Biomass Conversion and Biorefinery

https://doi.org/10.1007/s13399-020-00913-9

ORIGINAL ARTICLE

Optimization of bio-oil production from Pistacia lentiscus seed

liquefaction and its effect on diesel engine performance
and pollutant emissions
K. Khiari 1 & L. Tarabet 1 & S. Awad 2 & K. Loubar 2 & R. Mahmoud 1 & M. Tazerout 2 & M. Derradji 1

Received: 22 April 2020 / Revised: 11 June 2020 / Accepted: 23 July 2020

# Springer-Verlag GmbH Germany, part of Springer Nature 2020

Abstract
The development of biofuels from oleaginous biomass has attracted a great deal of interest not only because of the environment
pollution but also because of the rapid depletion of the fossil fuel reserves. Among the biomass conversion processes, the
solvolysis reaction has shown to be an interesting solution which allows the direct conversion of raw materials into biofuel. In
the present work, a solvolysis process is applied on Pistacia lentiscus (PL) seeds using ethanol as solvent for bio-oil production.
Several temperatures varying from 270 to 330 °C, reaction time in the range 15–45 min and ethanol:PL seed ratio values from
0.5–1.5 ml/g were considered. The response surface methodology (RSM) combined with Box-Behnken design (BBD) is used for
modeling and optimizing both the process yield and bio-oil viscosity. The results show that the optimum conditions are obtained
for a reaction temperature of 304.91 °C, a reaction time of 35.24 min, and an ethanol:PL seed ratio of 1.16. Under these
conditions, the predicted PL bio-oil yield is around 63.5% with a bio-oil viscosity of 5.88 mm2/s. The PL bio-oil physicochemical
properties showed a good agreement with those of diesel fuel and in conformity with the international requirements except for the
viscosity, whose value was found to be slightly higher than the standard. The engine tests show that the fuel specific consumption
increases around 9% with a mixture containing bio-oil up to 30%. On the other hand, slight increases in CO (13%), HC (25%) and
particulate (30%) emissions were recorded.

Keywords Pistacia lentiscus . Bio-oil . Solvolysis . Box-Behnken design . Response surface methodology . Engine test

1 Introduction fuels promote the emission and accumulation of greenhouse

The increasing industrialization of modern societies, the ex-
pansion of urbanization, and the rapid demographic growth of
populations around the world have led to constantly increas-
ing energy demands. The energy requirements of different
sectors of activity are mainly satisfied by petrochemical re-
sources [1]. Indeed, fossil fuels cover around 80% of the glob-
al energy consumption which are present in all developing
sectors and are the basis of the evolution, progress, and power
of so many nations [2]. The production and use of these fossil
* K. Khiari
k_khiari@yahoo.fr
1
LGP. Ecole Militaire Polytechnique, 16046 Bordj El Bahri,
Algiers, Algeria
2
GEPEA.UMR 6144. DSEE. IMTAtlantique, 04 rue Alfred Kastler,
44307 Nantes Cedex 3, France
gases, as well as CO2, SO2, and NOx, causing environmental
pollution and climate changes [3]. In this context, it is imper-
ative to orient global energy consumption towards new renew-
able and clean resources.
Biofuels from biomass are proven to be among the most
interesting solutions in order to overcome the current and
short-term needs against the energy resources. The develop-
ment of biomass has recently generated a remarkable enthusi-
asm, in particular for raw materials of a carbohydrates (ce-
reals, beets, and sugar cane) [4], lignocellulosic (wood, straw,
and fodder) [5], or oilseeds (vegetable oils) [6].
Several conversion processes have been achieved using
chemical or thermal treatments. The catalytic transesterification
reaction is a mastered technique and widely introduced under
industrial scale. It is an effective approach in the production of
biodiesel. Pyrolysis is a thermal process converting dry biomass
to bio-oil under an inert atmosphere. Most of the studies reported
in the literature on pyrolysis processes have focused on vegetable
and animal biomass [7–9] and wastes from various sources such
 Biomass Conv. Bioref.

as tires [10], lubricating oils [11], and plastics [12]. The water
present in the biomass leads to a negative effect on the pyrolysis,
since it would generate a great heat of vaporization. This limits
the possibilities of using wet biomass as a raw material and thus
affects the energy balance of the process. Furthermore, the py-
rolysis method needs a long reaction time and high operating
temperatures. This increases the concentration of free radicals
and the probability of repolymerization of fragmented species
leading to the formation of char [13]. In contrast, solvolysis can
liquefy biomass regardless of the moisture content, since water is
used as a solvent [14]. This technique, also called liquefaction,
converts solid matter into liquid or gaseous products and a char,
in the presence of a solvent. In the literature, it is reported that
various types of biomass were investigated as feedstock for bio-
oil preparation using solvolysis process such as Camellia
oleifera, Jatropha curcas, and macroalgae [15–17]. In the study
of Durak [18], Anchusa azurea biomass has been converted by
the hydrothermal liquefaction into solid (biochar) and liquid
products (heavy and light bio-oil) with catalyst (H3BO3,
Na2CO3, and Al2O3) and without catalyst at 300, 325, and
350 °C, respectively. It is reported that the highest liquid yield
was determined as 29.69% without catalyst at 350 °C. However,
the best calorific value of 31.32 MJ/kg was obtained from heavy
bio-oil, by applying Na2CO3 catalyst at the same temperature. In
another study achieved by Xu et al. [19], the catalytic pyrolysis
and liquefaction processes of microalgae for bio-oil production
are investigated by using rare earth metals. It has been reported
that Ce(II)/HZSM-5 at 5 wt.%. concentration leads to the optimal
bio-oil yield of 49.71 wt.% (Table 1).
Several parameters also affect the liquefaction process such
as the reaction temperature, nature and amount of solvent, type
and concentration of catalyst, and reaction time [14, 20]. As a

Table 1 Summary of recent liquefaction studies

Author Source Studied parameters Main results

Briones et al. [14] Solid rapeseed cake - Mass/solvent R - Opt. R = 0.2, Y = 82 wt.%
residue -t - Opt. t = 80 min, Y = 88 wt.%
-T - Opt. T = 170 °C, Y = 90 wt.%
Durak et al. [18] Anchusa azurea -T - Opt. T = 325 °C, without catalyst,
- Catalysts (H3BO3, Na2CO3 and Al2O3) Y = 29.91 wt.%
Xu et al. [19] Spirulina microalgae - Catalysts (Pr-Nd/HZSM-5, Ce(I)/HZSM-5, - Ce(II)/HZSM-5, Y = 49.71 wt.%
Ce(II)/HZSM-5,
La(I)/HZSM-5, La(II)/HZSM-5, HZSM-5 and Nil)
Kasargy et al. Pistacia atlantica -T - Opt. T = 375 °C, Y = 56.44 wt.%
[20] -P - Opt. P = 82 bar, Y = 56.44 wt.%
Karagöz et al. Wood biomass - Catalyst K2CO3 concentrations - Biomass/water R - Opt. K2CO3 concentration = 0.47 M,
[21] Y = 35.9 wt.%
- Opt. R = 1:6 g/ml, Y = 8.6 wt.%
Xu et al. [22] Jack pine powder -t - Opt. t = 60 min, Y = 35 wt.%
-T - Opt. T = 300 °C, Y = 44 wt.%
- Initial P of H2 - Opt. Initial P of H2 = 10 MPa, Y = 45 wt.%
- Catalysts (FeS or FeSO4) - Opt. FeSO4 = 5 wt.%, Y = 63 wt.%
Braz et al. [23] Pine wood sawdust -t - Opt. t = 120 min, Y = 92 wt.%
-T - Opt. T = 170 °C, Y = 92 wt.%
- Catalysts (H2SO4, p-toluenesulfonic - Opt. H2SO4 = 2.6 wt.%, Y = 92 wt.%
and trichlorocyanuric acids)
Bhaskar et al. Cherry wood - Aq. K2CO3 catalyst - Aq. K2CO3 catalyst = 1 M, Y = 43.2 wt.%
[24] Cypress wood - Aq. K2CO3 catalyst - Aq. K2CO3 catalyst = 0.5 M, Y = 52.0 wt.%
Bai et al. [27] Plastic waste -T - Opt. T = 490 °C, Y = 51 wt.%
-t - Opt. t = 60 min, Y = 37 wt.%
-P - Opt. P = 29 Mpa
Boocock et al. Poplar wood -t - Opt. t = 0 min, Y = 48.5 wt.%
[29] Water/wood R - Opt. water/wood R = 3/1
Yan et al. [30] Sawdust -T - Opt. T = 450 °C, Y = 63.9 wt.%
-t - Opt. t = 30 min, Y = 25 wt.%
- P of H2 - P of H2 = 5 Mpa, Y = 40 wt.%
Karagöz et al. Sawdust -T - Opt. T = 280 °C
[31] -t - Opt. t = 15 min, Y = 9.3 wt.%
Hadhoum et al. Oil mill waste water -T - Opt. T = 280 °C, Y = 58.09 wt.%
[32] -t - Opt. t = 30 min, Y = 58.09 wt.%

T reaction temperature, t reaction time, R ratio, P pressure, Opt. optimal, Y bio-oil yield
Biomass Conv. Bioref.
general rule, it is recognized that temperature adds the synergis-
tic effect on liquid yield, due to the fragmentation of biomass
with the rising temperature [21]. Xu et al. [22] reported that the
effect of sub-and supercritical conditions on the liquefaction of
Jack pine powder in a hydrogenated environment. Under the
pressure of 2.0 MPa of H2, a temperature change from subcrit-
ical (220 °C) to supercritical (350 °C) was made; it was observed
a 25% increase in bio-oil yield. Initially, the increase in temper-
ature triggers a bio-oil yield; after reaching a maximum of the
bio-oil yield, a further increase in temperature effectively in-
hibits the liquefaction of the biomass [23].
According to Bhaskar et al. [24], the presence of large
quantities of cellulose and hemicellulose in the raw material
leads to high yields of bio-oil. For example, samples of cherry
wood produce more bio-oil than cypress wood, due to the high
lignin content in the biomass. Lignin is difficult to degrade
and appears mainly in the residue fraction [25].
Pressure is another important parameter for the biomass
degradation in solvolysis. In fact, the idea is to maintain a
single phase during liquefaction to avoid the significant en-
thalpies involved during phase changes in the solvents.
By maintaining the pressure above the critical pressure of
the reaction medium, the rate of hydrolysis and the dissolution
of the biomass can be easily controlled, which thermodynam-
ically improves the reaction pathways favorable for the pro-
duction of liquid fuels or on the yield of gases. The pressure
also increases the density of the solvent, but once the super-
critical conditions are reached, the pressure exerts a small or
negligible influence on the yield of the liquid or gas. Indeed, in
the supercritical region, the influence of pressure on the prop-
erties of water or on the reaction medium (solvent) is very
weak [26, 27].
During the solvolysis process, the depolymerization of the
biomass is highly dependent on the used solvent. The interac-
tions between the solvent and the substrate increase when the
solvent is a product derived from the biomass itself, as is the
case for ethanol. In addition, the decomposition reactions
would be linked to the polarity of the liquefaction solvent
and the polar solvent such as ethanol contains hydrogen
bonds. Therefore, it could act as a hydrogen donor solvent
playing the role of an effective stabilizing agent, thus,
preventing the repolymerization reactions of small fragments
to form solid residues [28, 29].
The reaction time can influence the composition of the
products and the conversion of the biomass. During the lique-
faction of the biomass, short residence times are generally
desired. Various authors have reported results relating to the
bio-oil yield as a function of the residence time: according to
Boocock and Sherman [29], a long residence time reduces the
bio-oil yield, except for a very high biomass/water ratio. Yan
et al. [30] observed a slight increase in liquid yields for long
residence times. The residence time can also influence the bio-
oil composition [31].
To optimize the processes, many researchers use parametric
study, one factor at a time while keeping the other variables
constant [32]. This method does not allow the identification of
the interactions between variables and does not precisely evalu-
ate the optimum outcomes. Therefore, it involves a large number
of tests, which are lengthy and economically unsustainable. The
application of meta-modeling techniques such as RSM and ar-
tificial neural networks coupled with an optimization algorithm
is essential for reducing the cost of production processes and
taking into account the combined interactions between the var-
iables that provide an accurate experimental model of the system
being studied. Moreover, such type of tools can achieve a global
optimization within a reasonable cost.
In our previous work [20], a parametric study was achieved
for Pistacia atlantica bio-oil preparation using solvolysis pro-
cess and ethanol as a reagent and solvent. Nine experiments
were conducted under various temperature (300 to 450 °C)
and pressure (40 to 85 bars) conditions. The maximum bio-
oil yield of 56 wt.% was obtained at 375 °C and 43 bars. The
obtained bio-oil physicochemical properties are comparable to
those of conventional diesel with the exception of viscosity;
the obtained value is slightly higher than the standard.
Instead to transesterification process used in our previous
studies on Pistacia lentiscus (PL) valorization which need oil
extraction preliminary step [33], the present work aims to
directly valorize PL seeds by applying the solvolysis process.
The optimization of the solvolysis process parameters of this
PL non-edible oleaginous plant, very abundant in the
Mediterranean basin and proven a favorable energetic power
for the synthesis of a biofuel, is investigated in order to further
increase the bio-oil yield and improve its quality. It will be a
question of optimizing the reaction time (15–45 min), temper-
atures (270–330 °C), and ethanol:PL seed ratio (0.5–1.5 ml/g),
using RSM in combination with BBD. The physicochemical
properties of bio-oil, obtained at optimal conditions, are deter-
mined according to the standard methods and compared with
those of conventional diesel fuel. Thereafter, an experimental
investigation is carried out to study the effect of this bio-oil
blended with diesel fuel (30 and 50% by v.) on the perfor-
mance and the exhaust emissions (carbon monoxide CO, un-
burned hydrocarbon HC, nitrogen oxide NOx and soot) of a
single-cylinder DI diesel engine operating under various en-
gine load conditions. Results are compared with those of con-
ventional diesel operation, taken as a baseline.
2 Material and methods
2.1 Raw materials
The mature fruits of PL are collected in Mountains located in
Northern Algeria. Ethanol is purchased from Sigma-Aldrich
with a purity of 98%.

2.2 Experimental set-up
The solvolysis experimental set-up (Fig. 1) consists of a pres-
sure reactor from the company SAMCO, capable of reaching a
maximum temperature and pressure of 450 °C and 190 bars,
respectively. The reactor volume is 998 ml, made of stainless
steel and heated with 15 heating rods of 1250 W located in its
periphery. A safety valve is provided in the case that the pres-
sure in the reactor exceeds 190 bars. The reactor is equipped
with a gas injection network. The gases leaving the reactor are
purged or collected for analysis, through a valve.
Thermocouple is placed in the reactor to monitor and record
the evolution of the temperature. In addition, a pressure sensor
is used to measure the pressure in the reactor.
2.3 Bio-oil preparation
In each experiment carried out, the reactor is filled with the PL
seeds and ethanol, with a determined ratio, closed and purged
for 10 min with nitrogen in order to eliminate the presence of
oxygen inside. Once the autoclave is heated to the desired
reaction temperature and maintained up to the reaction time
end, the cooling period is switched on to room temperature.
Then, the gas phase is removed from a sampling valve and the
autoclave opening is preceded. Hence, the solid-liquid mix-
ture is recovered from the bottom of the reactor and filtered.
The solid product is washed with the same solvent, filtered
again and dried at 105 °C in an oven for 24 h. The collected
liquid is distilled to remove the solvent where the remaining
fraction is bio-oil (biofuel).
The bio-oil, solid residue, and gas yields are calculated
using Eqs. 1–3.
Bio−oil mass
Bio−oil yield ðwt:%Þ ¼  100 ð1Þ
PL seeds mass
Fig. 1 Experimental high-
pressure autoclave reactor
Biomass Conv. Bioref.
solid residue mass
Solid residue yield ðwt:%Þ ¼  100 ð2Þ
PL seeds mass
Gas yield ðwt:%Þ
¼ 100−ðBio−oil yield þ Solid residue yieldÞ ð3Þ
2.4 Experimental design
RSM is used to study the effect of temperature of the reaction
medium, reaction time, and ethanol:PL seed ratio on both the
bio-oil yield and its viscosity measured at 40 °C. For this
purpose, the mathematical model describing the relationship
between the predicted responses y and the reaction conditions
x is given in Eq. (4).
y ¼ β 0 þ ∑31¼1 βi xi þ ∑3i¼1 βii x2i þ ∑2i¼1 ∑3j¼iþ1 βij xi x j ð4Þ
where β0, βi, βii, and βij are constant coefficients [33].
The mathematical model was tested with the analysis of
variance (ANOVA) which determines the significance of each
parameter on the objective function.
A three-level-three-factor BBD has been employed in this
study, requiring 15 experiment combinations including three
center points. The working interval for each variable was chosen
based on preliminary tests. All experiments on liquefaction were
replicated three times under the same conditions for ensuring the
viability of the obtained values. The considered variable levels
and corresponding coded values are given in Table 2.
2.5 PL bio-oil analysis and characterization
The chemical composition of PL bio-oil is determined using a
gas chromatography GC Clarus 600 coupled to a Perkin
Elmer Turbo Mass Gold Mass Spectrometer and a Flame
Biomass Conv. Bioref.
Table 2 Considered variables levels
Variable Symbol Coded level
−1 0 1
Temperature (°C) A 270 300 330
Time (min) B 15 30 45
Ethanol:PL seed ratio (ml/g) C 0.5 1.0 1.5
Ionization Detector (GC-MS-FID) using a PE-5MS column
with a split ratio of 1:100. Column temperature is pro-
grammed from 30 to 100 °C at 2 °C/min after from 100 to
300 °C at 5 °C/min. The elemental composition analysis is
performed using a CHNS-O Analyzer FLASH 1112 series E.
The high heating value (HHV) is determined using a PARR
6200CLEF calorimeter. Viscosity is measured using a vibro
viscometer SVM 3000/G2. Densimeter DMA 4500 is used to
determine the density. Flash point is determined with a
PENSKY MARTENS NPM440 apparatus. Eraflash of
Eralytics is used to measure the cetane number. Karl Fisher
apparatus is used to measure the water content. Acid values
are determined by titrimetry. A micro-chromatograph (micro-
GC) Agilent 3000A is used to analyze the gaseous product,
which is collected in a gas sampling bag. This instrument is
equipped with two detectors. The first is a flame ionization
detector (FID) to analyze hydrocarbons gas, and the second is
a thermal conductivity detector (TCD) for H2, CO, and CO2
analysis. The first channel (10 m × 0.32 mm × 12 μm) is a 5 Å
molecular sieve; the second channel is PLOT Q column
(PLOT Q, 10 m × 0.32 mm × 10 μm).
2.6 Test engine facility
The engine tests are carried out on a test bench mainly com-
posed of:
– A single-cylinder diesel engine, Lister Petter (TS1) with
natural aspiration, air-cooled, with a compression ratio of
18, a fuel injection timing of 13 BTDC, injection pressure
of 250 bar and rated power output of 4.5 kW at1500 rpm.
– An automatic controlled eddy current dynamometer
(Eurotherm PARVEX/132 M-G model) coupled to the
engine.
– An SA exhaust gas analysis bay, placed at the engine
exhaust, to quantify the main pollutant gases: CO, CO2,
NOx and unburned hydrocarbons (HC) with the uncer-
tainties of the sensors of ± 50 ppm, ± 0.25%, and ±
100 ppm, respectively.
– A PPS Pegasor particulate analyzer which measures the
mass and number concentration in real time, up to
100 Hz, with an uncertainty of 10 ng/s.
– Two (low and fast) acquisition systems, intended for mea-
surements of combustion characteristics, engine perfor-
mance and exhaust emissions. A rapid digital data acqui-
sition system is used for measuring the cylinder pressure
and the fuel injection pressure. The second data acquisi-
tion system is carried out for low frequency measure-
ments, which concerns the engine speed, the power out-
put, the temperatures, the flow rate of air and pilot/
gaseous fuels, the exhaust emissions (CO, HC, CH4,
NOx and particulate matter).
The details of the engine test bench are well explained in
previous works [34, 35].
3 Results and discussion
3.1 PL seed characteristics
The determination of the PL seeds characteristics is of crucial
importance. It provides the energetic potential of this biomass
for use as a substitute source of biofuel production.
HHV value of 28.13 MJ/kg is promising for the use of PL
seeds as a raw material in the production of a biofuel. Elementary
analysis allowed to determine the mass composition, mainly car-
bon (61.98%), hydrogen (8.82%), oxygen (28.03%) and nitrogen
(1.17%). This analysis makes it possible to calculate the H/C
ratio of the number of hydrogen atoms over the number of car-
bon atoms, a characteristic ratio of a hydrocarbon.
3.2 Conditions optimization by RSM
The experimental values of yield and viscosity of bio-oil ob-
tained at three factor BBD points are given in Table 3. The
bio-oil yield values were found to range between 30 and
62.89% and are comparable to those found in the literature
[20, 36]. The bio-oil viscosity values were found to range
from 5.89 to 13.61 mm2/sand are slightly higher than the
upper limit of the standard (EN 14214). This may be ex-
plained by the fact that after the decomposition of the biomass
under the effect of the temperature leading to the formation of
free radicals, the combination reaction of these species can
take place and negatively affects the recovered bio-oil quality.
Equations (5) and (6) give the quadratic regression models
fitted to the experimental data. These formulas link the effects
of the operating variables on the bio-oil yield and viscosity,
respectively.
Y ¼ −1615:19 þ 10:66A þ 1:21B þ 16:06C−0:0017AB
þ 0:0058AC
þ 0:35BC−0:017A2 −0:015B2 −13:56C 2 ð5Þ
 Biomass Conv. Bioref.

Table 3 BBD matrix of the three variables with the experimental bio-oil In order to find the sources of variation of the responses
yield and viscosity values
considered, namely the bio-oil yield and its viscosity, the anal-
Run Factor 1 A: Factor Factor 3 C: Response Response 2 V: ysis of variance was made. Response variance analysis for
temperature 2 B: ethanol:PL 1 Y: bio- bio-oil viscosity bio-oil yield (Y) is shown in Table 4.
°C time seed ratio oil yield (40 °C) mm2/s The Model F-value of 215.61 means that the model is sig-
min ml/g %
nificant. P values less than 0.05 imply that the model terms are
1 270 15 1 30.50 13.26 significant. In this case A, B, BC, A2, B2, and C2 are signifi-
2 330 15 1 52.36 9.32 cant model terms. A value of the R2 of 0.9974 (close to 1.0)
3 270 45 1 35.65 11.84 indicates that bio-oil yield is well correlated by the quadratic
4 330 45 1 54.38 10.02 model. The predicted R2 of 0.9694 is in agreement with the
5 270 30 0.5 32.46 13.61 adjusted R2 of 0.9928; the difference is less than 0.2. In addi-
6 330 30 0.5 51.85 12.36 tion, the small value of CV of 1.90% indicates that the results
7 270 30 1.5 34.52 10.96 provided by the adapted model are satisfactory.
8 330 30 1.5 54.26 10.33 Response variance analysis for bio-oil viscosity (V) is
9 300 15 0.5 56.33 9.01 shown in Table 5. The Model F-value of 16.59 implies that
10 300 45 0.5 54.33 8.54 the model is significant. In the present case, the significant
11 300 15 1.5 51.00 8.36 model terms are A, C, A2, and C2. A coefficient of determi-
12 300 45 1.5 59.36 7.32 nation R2 of 0.9676 means that the model allows to predict the
13 300 30 1 61.25 6.12
measured response values satisfactorily.
14 300 30 1 62.12 5.99
The two considered responses in this study (yield and vis-
15 300 30 1 62.89 5.89
cosity) are influenced by the three variables (temperature,
time, and the ethanol:PL seed ratio). To minimize energy con-
sumption, it is necessary to work at low temperature and at a
reduced time. But if the profitability of the process is request-
V ¼ −470:98−2:95A−0:57B−16:22C þ 0:0012AB ed, the bio-oil yield should be high enough with an acceptable
viscosity. It will be necessary to choose the best compromise
þ 0:01AC−0:019BC þ 0:0048A2 þ 0:0036B2 which ensures profitable production with reduced production
costs and obtain a biofuel which meets the standards.
þ 6:03C 2 ð6Þ
Experimentally, this compromise is reached if the temperature

Table 4 Response variance

analysis for bio-oil yield (Y) Source Sum of squares df Mean square F-value p value

Model 1761.57 9 195.73 215.61 < 0.0001

A-temperature 794.41 1 794.41 875.09 < 0.0001
B-time 22.88 1 22.88 25.21 0.0040
C-ethanol:PL seed ratio 2.17 1 2.17 2.39 0.1824
AB 2.45 1 2.45 2.70 0.1614
AC 0.0306 1 0.0306 0.0337 0.8615
BC 26.83 1 26.83 29.56 0.0029
A2 878.32 1 878.32 967.52 < 0.0001
B2 43.71 1 43.71 48.15 0.0010
C2 42.45 1 42.45 46.76 0.0010
Residual 4.54 5 0.9078
Lack of fit 3.19 3 1.06 1.58 0.4101
Pure error 1.35 2 0.6732
Cor total 1766.11 14
Fit statistics
Std. Dev. 0.9528 R2 0.9974
Mean 50.22 Adjusted R2 0.9928
C.V. % 1.90 Predicted R2 0.9694
Adeq precision 40.2377
Biomass Conv. Bioref.

Table 5 Response variance

analysis for bio-oil viscosity (V) Source Sum of squares df Mean square F- p value
value

Model 88.81 9 9.87 16.59 0.0032

A-temperature 7.30 1 7.30 12.27 0.0172
B-time 0.6216 1 0.6216 1.05 0.3535
C-ethanol:PL seed ratio 5.36 1 5.36 9.02 0.0300
AB 1.12 1 1.12 1.89 0.2277
AC 0.0961 1 0.0961 0.1616 0.7043
BC 0.0812 1 0.0812 0.1366 0.7268
A2 68.55 1 68.55 115.27 0.0001
B2 2.37 1 2.37 3.99 0.1024
C2 8.38 1 8.38 14.09 0.0132
Residual 2.97 5 0.5947
Lack of fit 2.95 3 0.9823 73.86 0.0134
Pure error 0.0266 2 0.0133
Cor total 91.79 14
Fit statistics
Std. Dev. 0.7712 R2 0.9676
Mean 9.53 Adjusted R2 0.9093
C.V. % 8.09 Predicted R2 0.4857
Adeq precision 12.2985

is around 300 °C with a reaction time of 30 min. The models about the response for given levels of each factor. The opti-
established by Eqs. 5 and 6 can be used to make predictions mum conditions for the process obtained par solution of two

Fig. 2 Effects of reaction

temperature and reaction time on
the bio-oil yield: ethanol:PL seed
ratio = 1.0 ml/g
 Biomass Conv. Bioref.

Fig. 3 Effects of reaction

temperature and reaction time on
the bio-oil viscosity: ethanol:PL
seed ratio = 1.0 ml/g

Fig. 4 Effects of reaction time

and ethanol:PL seed ratio on the
bio-oil yield: reaction tempera-
ture = 300 °C
Biomass Conv. Bioref.
models are as follows: process temperature, reaction time and
ethanol:PL seed ratio of 304.91 °C, 35.24 min, and 1.16:1.0,
respectively. Under these conditions, a theoretical bio-oil
yield of 63.55% and viscosity of 5.88 mm2/s are obtained.
The response surface contour plots show how the bio-oil
yield and its viscosity are affected when the experimental
conditions are varied (Figs. 2, 3, 4, 5, 6, and 7). Figures 2
and 3 show the influence of temperature and time on the yield
and on the viscosity of the bio-oil, respectively, obtained by
the solvolysis process of PL seeds at 1.0 ethanol:biomass ra-
tio. Experimental results have shown that the transformation
rate of PL fruit into bio-oil is low at reduced temperature
(around 270 °C). This rate improves with increasing temper-
ature until reaching a maximum of 62.69% at a temperature of
the reaction medium of 300 °C. Above this temperature, a
slight decrease in yield has been observed. On the other hand,
the viscosity of the bio-oil reaches an optimal of 5.89 mm2/s at
300 °C. When the temperature is high enough, depolymeriza-
tion of biomass occurs, increasing thereby the concentration
of free radicals and the likelihood of repolymerization of the
fragmented species. The duality between the fragmentation
and the repolymerization reactions highlights the role of tem-
perature during solvolysis process. The depolymerization of
Fig. 5 Effects of reaction time
and ethanol:PL seed ratio on the
bio-oil viscosity: reaction
temperature = 300 °C
biomass is a predominant reaction during the initial stages of
solvolysis. The repolymerization is activated at later stages
leading to the formation of solid char, resulting in a reduction
in yield and an increase in the viscosity of the bio-oil (liquid).
An intermediate temperature generally gives higher amounts
of biofuel. The high temperatures are generally not suitable for
the production of liquid bio-oil, in terms of operating costs and
yield. There are two reasons for this behavior: decompositions
and secondary reactions become active at high temperatures
and lead to the formation of gases [23]. The recombination of
free radicals is believed to lead to the formation of carbon, due
to the high concentration of these radicals. These two mecha-
nisms become predominant at high temperatures, which de-
crease the production of bio-oil from biomass. In addition, at
temperatures below 280 °C, the incomplete decomposition of
the biomass components would decrease the bio-oil yield.
Under liquefaction conditions, lignin and cellulose rapidly
fragment at temperatures above 280 °C [37].
Figure 4 shows the effect of time and ethanol:PL seeds on
the bio-oil yield at 300 °C of temperature. It is obvious that the
bio-oil yield increases when the reaction time increases until
the optimal value (around 30 min). Beyond this value, the
trend is overturned. On the other hand, the viscosity has

Fig. 6 Effects of reaction
temperature and ethanol:PL seed
ratio on the bio-oil yield: reaction
time = 30 min
become important for the products obtained from the longer
reaction times. This result is due to the fact that a long time in
the solvolysis process would favor the repolymerization of the
radicals, leading to the formation of carbon (solid) and, con-
sequently, to a reduction in yield and to an increase in the
viscosity of the bio-oil (Fig. 5).
The contour plots in Fig. 6 display the effects of both tem-
perature and ethanol:biomass ratio on the yield of bio-oil at
30 min. For a fixed temperature, an excess of PL seeds (ratio
around 0.5: 1) would not allow the solvent to realize enough
H+ ions, which induces repolymerization reactions between
free radicals, resulting in a significant molecular mass in the
solvolysis products, thereby forming solid products. A maxi-
mum bio-oil yield is recorded for a 1:1 ratio leading to an
optimal viscosity value of 5.89 mm2/s (Fig. 7). Beyond this
ratio, the production of bio-oil continuously decreases, with
an increase in the ethanol:PL seed ratio. These results are
similar to those achieved by Huang et al. [38] whom was
reported that the excess solvent would lead to a greater amount
of solid residue by self-condensation reaction [20].
3.3 Bio-oil, solid, and gas characteristics
It is interesting to note that the optimal liquefaction process
conditions lead to produce an important part of a liquid frac-
tion (63.5%). It should be also noted that the PL conversion
Biomass Conv. Bioref.
generates low proportions of solid residue (23.1%) and gas-
eous fractions (13.4%), as compared with liquid fraction.
Analysis of the gases produced by the liquefaction process
showed the presence of CO2 (6.5%), CO (1%), saturated and
unsaturated hydrocarbons (5.9%), whose chain is between C1-
C4, as well as traces of H2 and CH4. In hydrothermal lique-
faction of biomass, dehydration and decarboxylation are two
main reactions that can eliminate the oxygen atom in the form
of H2O and CO2. The severe operating conditions cause the
dehydrogenation of the components of the biomass, while the
decarboxylation is reduced to a thermal cracking of the long
chain of carboxylic acids, which releases the CO2 and reduces
the chain size.
For the solid residue, the elemental composition analysis
has shown that it is composed of the following: C: 59.0%; H:
6.6%; O: 32.2%; and N: 2.2% corresponding to an interesting
calorific value (29.03 MJ/kg) that allows to use this residue as
an alternative solid fuel to produce heat or for the preparation
of activated carbon.
The chromatogram presented in Fig. 8 shows that the PL
bio-oil mainly consists of fatty acid ethyl esters, characterized
by intense peaks. For a quantitative analysis, it would be suf-
ficient to calculate the area of each peak of the chromatogram
of the FID detector, in order to determine its proportion rela-
tive to the total composition of the bio-oil. Fatty acid com-
pounds represent more than 93% of the bio-oil fraction: ethyl
Biomass Conv. Bioref.
Fig. 7 Effects of reaction
temperature and ethanol:PL seed
ratio on the bio-oil viscosity:
reaction time = 30 min
cis-9-hexadecenoate (1.38%), ethyl cis-11-hexadecenoate
(1.66%), ethyl hexadecenoate (18.53%), ethyl cis-9-
octadecanoate (69.72%), and ethyl octadecenoate (1.91%).
The results of this analysis provide an idea about the predom-
inant reactions occurring during the solvolysis process, name-
ly the transesterification of the oil found in PL seeds. This
reaction mechanism was favored by the presence of ethanol
as a solvent. At the same time, thermal cracking took place
transforming the lignocellulosic materials into liquids by
Fig. 8 PL bio-oil chromatogram
depolymerization and into gases by reactions of
decarbonylation and decarboxylation. As a result of these re-
action paths, biomass is converted into linear and cyclic hy-
drocarbons (6.80%). Interestingly, the same behavior was ob-
served in our previous study [12].
The main properties of PL bio-oil, diesel fuel, and
EN14214 standards are presented in Table 6. The viscosity
value of this biofuel of 5.89 mm2/s is slightly higher than
standard EN14214, for which it must be between 3.5 and
 Biomass Conv. Bioref.

Table 6 Properties of diesel fuel

and PL bio-oil Properties Units Diesel PL bio-oil EN 14214

Density at 15 °C kg/m3 840 900 860–900

Kinematic viscosity at 40 °C mm2/s 3.2 5.89 3.5–5.0
High heating value MJ/kg 43.29 38.05 -
Cetane number 49 47.5 51 min
Flash point °C 55 48 101 min
Acid value mg KOH/g – 0.41 0.5 max

5 mm2/s. The density of PL bio-oil at 15 °C is equal to
0.90 kg/m3. The high heat value of bio-oil (38.05 MJ/kg) is
comparable to that of conventional diesel, which justifies the
choice of this biomass as a source of innovative fuel.
However, a flash point value of 48 °C is measured; it is com-
parable to that of conventional diesel. Indeed, such a flash
point value is synonymous with safety during storage, use,
and handling of the product. A high cetane number (47.5)
generates a short ignition delay and improves the ignition
ability of the engine. A low acid number is obtained, in the
order of 0.41 mg KOH/g; this value is satisfactory; it is lower
than the maximum limits required by the standard.
3.4 Engine tests
In Table 7, brake-specific fuel consumption (BSFC) and
brake thermal efficiency (BTE) are given as the engine per-
formance at various load conditions for diesel fuel and its
blends containing 50% and 30% bio-oil. Conversely to
BSFC evaluation, based on the ratio of the total fuel flow
rate and the engine brake power, the difference in the
heating values between test fuels (diesel, BO30, and
BO50) is taken into account in the BTE calculation. It is
noticeable that the BSFC increases with the bio-oil content
in the mixture for all the tested engine load conditions. The
BSFC of a diesel engine is particularly sensitive to the
physicochemical properties of the fuel particularly viscosi-
ty and calorific value as well as the volumetric fuel
injection conditions [35]. The increase in the proportion
of bio-oil in the mixture leads to a decrease in the value of
the calorific value and an increase in the viscosity, requiring
more fuel quantity for maintaining the same operating con-
ditions. As a result, the specific fuel consumption is in-
creased and the BTE is decreased as compared with diesel
fuel at all examined engine loads. In comparison to BO50,
blending diesel fuel with 30% of bio-oil leads to an im-
provement in the engine performance (BTE and BSFC)
approximately 5% in all engine load conditions. Such be-
havior is in agreement with the results reported in the liter-
ature [34].
The main pollutant emissions (HC, CO, NOx, and par-
ticulate matters) are also shown in Table 7 for diesel fuel
and its blends containing 50% and 30% bio-oil. As usually
reported, the formation of NOx mainly depends on the com-
bustion temperature, the oxygen availability, and the resi-
dence time for which oxygen-nitrogen reactions occurring
to a significant completion level. Even with high oxygen
content, BO50 blend results in a considerable low NOx
emissions level as compared with neat diesel fuel: approx-
imately 14% at medium load and 25% at high engine load
conditions. In fact, the tallness of air/bio-oil blend mixture
preparation during the ignition delay period, due to the high
bio-oil viscosity and poor volatility, leads to the inferior
burning rate at the earlier stages of combustion resulted in
reduced peak cycle temperature and consequently reduced
NOx emissions.

Table 7 Performance and pollutant emissions at various load conditions for diesel and its blends with bio-oil

Fuels HHV (MJ/ Flash point Viscosity (mm2/ Load BSFC BTE HC NOx CO Particulate (mg/
kg) (°C) s) (kW) (g/kW h) (%) (ppm) (ppm) (ppm) m3)

BO50 40.17 52 4.36 1.17 540.53 17.0 313 487 254 26.0
2.25 374.02 24.6 336 607 358 37.0
4.50 337.00 27.2 436 683 1883 142.0
BO30 41.66 53 3.91 1.17 536.12 16.5 302 481 246 16.0
2.25 384.96 23.0 307 750 352 22.0
4.50 320.96 27.6 389 845 1745 133.0
Diesel 43.29 55 3.20 1.17 465.26 18.0 272 477 217 6.1
2.25 335.84 24.8 282 702 301 17.9
4.50 281.89 29.5 348 902 1652 104.8
Biomass Conv. Bioref.
In Table 7, it is clearly shown that the increase in bio-oil
quantity in the blend, particularly the blend with 50% bio-oil,
leads to the combustion process weakening expressed by the
increase up to 19% in HC emissions and 12% in CO emissions
when loading the engine at full engine load condition. The
trend of HC emissions has been observed by a number of
researchers with different vegetable oils as fuel [39, 40]. In
addition to the presence of polycyclic aromatic hydrocarbons,
the high viscosity of the bio-oil leads to poor spraying of the
fuel into the engine cylinder and subsequently to poor com-
bustion [35]. For carbon monoxide (CO) emissions, highest
levels are recorded for BO50 blend at all power outputs as
compared with BO30 and neat diesel fuel. In diesel engine,
CO emissions are formed due to rich pockets present in the
combustion chamber. Combustion of rich mixture leads to
partial oxidation of carbon atoms and results in CO emissions.
The low energy content (38.05 MJ/kg) of the neat bio-oil has
led to more blend quantity to be injected for maintaining the
same running point conditions. Hence, the air fuel mixture
present in the combustion chamber became rich and resulted
in more CO emissions.
This combustion default, particularly noticed with blends
containing higher bio-oil quantity (i.e., 50% by v.), is con-
firmed by the particulate matter measurements. The main
cause of particulate matter formation in diesel engine is the
high-temperature pyrolysis of the heavy hydrocarbons in the
diesel fuel. Despite the presence of the fuel bound oxygen of
PL bio-oil (smoke reducing agent), the lower volatility, the
high viscosity and density of BO50 seem to have the domi-
nating effect in the increasing of fuel size droplets (poor at-
omization) and the slowing of evaporation rate, a fact which
promotes soot emissions.
Hence, diesel/bio-oil’s CO and HC emissions can be suc-
cessfully managed and reduced by the adjustment of injection
pressure and using after-treatment system–based catalysts
which help to promote the chemical oxidation of CO and
HC as well as the organic fraction of diesel particulates.
4 Conclusion
The solvolysis process adopted in this experimental study is
based on a thermochemical conversion of PL seeds into a bio-
oil suitable as fuel for diesel engine. From the present work,
the following results can be drawn:
– The optimization by RSM of the solvolysis process in the
production of bio-oil from PL seeds made it possible to
identify the optimum conditions: a reaction temperature
of 304.91 °C, a reaction time of 35.24 min, and an
ethanol:PL seed ratio of 1.16:1 ml/g. These conditions
ensure both a maximum bio-oil yield of 63.5% and a
minimum viscosity value of 5.88 mm2/s.
– The characterization of PL bio-oil according to the stan-
dard methods shows that the obtained physicochemical
properties are comparable to those of diesel fuel and in
conformity with international requirements with the ex-
ception of viscosity; the obtained value of 5.89 mm2/s is
slightly higher than the standard.
– In bio-oil/diesel blend engine tests, the BTE decreases up
to 7% as compared with that of conventional diesel fuel
operation. For pollutant emissions, a slight increase in
CO, HC, and particulate emissions was recorded with a
decrease in NOx emissions, for all considered engine
loads.
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