Chemical Papers (2019) 73:1823–1832

https://doi.org/10.1007/s11696-019-00755-4

ORIGINAL PAPER

Engine performance and emission of biodiesel fuel prepared

from different Ukrainian natural oils
Lyubov K. Patrylak1 · Mykhailo V. Okhrimenko1 · Anton M. Levterov2 · Serhiy V. Konovalov1 · Angela V. Yakovenko1 ·
Stepan O. Zubenko1

Received: 26 June 2018 / Accepted: 1 February 2019 / Published online: 30 March 2019
© Institute of Chemistry, Slovak Academy of Sciences 2019

Abstract
A range of natural oils such as rapeseed, sunflower, corn, linseed, and mustard ones has been used for fatty acid ethyl esters
synthesis. The last as pure biodiesel B
­ 100 were mixed with fossil diesel B
­ 0 to form blends B
­ 20, ­B40, ­B60, and B
­ 80. This study
reports the effects of engine load and biodiesel percentage on the performance and emission of a tractor diesel engine fueled
with biodiesel–diesel blends. It is stated that mixed fuels little inferior to mineral diesel in engine performance, but the
observed reduction is not critical. The results showed that the engine performance (effective power and torque) depends
primarily on the content of acids with ­C18 carbon chain in the oil. It was also found that the highest performance among
the blended fuels is introduced by ethyl esters of rapeseed oil, while corn and mustard oil ethyl esters presented the lowest
emissions level. The emissions of rapeseed, sunflower, corn, linseed, and mustard ethyl esters are all lower than the base
mineral fuel.

Keywords  Biodiesel · Natural oil · Fatty acid composition · Ethyl esters · Engine performance · Emission

List of symbols and abbreviations KOH Potassium hydroxide

B100 100% Biodiesel HHV Higher heating value (MJ.kg−1)
B20 20% Biodiesel + 80% mineral diesel LHV Lower heating value (MJ.kg−1)
B40 40% Biodiesel + 60% mineral diesel Θ Injection timing angle (°)
B60 60% Biodiesel + 40% mineral diesel
B80 80% Biodiesel + 20% mineral diesel
KA Potassium form of zeolite A Introduction
GC Gas chromatograph
SFC Specific fuel consumption (kg/kW.hr) Rising prices, decrease of fossil fuels resources, and envi-
CO Carbon monoxide ronmental advantages have created great interest on alterna-
CO2 Carbon dioxide tive sources of fuels, for example, biodiesel (Knothe et al.
NOx Nitrogen oxides 2010; Atabani et al. 2012; Godwin et al. 2017). The various
PM Particulate matter studies have been carried out using lot of natural oils as feed-
T Torque (N.m) stock material (Makareviciene and Janulis 2003; Koh and
Ne Engine effective power (kW) Ghazi 2011; Volpato et al. 2012)  alcohols such as metha-
ηe Engine efficiency nol, ethanol or buthanol (Issariyakul et al. 2007, Brunschwig
et al. 2012) as well as different catalysts, homogeneous ones
(sodium/potassium hydroxide, sulfuric acid), and heteroge-
* Lyubov K. Patrylak neous ones including lipases (Li et al. 2009; Jegannathan
lkpg@ukr.net
et al. 2008).
1
V.P. Kukhar Institute of Bioorganic Chemistry Triglycerides (or triacylglycerols) are the main compo-
and Petrochemistry, National Academy of Sciences nents of vegetable oils and animals fats. Usually, they con-
of Ukraine, 1 Murmanska str, Kyiv 02660, Ukraine tain several different fatty acids. The most important param-
2
A.M Podgorny Institute for Mechanical Engineering eter influencing the properties of biodiesel fuel as product
Problems, National Academy of Sciences of Ukraine, 2/10 of transesterification of fatty acids is different chemical
Dm. Pozharsky str, Kharkiv 61046, Ukraine

13
Vol.:(0123456789)

1824
and physical properties of fatty acids. Nowadays, climate
and economics factors determine using of feed stock oils in
Europe and America.
The aim of the present work was to compare diesel engine
performance and emission of biodiesel blends prepared on
the basis of ethyl esters of traditional for Ukrainian agricul-
ture oils.
Experimental
Synthesis and analysis of ethyl esters of fatty acids
Unrefined rapeseed (ISO 46.072:2003), sunflower (ISO
4492:2005), and linseed (ISO 5791-81) oils produced
by JSC “Nizhynskyi zhyrkombinat”, corn oil (“Trading
House—Tavria miller”, Odessa, TU 10.4-36553354-001:
2012), mustard oil (“Eurostandard”, Bila Tserkva, ISO
4598-2006), and rectified ethanol alcohol (95.6%) have been
used for the synthesis of fatty acids ethyl esters.
Conditions of the homogeneous-catalytic transesterifica-
tion of rapeseed oil were found earlier (Patrylak et al. 2013;
Patrylak et al. 2015): temperature 10–50 °C, atmospheric
pressure, reaction time 15–60 min, catalyst content (KOH)—
1.5–2.0 wt% of reaction mixture, molar ratio ethanol/oil is
equal 6–10. Such conditions were close and for sunflower,
corn, linseed, and mustard oils. Ethanol was dried previously
over zeolite KA to required minimum concentration of 99.0
wt%. The representative batches (50–100 kg) of ethyl esters
of each oil studied have been synthesized for engine testing.
Prepared samples of ethyl esters of abovementioned
oils have been suggested to GC analysis. Agilent 7890A
Series GC with flame ionization detector and HP-5 Col-
umn (30 m × 0.32 mm, 0.25 μm) has been used. Ethyl ester
content was determined. Using the revised EN 14103:2011
method with internal standard, methyl heptadecanoate
­(C17:0), at such analysis conditions: helium at 1.36 mL/min
constant flow, detector temperature—250 °C, and column
temperature—210 °C. First of all, 0.05–0.1 g of each sample
was weighed into individual vials followed by the addition of
0.02 g of methyl heptadecanoate dissolved in n-hexane. The
recorded weights of the samples and standard solutions were
the nearest 0.05 mg. For measuring the reproducibility of the
Table 1  Fatty acid composition Oil Content, wt. %
of Ukrainian natural oils
C14:0 C16:0
Rapeseed 1.5 5.0
Sunflower 0.2 7.0
Corn 0.46 11.07
Linseed 0.6 6.4
Mustard – 3.62
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Chemical Papers (2019) 73:1823–1832
analysis, duplicates of the biodiesel samples were prepared.
The biodiesel samples were analyzed by injecting 1 μL of
each sample using microsyringe onto the GC and recording
the chromatogram. The resulting chromatogram showed the
elution order of the ester peaks typically found in biodiesel
samples. The total ester contents were then calculated from
resulting chromatogram using the peak areas of the ethyl
esters identified in the samples.
In Table 1, defined fatty acid composition of oils is given.
The conversion of oils was near 100%, whereas content of
ethyl esters was 97%. Iodide value was found by chemical
analysis. Physico–chemical characteristics of ethyl esters of
fatty acids in comparison with methyl esters and mineral
diesel are shown in Table 2. Cetane number of biodiesel
mixture with content of rapeseed oil ethyl esters of 20, 40,
and 60 vol.% in their blends with mineral diesel fuel (cetane
number 45) was determined in 10 Chimmotology Center
of the Ministry of Defense of Ukraine. It amounted to 45,
47, and 48 units, respectively, that corresponding 51 cetane
number unit for 100% biodiesel.
Higher heating value (HHV) for biodiesel samples
has been determined by isoperibolic calorimetry accord-
ing to ASTM D 240 at 22 °C. HHV measured for fossil
diesel fuel was 46 MJ.kg−1. Lower heating value (LHV,
kJ.kg−1) has been calculated according to Greenhouse Gas
Protocol advice for liquid fuels, as follows: lower heating
value = higher heating value/1.05.
Performance and emission characteristics
of biodiesel fuelled diesel engine
Performance and emission characteristics of diesel engine
fueled by pure biodiesel samples ­(B100)—ethyl esters of
different natural oils and their mixtures B ­ 20, ­B40, ­B60, and
­B80 (20, 40, 60, and 80 vol.%—for rapeseed, sunflower, and
corn oils as well as 20, 40, and 60 vol.%—for linseed and
mustard oils) with mineral diesel fuel were determined by
comparative bench testing on tractor diesel engine (Table 3).
The high-quality mineral diesel (Euro) brand and type C
(ISO 4840:2007) were used as the mineral component in
the mixtures.
For abovementioned mixed fuels on the basis of different
natural oils, the series of characteristics have been taken.
C18:0 C18:1 C18:2 C18:3 C20:0 C22:0 C22:1 C24:0
– 87.0 2.0 0.2 – 3.3 – 1.0
– 40.7 44 – 7.4 0.3 – 0.4
– 47.48 37.75 2.46 – 0.32 0.46 –
2.6 14.4 8.1 60.5 6.5 0.9 – –
0.99 66.77 2.24 – 10.46 – 14.3 1.62
Chemical Papers (2019) 73:1823–1832 1825

Table 2  Physico–chemical characteristics of ethyl (methyl) esters of fatty acids

No Characteristic Ethyl esters Ethyl esters Ethyl Ethyl esters Ethyl esters Methyl esters Mineral diesel Improved min-
of rapeseed of sunflower esters of of linseed of mustard of rapeseed (ISO 386-99) eral diesel (ISO
oil oil corn oil oil oil oil (EN 4840:2007)
14214:2003)

1 Density at 877 876 875 877 875 860–900 840–860 820–845

20 °C, kg/m3 (at 15 °C)
2 Kinematic 4.74 4.43 4.48 3.6 4.93 3.5–5.0 1.8–6.0 2.0–4.5
viscosity (at 20 °C)
at 40 °C,
­mm2/s
3 Cetane num- 51 52a 52a 52a 52a 51 45 51
ber
4 Copper band Class 1 Class 1 Class 1 Class 1 Class 1 Class 1 Class 1 Class 1
corro-
sion (3 h
at 50 °C),
rating
5 Oxidation 6 6 6 6 6 6 – < 25 g/m3
stability at
110 °C, h
6 Iodine value, 107 99 109 175 110 ≤ 120 6 –
g J2/100 g
a
 Calculated theoretically, based on the data of fractional distillation and using the known empirical dependences for mineral diesel (Anisimov
et al. 1999; Gureev et al. 1993; Kuznetsov and Kulchiy 1987)

Table 3  Specifications of the engine used rotational speed of electrobalancing machine shaft is con-
Manufacturer Volgograd Engine Ltd., Russia
trolled by means of a built-in electronically optical discrete
sensor, the signal from which comes to the stabilization unit
Engine type Two cylinder diesel engine of the rotational speed, placed in the control cabinet, and
Model D21A further from it to the arrows tachometer on the control panel.
Rated power 18 kW Simultaneously, the information about the rotation speed
Compression ratio 16.5 from the control cabinet comes to the digital speed meter
Displacement volume 2.1 dm3 XP 1506A placed on the control panel. The motor’s torque
Engine stroke 4 is recorded by the weight unit and by digital torque meter of
the type UR 1207 V on the control panel. The engine load
is caused by the rheostat on the control panel.
The last consists of an external speed, three load (for fre- The engine is supplied by liquid fuel from the fuel tank.
quency of crankshaft turns n = 1200, 1400 and 1600 min−1), Air supply to the engine is provided through an air filter and
and no load characteristics. Maximum effective power of flow meter RG-40. The engine exhaust gases are discharged
the engine Ne, maximum torque T, and maximum engine into the atmosphere through the release system. The last
efficiency ηe was selected as engine performance criteria. employs the receiver, which reduces the pressure pulsations
Moreover, the emission characteristics such as content in and the resistance thermometer which monitors the tempera-
the exhaust gases of nitrogen oxides ­NOx, carbon monoxide ture of the exhaust gases.
CO, carbon dioxide ­CO2, unburned hydrocarbons CH, and The test bench also includes measuring instruments that
particulate matter D have been determined. provide measurement of engine parameters and test condi-
tions. Characteristics of the measured values and measuring
Description of the test stand instruments are given in Table 4.

The comparative experimental studies of the D21A engine
work were performed on the engine stand (Fig. 1) with the
DSB 742-4/N electrobalancing machine BM, consisting of
a control cabinet of the type VH 136, a dual-engine unit
(engine generator) type IDR 924-1 and control panel. The
Description of the test procedure
First, the engine was started with mineral diesel as fuel at
no load. It was allowed to run about half an hour until the
steady-state conditions reached. The engine was then loaded

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1826 Chemical Papers (2019) 73:1823–1832

Fig. 1  General view of the stand

with engine D21A

Table 4  Characteristics of the measured values and measuring instruments

Measured parameter Designation The boundaries of measure- Measurement tool
ment

1. Rotation speed n 800–1600 min−1 Measuring complex IDS-742 4/N

2. Torque Mк 0–120 N·m Measuring complex IDS-742 4/N
3. Dose fuel expenditure Bd 44.84 g Scales technical, grade 1 VNTS
4. Measurement time of fuel consumption τ 30–120 s Frequency chronometer F5041
5. Fuel density ρf 0.800–0.940 g/cm3 Areometer AON–1
6. The volume of the measuring vessel V 250 cm3 Cylinder dimensional
GOST 1770–74
7. Air flow Vair 30–100 m3/h Gas meter RG-40
8. The pressure drop on the air inlet ∆p 0–300 mm WC Difemanometer
type DM
9. Pressure drop on exhaust gases ∆pg 0–300 mm WC Difemanometer
type DM
10. Oil pressure po 0.05–0.35 MPa Manometer
11. Exhaust gases temperature tg 0–1400 °C Chromal–copel device A565
12. Oil temperature to 80–100 °C Device
A566, 10011
13. Fuel temperature tf 10–40 °C Device
A566, 10011
14. Air temperature tair 5–40 °C Device
A566, 10011
15. Atmosphere air temperature to 0–50 °C Thermometer TL–4 GOST 215–73
16. Atmosphere pressure Bo 80–106 kPa Barometer–aneroids BAMM-1
17. Content in exhaust gases Gas analyzer auto test—02.03.P
 NOx CNOx 0–5000 ppm
 CO CCO 0–5%
 O2 CO2 0–21%
 CO2 CCO2 0–16%
 CH CCH 0–2000 ppm

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Chemical Papers (2019) 73:1823–1832 1827

gradually from no load to full load keeping the speed within Effective engine power, kW
the permissible range and the observations of different
T ×n
parameters were recorded. Using the fuel measuring appara- Ne = , (1)
9550
tus and stop watch, the time elapsed for the fuel consumption
for 44.84 g of fuel was measured. The gas emissions were where T—torque, N∙m; n—frequency of crankshaft turns,
also measured. This experiment was taken into account to ­min−1.
prepare base line data for mineral diesel. The various blends Fuel consumption, kg/h:
of ethyl ester with diesel that was tested on same engine in
3.6 × Bd
the same manner as described above. For each testing series Gf = , (2)
for esters on the basis of different oils, different batches of 𝜏
mineral diesel fuel have been taken. Experimental errors are where B d —dose fuel expenditure, g (B d  = 44.84  g);
presented in Table 5. τ—measurement time of fuel consumption, s.
The maximum possible effective power of the engine at Air consumption, kg/h
n = 1600 min−1 can be reached after optimization of fuel
injection timing angle (Θ). Therefore, biodiesel samples
( )
f Bo − Δp × 9.81 × 10−3
testing the optimization of Θ have been carried out. The Gair = 0.0752 , (3)
Rair × T
measured optimum Θ was 22° of crankshaft rotation to top
dead center both for fossil diesel fuel and for biodiesel mix- where f—frequency meter readings, Hz; Bo—atmospheric
tures. Such identity is caused by the same cetane number of pressure, kPa; ∆p—pressure drop in the inlet air path, mm
conventional diesel fuel and biofuels. WC; Rair—universal gas constant for air, R = 0.287  kJ/
At full fuel supply to the engine cylinders, and at a (kg·K); T—temperature before engine inlet, K.
frequency of crankshaft turns from n = 1000  min −1 to The coefficient of air excess
n = 1600 min−1 with an interval of 200 min−1, external speed
Gair
characteristic has been obtained. Three load characteristics 𝛼= , (4)
have been defined for n = 1200, 1400, and 1600 min−1. For Lair × Gf
such a purpose successive, increase in fuel supply within where Lair—theoretically required amount of air for com-
the load changes from zero to a value corresponding to full plete combustion of 1 kg of mixed fuel, kg/kg
feed has been used. While for the variable option, the aver-
(5)
( )
age effective pressure (engine load) has been obtained. No Lam = Lad × vd × 𝜌d + Lab × vb × 𝜌b ∕𝜌m,
load characteristics have been fixed at no load engine opera- where Lad—theoretically required amount of air for com-
tion range from n = 1600 min−1 to the minimum sustained plete combustion of 1  kg of mineral diesel fuel, kg/kg,
frequency of crankshaft turns with interval of 200 min−1. Lad = 14.55 kg/kg.
These external speeds, three load characteristics, and no Lab = 12.77  kg/kg—theoretically required amount of
load characteristic cover much of the most typical engine air for complete combustion of 1 kg of biodisel fuel; vd,
operating conditions, and therefore, they can be used for vb—volume content of diesel fuel and biofuel in the mixed
acquiring integrated environmental characteristics. fuel, respectively, ρd, ρb, ρm—density of fossil diesel, bio-
Experimental characteristics obtained for mixed fuels diesel and mixed fuels, respectively, kg/m3 (ρd = 842 kg/m3,
have been led to the standard atmospheric conditions. ρb = 875 kg/m3):
The following diesel engine performance can be deter-
mined from the results of bench testing.
𝜌m = vd × 𝜌d + vb × 𝜌b . (6)
Specific efficient fuel consumption, g/(kW·h):
Gf
Table 5  Errors for some measured parameters ge = . (7)
Ne
Measured variable Uncertainty, %
Lower combustion heat, kJ/kg:
­ in−1
1. Rotation speed, m ± 1
(8)
( )
2. Engine torque, N m ± 2 Qlm = Qld × vd × 𝜌d + Qlb × vb × 𝜌b ∕𝜌m ,
3. Fuel consumption, g ± 2 where Qlm, Qld, and Qlb—lower combustion heat of mixed
4. Temperature,  °C ± 1 fuel, diesel fuel, and biodiesel, respectively (Qld = 43,800 kJ/
5. CH ± 1.5 kg, Qlb = 37,800 kJ/kg).
6. CO ± 2.5 Engine efficiency (ηe):
7. ­NOx ± 2.5
8. Particulate matter ± 2 3.6 × 106
𝜂e = . (9)
ge Qlm

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1828 Chemical Papers (2019) 73:1823–1832

Average effective pressure, MPa: a 18,8

rapeseed
30 × Ne × 𝜏e sunflower
pe = , (10) 18,4 corn
i × Vh × n mustard
linseed
where τe—engine stroke; i—number of cylinders; and Vh— 18,0
engine cylinder capacity, l. For engine D21A, τe = 4; i = 2;

Ne, kW
Vh = 1.04 l. 17,6

17,2

Results and discussion 16,8

Bench testing of tractor engine D21A-fueled ethyl esters of B0 B20 B40 B60 B80 B100

different oils shows some decrease of maximum effective

power Ne (Fig. 2a), the maximum torque T (Fig. 2b), and the rapeseed
maximum engine efficiency ηe (Fig. 2c) with increasing vol- b sunflower
114
ume fraction of the biofuel in the mixed fuels. This drop is corn
mustard
amounted for ethyl esters of rapeseed oil up to 6.5% relative 112 linseed
for Ne, up to 3.4% relative for T, and up to 5.6% relative for
ηe. A reduction of Ne, T, and ηe for ethyl esters of sunflower 110

T, N.m
oil up to 7.5, 4.4, and 5.7% relative, respectively, has been
observed. For biodiesel on the basis of corn oil, a decrease 108
of the same characteristics is reached up to 7.65, 5.4, 5.9%
relative. For biodiesel on the basis of linseed oil, a reduction 106
of Ne up to 7.1% relative, T up to 6.0% relative, and ηe up to
8.8% relative has been observed. For biodiesel on the basis
B0 B20 B40 B60 B80 B100
of mustard oil, a decrease of Ne up to 8.7% relative, T up to
6.0% relative, and ηe up to 8.7% relative takes place.
Changes of the first and second indicators occur due to rapeseed
c 0,36 sunflower
reduction of power filling of cylinder because of signifi-
corn
cantly lower value of combustion heat of mixed fuels com- mustard
0,35
pared to such a characteristic for standard oil fuel, which is linseed
caused by oxygen content in the biofuel. However, the dete-
0,34
rioration of the power characteristics is not essential. Due to
the fact that for each series of experiments, a new batch of
ηe

0,33
oil fuel (ISO 4840:2007) was used, and we can see different
powerful and ecological indicators for zero biofuel content
0,32
(Figs. 3, 4, 5, 6, 7). Therefore, then comparing the different
esters’ efficiency, we operate with increase or decrease of
0,31
characteristics in relative percentages only.
It is discovered that the optimal fuel injection timing B0 B20 B40 B60 B80 B100

angle into the engine cylinders is the same as for standard

fuel oil, all mixed fuels, as well as for pure biodiesel sam-
ples. Therefore, diesel engine can be operated without cor-
rection of fuel system settings.
In contrast to methyl esters’ biodiesel (Kiss et al. 2006),
the decrease of nitrogen oxides content in the exhaust gases
with increasing proportion of ethyl esters in mixed fuels
takes place (Figs. 3, 4, 5, 6, 7a). The last displays low tem-
perature of combustion of biodiesel–air mixture. It is mini-
mum 16.5% for rapeseed oil and maximum 20.3% for mus-
tard oil. Yilmaz (2012) reported that with increase of ethanol
Fig. 2  Performance (a Ne maximum engine power, b T maximum
torque, c ηe maximum engine efficiency) of diesel engine with bio-
diesel blends on the base of ethyl esters of rapeseed, sunflower, corn,
mustard, and linseed oils
concentration in blends, biodiesel–ethanol–diesel CO and
HC emissions increase, while ­NOx emission reduced. Klaus-
meier (2009) claims that ethanol contributes to the mod-
eration of combustion temperature and can, thereby, reduce
­NOx emissions by 10% or more. Above the decrease of ­NOx,

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Chemical Papers (2019) 73:1823–1832 1829

a 1000 a

NOx, ppm
NOx, ppm 1200

800
1000

40
D, %

D, %
50
20

0 0
B0 B20 B40 B60 B80 B100 B0 B20 B40 B60 B80 B100

b b 10 CO2
5
CO
8 CH
4 CO 2
CO2 (CO, CH), %

CO2 (CO, CH), %

СО
3 СН 6

4
2

2
1

0
0
B0 B20 B40 B60 B80 B100 B0 B20 B40 B60 B80 B100

Fig. 3  Emissions (a nitrogen oxides and particulate matter D; b car- Fig. 4  Emissions (a nitrogen oxides and particulate matter D; b car-
bon dioxide/monoxide, unburned hydrocarbons) vs rapeseed bio- bon dioxide/monoxide, unburned hydrocarbons) vs sunflower bio-
diesel blending compositions diesel blending compositions

hydrocarbons. The peculiarity of sunflower, corn, linseed,

content in exhausts’ gases than using ethyl esters of fatty
acids is reported by Makareviciene and Janulis (2003).
An effect on combustion efficiency of the residual etha-
nol has been studied by Patrylak et al. (2013). Because the
decrease in N ­ Ox is not proportional to the ethanol content,
it was concluded that for reducing the concentration of
nitrogen oxides just ester, not the ethanol component of
fuels is responsible one. That is, exactly ethyl esters, in
contrast to the methyl ones (Kiss et al. 2006), lead to a
decrease in the ­NOx content in the exhaust gases.
In the same Figs. 3, 4, 5, 6, 7b, other emissions’ charac-
teristics of a diesel engine fueled with biodiesel blends are
presented also. Thus, with an increase in the proportion of
biofuels in the mixed fuel, there is some increase in smoke
emissions for rapeseed products, whereas for other oils,
we have decrease in particulate matter content. Because
of the lower carbon content in biofuels in comparison with
mineral ones, there is a reduction of carbon dioxide in the
exhaust gases. The oxygenated nature of biodiesel is found
to enhance the complete combustion of the fuel, result-
ing in the reduction of carbon monoxide and unburned
and mustard oil ethyl esters is the lack of CH in exhaust
gases for a number of mixtures. The above figures show
that all emissions with biodiesel are lower than diesel.
The comparison of ethyl esters of different oils indicates
that the use of mixed fuels on their base causes some dete-
rioration in engine performance, i.e., reducing the effective
power, torque, and engine efficiency with the increase of the
biofuel volume content in the blend. However, such reduc-
tion of diesel engine power performance using biodiesel fuel
compositions is not critical. This applies primarily to fuel
mixtures with a low content of a biodiesel component. Thus,
­B20 and ­B40 mixed fuels characterized by less than 3 relative
% drop of the nominal effective power, which at operation
conditions may remains invisible at all.
In Table 6, calculated specific fuel consumption (SFC) for
batches of fossil diesel and pure ethyl esters on the basis of
different oils is presented. We can see rising of SFC from 10
to 13% for rapeseed esters up to 20–22% for linseed esters.
Based on fatty acids’ content (Table 1) in original oils, the
medium molecular weight of ethyl esters and oxygen content
has been calculated (Table 7). In Table 7, the HHV and LHV
for different ethyl esters are shown also.

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1830 Chemical Papers (2019) 73:1823–1832

1200 a 1600

NOx, ppm
1400
NOx, ppm

1000 1200

1000
40 40
30

D, %
20 20
D, %

10
0 0
B0 B20 B40 B60 B80 B100 B0 B20 B40 B60 B80 B100

10 b 12 CO2
CO2 CO
CO 10 CH
8 CH

CO2 (CO, CH), %

8
CO2 (CO, CH), %

6
6

4 4

2 2

0
0 B0 B20 B40 B60 B80 B100
B0 B20 B40 B60 B80 B100

Fig. 6  Emissions (a nitrogen oxides and particulate matter D; b car-

Fig. 5  Emissions (a nitrogen oxides and particulate matter D; b car- bon dioxide/monoxide, unburned hydrocarbons) vs mustard biodiesel
bon dioxide/monoxide, unburned hydrocarbons) vs corn biodiesel blending compositions
blending compositions

Rapeseed and sunflower esters have practically close Conclusions

molecular weights. Corn biodiesel characterized by the low-
est weight, whereas esters based on mustard oil character-
ized by the largest weight, the latest due to the high erucic
acid content. The oxygen content for all esters is near 10%.
As a result, the obtained higher and lower heating values for
all samples are very similar.
It will be interesting to analyze the impact of fatty acid
composition of different oils on diesel engine performance.
The main components of all oils are acids with a carbon
chain of 18 atoms. These are stearic, oleic, linoleic, and lino-
lenic acids. The larger fraction of ­C18 in the original oil, the
less loss of engine power, and torque (Fig. 8). It is natural
that carbon dioxide content increases with increasing carbon
content in esters (Fig. 9).
Thus, engine performance depends primarily on the frac-
tional composition of fatty acids, such as the content of acids
with ­C18 carbon chain.
Among investigated esters, the rapeseed ethyl esters
characterized by the best power performance, whereas the
corn and mustard oil ethyl esters are the best in ecological
aspects.
A range of ethyl esters of rapeseed, sunflower, corn, linseed,
and mustard oils has been synthesized.
Bench testing on a diesel tractor engine D21A of mixed
fuels on the basis of ethyl esters of different oils with petro-
leum diesel fuel showed that fuels obtained by power perfor-
mance inferior to conventional diesel fuel of high quality. An
effective power drop up to 6.5–8.7%, a torque up to 3.4–6.0%
and engine efficiency up to 5.6–8.7% when working on
pure ethyl esters have been monitored. However, observed
reduction up to three relative % of engine performance using
mixed biodiesel fuel ­B20 and ­B40 compositions is not critical
and may be invisible in practical use.
It is found that such power characteristics as effective
power and torque depend primarily on the content of acids
with ­C18 carbon chain.
By the best energy performance characterized rapeseed
esters, while the corn and mustard oil ethyl esters are the
best in the environmental sense. At the same time, rapeseed
and corn oils demonstrate the minimal rising up to 10–14
rel. % of specific fuel consumption. Linseed oil with high

13
Chemical Papers (2019) 73:1823–1832 1831

a 1600 Table 7  Medium molecular weight of ethyl esters, oxygen content,

and heating values
1400
NOx, ppm
Oil M, g/mol Oxygen HHV, MJ.kg−1 LHV, MJ.kg−1
1200 content,
%
1000
Rapeseed 311.66 10.26 39.79 37.89
40
Sunflower 309.83 10.33 39.83 37.93
30
Corn 300.79 10.64 39.37 37.49
20
D, %

Linseed 301.23 10.62 39.43 37.55

10
Mustard 322.78 9.91 39.76 37.86
0
B0 B20 B40 B60 B80 B100

9
b 12
CO2 1
10 CO 8
CH
CO2 (CO, CH), %

8 7

N (T), %
6
6 2
4
5
2
4
0
B0 B20 B40 B60 B80 B100 3
70 75 80 85 90
C18, %
Fig. 7  Emissions (a nitrogen oxides and particulate matter D; b car-
bon dioxide/monoxide, unburned hydrocarbons) vs linseed biodiesel
blending compositions Fig. 8  Dependence of decrease of maximum effective power (1) and
torque (2) on ­C18 fatty acid content in oil

Table 6  Specific fuel No Fuel sample SFC at n = 1000 min−1, SFC at

consumption for mineral diesel kg/kW.hr n = 1600 min−1,
samples and different ethyl kg/kW.hr
esters
1 Ethyl esters of rapeseed oil (­ B100) 0.310 0.281
Mineral diesel sample 1 0.281 0.247
Raised,  % + 10% + 13%
2 Ethyl esters of sunflower oil (­ B100) 0.314 0.294
Mineral diesel sample 2 0.284 0.243
Raised,  % + 18% + 21%
3 Ethyl esters of corn oil ­(B100) 0.300 0.281
Mineral diesel sample 3 0.272 0.245
Raised,  % + 10% + 14%
4 Ethyl esters of mustard oil (­ B100) 0.313 0.288
Mineral diesel sample 4 0.261 0.252
Raised,  % + 19% + 14%
5 Ethyl esters of linseed oil (­ B100) 0.333 0.296
Mineral diesel sample 5 0.272 0.247
Raised, % + 22% + 20%

13

1832
16
14
12
CO2, %
10
8
6 diesel production—towards sustainable energy. Adv Synth Catal
4 Klausmeier WH (2009) Biodiesel and diesel composition. US Patent
77,2 77,4 77,6 77,8 78,0 78,2
C, %
Fig. 9  Correlation of C­ O2 decrease on exhaust gases on carbon con-
tent (C) in ethyl esters
content of unsaturated structures is the worst raw material
practically in all respects.
In the context of engine performance and emissions, these
data suggest the suitability of the ethyl esters of traditional
Ukrainian natural oils as a diesel fuel.
Acknowledgements  The authors wish to express their gratitude to R.V.
Likhniovsky for assistance in calorimetric analysis of ethyl esters.
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