that changes of reaction parameters produce
FAMEs with different compositions [3,18], the qualitative analysis
through acoustic parameters confirms the validity of the ultrasound
technique as sensitive a means of monitoring changes in composition.
3.3. Blends
Despite the low concentration of contaminants in the blends de-
scribed in Table 2, ultrasound was able to discriminate them from the
reference fuel (sample A). The values of En are reported in Table 7. The
uncertainties for pure rapeseed biodiesel (sample A) at 11 MHz and
20 °C are 0.29% for SoS and 3.9% for Att. This implies that blends
whose results differ more than 0.42% for SoS and 5.5% for Att, will
show a En greater than 1.0, and cannot be considered equivalent to the
pure biodiesel. This analysis does not quantify how far the fuel is out of
specifications, but it could be used to confirm the quality of the bio-
diesel is within the requirements or technical specifications. It is worth
noticing that the setup and the method used is optimized for bandwidth
and allowed the measurement of the absolute value of SoS and Att

Table 6
Normalised error analysis matrix for produced FAMEs.
0.2% KOH 1.5% KOH

Temperature is fixed/ stirring changes 40 °C* 50 °C* 40 °C* 50 °C*

Equivalent (I and II) Not equivalent (IA and IIA) Equivalent (III and IV) Equivalent (IIIA and IVA)
Stirring is fixed/ temperature changes 200 rpm* 550 rpm* 200 rpm* 550 rpm*
Not equivalent (I and IA) Not equivalent (II and IIA) Equivalent (III and IIIA) Equivalent (IV and IVA)
Change stirring and temperature Equivalent (II and IA) Equivalent (IV and IIIA)
Not equivalent (I e IIA) Equivalent (III and IVA)

* Fixed parameter.

Table 7
Normalised error for blends described in Table 2.
Frequency (MHz) En (A - B) En (A - C) En (A - D) En (A - E) En (A – IV*)

Att SoS Att SoS Att SoS Att SoS Att SoS

3 1.32 0.27 1.72 0.46 1.21 0.82 1.62 2.41 5.27 2.27
5 1.86 0.28 2.42 0.55 1.97 0.84 2.72 2.44 4.28 2.36
10 2.46 0.25 2.91 0.61 5.11 0.85 5.75 2.47 0.82 2.45
13 1.32 0.26 1.48 0.63 2.40 0.83 2.75 2.45 1.45 2.48
15 1.44 0.28 2.58 0.67 1.06 0.80 1.93 2.40 0.89 2.46
17 1.32 0.30 1.67 0.70 1.35 0.78 1.50 2.37 0.37 2.43

* Reaction IV described in Table 1.

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between 1 MHz and 20 MHz, and for solid and liquid materials. A
dedicated instrument can significantly reduce the uncertainty in the
measurements, thus allowing the detection of smaller variations. This
could be a first fuel check before leaving the processing plant. Fur-
thermore, changes are easier to measure compared to absolute prop-
erties, which could further boost the sensitivity of an in-line device.
The establishment of a reference SoS and Att will allow a biodiesel
producer to monitor fuel production and confirm the production pro-
cess and product quality. Furthermore, this could be in real time, in-
line, using a modification of the described reference measurement
method, prior to the application of the various chemical analyses
needed to quantify the fuel quality.
4. Conclusion
An ultrasound method based on speed of sound (SoS) and at-
tenuation (Att) measurement was presented as the basis of an accurate
tool for biodiesel analysis. The experimental results led to the following
conclusions.
• The edible oils used in this research (vegetable, corn, and sunflower)
are equivalent with regard their speed of sound and attenuation
coefficient over the frequency range of 2 MHz to 18 MHz based on
the normalized error statistics;
• Reference values have been provided for edible oils, specific FAMEs
and pure biodiesel, also blended with contaminants, between 2 MHz
and 18 MHz both for SoS and Att.
• There is a correlation between the acoustic properties, the ad-
vancement of the reaction and the quality of the final product.
Different quality FAMEs were generated by varying stirring rotation
(200 rpm and 550 rpm), temperature (40 °C and 50 °C), and KOH
catalyst concentration (0.2% and 1.5%). Ultrasound was able to
discriminate between the different products.
• It is possible to identify contaminants and by-products, such as
methanol (0.10% and 0.20%), glycerol (0.10% and 0.15%) and
triglyceride (2%) with good sensitivity.
•
The accurate knowledge of the uncertainty in the measurements is a
powerful tool to determine whether or not the test sample is within
specification.
Therefore, the method could be further optimised and applied by a
biodiesel manufacturer industry as an accurate analytical tool for
monitoring and assessing biodiesel quality and purity. Dedicated in-
struments and techniques can produce better uncertainty, thus boosting
the sensitivity of the method suggested. The work presented can be
considered a first guideline for the specifications of such devices.
Acknowledgment
This work was conducted during a scholarship supported by the
Brazilian Sandwich Doctorate Program (PDSE) at the United Kingdom
National Physical Laboratory. Financed by CAPES – Brazilian Federal
Agency for Support and Evaluation of Graduate Education within the
Ministry of Education of Brazil. The authors thank the Carlos Chagas
Filho Research Support Foundation (Faperj, grant number E-26/
201.563/2014), the National Council for Scientific and Technological
Development (CNPq, grant number 312.501/2017-0) and CAPES (PDSE
- 88881.132961/2016-01).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.fuel.2018.12.032.
162
Fuel 241 (2019) 155–163
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