Renewable Energy 170 (2021) 964e973

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Renewable Energy
journal homepage: www.elsevier.com/locate/renene

One-pot conversion of sesame cake to low N-content biodiesel via

nano-catalytic supercritical methanol
Tahereh Nematian a, Milad Fatehi b, Morteza Hosseinpour c, Mohammad Barati b, *
a
Department of Applied Chemistry, School of Chemistry, College of Science, University of Tehran, Tehran, Iran
b
Department of Applied Chemistry, Faculty of Chemistry, University of Kashan, Kashan, Iran
c
Renewable Energy Department, Niroo Research Institute (NRI), Tehran, Iran

a r t i c l e i n f o a b s t r a c t

Article history: The fatty acid methyl esters (FAMEs) and H2 were produced from sesame cake in supercritical mixture of
Received 28 August 2020 methanol and water using alumina supported CaO and MgO nanoparticles. The fresh and used catalysts
Received in revised form were characterized by ICP-OES, BET, XRD, and TEM techniques. The significant influence of catalysts on
22 January 2021
the gas production was revealed. Further, the highest amounts of H2, CO, and CO2 was achieved by MgO/
Accepted 7 February 2021
Available online 10 February 2021
g-Al2O3 with the hydrogen fraction more than 7.6 times, compared with the non-catalytic process. For
biodiesel, CaO/g-Al2O3 showed the best performance where 35.3% of the liquid product was FAMEs, more
than 2.3 times relative to the non-catalytic process. In order to reduce the amounts of nitrogenate
Keywords:
Hydrogen
content in the liquid fuel, an efficient and scalable method implemented with the Soxhlet apparatus and
Biodiesel the absorption tube equipped with CO2 gas flow system. Accordingly, the N-contents of the liquid
Upgrading products were reduced to highest degree of 65.2%, asserting that the reduced amount of the N-content
Supercritical methanol strongly depends on the catalyst during the production process.
Sesame cake © 2021 Elsevier Ltd. All rights reserved.
CaO
MgO

1. Introduction
Climate change as a result of greenhouse gas (GHG) emissions is
a troublesome for humankind future life. The crisis occurred
because the carbon content of the atmosphere is rising which
anticipated to continue. Releasing carbonaceous gases such as CO,
CO2, CH4, aromatics, other hydrocarbons with heteroatoms, SOx,
and NOx to the environment is directly or indirectly relative to the
fossil fuels consumption. Transportation is one of the largest
sources of the gas emission and subsequently, global warming.
Petroleum-based fuel replacement with sustainable energies has
several advantages that can help us save our health and environ-
ment. Since plants consume CO2 of the atmosphere to grow up,
biofuels in a wide range of solid, liquid, and gaseous transportation
fuels are nice candidate for sustainable utilization of our bio-
resources. It is the golden key to use biofuels for transportation
because their net carbon emissions to the environment is zero. In
this way, several chemical and biochemical processes have been
performed to produce biofuels [1,2].
* Corresponding author.
E-mail address: barati.m@kashanu.ac.ir (M. Barati).
Among the biofuels, fatty acid methyl esters (FAME) are favorite
candidate, the oily compound created via transesterification in
which free fatty acids and triglycerides react with methyl alcohol.
The reaction has been performed in the presence of CH3ONa, NaOH,
and different metal oxides. The studies have reported suitable flash
and boiling points of the produced biodiesel to use as trans-
portation fuel [3]. Lipase also has been used as a biocatalyst for
biodiesel production in the lower temperatures. The recent studies
have focused on the conversion of microalgae bio-oil to fatty acid
methyl esters in the presence of enzyme. The enzyme immobili-
zation on the superparamagnetic supports with nano-scale struc-
tures is a promising approach for using these expensive catalysts in
the biodiesel production processes [4].
The supercritical fluids have been noticed as solvent and reac-
tion medium for biomass conversion to fuels. Liquid (hydrocarbons,
alcohols, and ethers) and gaseous (H2 and CH4) fuels have been
produced in supercritical water with temperatures higher than
374
C and pressures more top than 24 MPa. Water plays both
solvent and reactant roles in reactions that occur in supercritical
gasification (SCWG) and liquefaction (SCWL) of biomass. Carbon
monoxide and methane steam reforming are two main reactions
for hydrogen production in the SCWG process that supercritical
water has the reactant role [5]. Different catalysts have been used in

https://doi.org/10.1016/j.renene.2021.02.042
0960-1481/© 2021 Elsevier Ltd. All rights reserved.
T. Nematian, M. Fatehi, M. Hosseinpour et al.
SCWG process in which metal oxides are used more than others.
Recently, in a comparative study, several metal oxides (V2O5, WO3,
Co2O3, ZnO, CuO, and Fe2O3) have been used for supercritical con-
version of soda black liquor to H2 rich gas. Results showed
21.67 mol kg1 hydrogen production yield for V2O5 as the best
catalyst [6].
For biodiesel production through transesterification, supercrit-
ical methanol has been used as both reaction medium and reactant.
It has been demonstrated that in temperatures and pressures over
240
C and 7.85 MPa, methanol could convert oil content to FAMEs
with high yields even in the absence of catalyst. It has been sug-
gested that methanol in supercritical condition facilitates nucleo-
philic substitution of methoxy group by increasing in the possibility
of suitable attacks of the nucleophile. The fact decreases reaction
time and increases conversion yield [7]. The conversion of waste
cooking oil is also an interesting process for the production of
biodiesel. The biodiesel production in supercritical methanol using
waste cooking oil has been performed with 91 and 98% yields [8].
This feedstock was also used for biodiesel production using a
simple and robust derivatization-free method. In this method, the
free fatty acids of the waste cooking oil were pretreated and con-
verted to fatty acid methyl esters in a non-catalytic process. The
optimum parameters, methanol to oil ratio, temperature, pressure,
and time reaction were achieved 25, 256
C, 11 MPa, and 16.6 min,
respectively [9]. The sesame cake oil also has been used for bio-
diesel production via transesterification in supercritical conditions.
The conversion of 97% in the temperature range of 380e480
C has
been reported [10].
Many reactive and non-reactive co-solvents have been used in
the supercritical conversion of oily feedstocks to biodiesel. Four
different co-solvents for supercritical methanol (normal hexane,
water, diethyl ether, and chloroform) have been used for FAMEs
production using microalgae bio-oil. The best production of FAMEs
occurred in the medium supercritical methanol/n-hexane with
16.65 mg.g1biomass [11]. The isopropyl alcohol as a reactive co-
solvent has been added to methanol and the mixture used in su-
percritical conditions for biodiesel production from palm oil. This
alcohol in such conditions has a similar role with methanol in the
transesterification reaction. It has been reported that the addition
of isopropyl alcohol to supercritical methanol helped the reaction
to be performed in milder temperatures and pressures [12]. Water
is another reactive material used as a methanol co-solvent in su-
percritical condition for biofuel production. A mixture of super-
critical methanol-near critical water has been used to produce gas
and liquid fuels from sugarcane bagasse. Alcohols, ethers, and H2
were the main products of this process. It also has reported that
water plays a key role in the reaction pathways of this type of
biofuels production [13].
However, the emission of NOx (Nitrogen oxides) because of
nitrogenates content of crude biodiesel is one of the most impor-
tant problems of this biofuel combustion. The NOx content quantity
of biofuel relates to the feedstock composition and the parameters
of the conversion medium. Protein macromolecules in the biomass
structure are responsible for the N-containing compounds in the
final produced biofuel. Different methods have been used for
upgrading biodiesel for the purpose of eliminating NOx emission
[14]. The NOx emission from the rice barn methyl ester blend has
been reduced using an alumina coated diesel engine by changing
the volumetric compression ratio. This method could reduce the
NOx emission from this kind of biodiesel blend up to 9.4% [15]. A
water-in-biodiesel microemulsion has been used to upgrade the
biodiesel produced from cooking oil waste. By using Span 80 sur-
factant, the nitrogenate content of the biodiesel mixture was
reduced so that emulsification could increase FAMEs content by up
to 96.3% [16].
965
Renewable Energy 170 (2021) 964e973
Hydrogen gas production in a mixture of methanol and water at
high temperature and pressure proceeds through different mech-
anisms. Methanol reforming in the presence of hot water is a re-
action which in hydrogen gas is produced. In this reaction,
methanol and water produce hydrogen and carbon dioxide gases
[17]. For biomasses with cellulose content such as agricultural
biomass wastes, the conversion of cellulose to hydrogen/syngas can
be occurred in the higher temperatures through pyrolysis pro-
cesses. Therefore, the conversion of oily-cellulose base biomasses in
the mentioned condition can be a promising method for producing
both liquid and gaseous biofuels, simultaneously [18]. A one-put
production of hydrogen gas and aromatic alcohols from kraft
lignin in the supercritical condition has been conducted using Rh/
La2O3/CeO2eZrO2 catalyst. The aromatic alcohols and hydrogen gas
have been produced up to 57% and 29.47 mmol, respectively [19].
In this study, a supercritical methanol-hot water medium was
used to convert sesame cake as an oily-cellulosic feedstock to liquid
and gaseous fuels. The FAMEs and hydrogen gas production was the
one of the purposes of this research. The process was performed
without catalyst and with different compositions of metal oxides as
catalysts. Gamma alumina (g-Al2O3), CaO/g-Al2O3, and MgO/g-
Al2O3 were prepared and used as heterogeneous catalysts of the
process for investigating and comparison of each catalyst effects on
the products. The other aim of this research was to upgrade the
produced biodiesel via reducing its N-content. The efficiency and
scalability of the method was intended, and it was based on the
alkaline nature of the produced nitrogenates.
2. Experimental
2.1. Materials
The Mg(NO3)2$6H2O and Ca(NO3)2$4H2O salts as the catalysts
precursors were purchased from Merck company. The g-Al2O3, as
catalyst support (Condea Vista Chemical Company) with
212.4 m2 g1 surface area was purchased and treated. Methanol
anhydrous with 99.8% purity was purchased from Sigma-Aldrich.
Silica gel with high purity grade (99%) and 48 m2 g1 surface area
was purchased from Merck company. Deionized water was used as
the water content of the reaction medium. The CO2 gas with the
purity of 99.99% was used for upgrading step.
2.2. Methods
2.2.1. Catalyst preparation
The catalysts were prepared using wet impregnation technique.
First, g-Al2O3 was treated in a laboratory furnace at 400
C to burn
and remove possible organic impurities. The magnesium and cal-
cium salts were dissolved in deionized water with the considered
amounts. For CaO/g-Al2O3 (10 wt% of CaO), and MgO/g-Al2O3 (10 wt
% of MgO) preparation, the prepared solutions were added to g-
Al2O3 to make sludge. The sludges were dried for 2 h at 120
C and
then calcined for 4 h at 400
C. The sesame cake as the feedstock of
the process was obtained from a cold pressing of Iranian sesame
seeds which were purchased from KRALICIN Company, Iran. Table 1
shows the abbreviations for prepared catalysts.
Table 1
The abbreviations for catalysts names.
Catalyst Abbreviation
No catalyst No Cat.
g-Al2O3 g-Al
CaO/g-Al2O3 CaeAl
MgO/g-Al2O3 MgeAl
T. Nematian, M. Fatehi, M. Hosseinpour et al. Renewable Energy 170 (2021) 964e973

2.2.2. Catalyst characterization 2.2.6. Reaction setup

After calcination, the characterization of catalysts was per-
formed using XRD, ICP-OES, BET, and TEM. The CaO and MgO
loaded amounts on g-Al were analyzed using the ICP-OES instru-
ment (Varian VISTA-MPX). The XRD was performed using X’Pert
Philips X-ray diffractometer type: 3040/60, Cu/Ka. The surface area,
average pore sizes and pore volume of catalysts that are effective
parameters in catalytic performance were measured by BELSORP-
mini II, MicrotracBEL Company, Japan. For this purpose, the 50
mTorr vacuum for 4 h was used for degasification of the calcined
catalysts at 200
C, and then parameters were determined. The TEM
(Philips CM20 (100 kV) micrography was used to illustrate particles
present in the bulk of nano-porous support. Samples for TEM were
dispersed in ethanol using ultrasonic waving, and the mixture was
dropped on the TEM grid made of copper coated with a thin layer of
carbon.
2.2.3. Sesame cake oil content measurements
The oil extraction from sesame cake was performed using a
reflux column in the presence of chloroform followed by a rotary
evaporation. The sesame cake (50 g) was mixed with 100 mL
chloroform and transferred to a 250 mL round flask. The flask was
coupled with a reflux column and heated until the mixture started
to boil at around 65
C. The process took 12 h. The contents of the
flask were then centrifuged, and the liquid portion transferred to a
rotary for solvent evaporation. The experiment was repeated three
times, and in average, 2.36 g oil was achieved from 50 g sesame
cake.
2.2.4. Sesame cake CHNSO analysis
The CHNSO analysis (instrument) on sesame cake was per-
formed to find carbon, hydrogen, nitrogen, sulfur, and oxygen
content of the feedstock. Table 2 shows the result of CHNSO
analysis.
A stainless-steel tubular batch reactor with 50.0 mL volume was
used for performing the reaction at 300
C and a pressure range
from 9.0 to 10.0 MPa. The reaction medium was a mixture of 1.5 mL
water and 13.5 mL methanol. The feedstock, catalyst and water-
methanol solution were loaded with 1.00 g, 0.50 g, and 15.0 mL
amounts, respectively. The process was also performed with no
catalyst for a better description of catalysts effects. For this purpose,
all other materials amounts were used as same as the catalytic
processes. The needed temperature and pressure were supplied
with a molten mixture of sodium and potassium carbonate salts
bath with 300
C temperature. The reactor pressure was raised to
10.0 MPa in 2e3 min. After 30 min, to perform an immediate re-
action quenching, the reactor vessel was quickly cooled by
immersing in a cold-water bath. A low-pressure gauge was used for
the measurement of non-condensable gaseous products. The
compositions of gas mixtures were determined with GC-TCD. The
fatty acid methyl esters, hydrocarbons, oxygenates, and aromatics
were extracted from water-methanol mixture to n-hexane via
liquid-liquid extraction. For this purpose, the reactor content was
centrifuged to separate the solid phase. The liquid phase was
transferred to a separatory funnel, and 15 mL of n-hexane was
added to it. The funnel was shaken to mix its content, and left for
24 h to separate n-hexane phase from methanol/water. The upper
phase containing soluble components in n-hexane (including
FAMEs) was injected into the GC-MS to find its compositions. Fig. 1
illustrates a schematic view of the process setup.
2.2.7. N-content reducing
A non-polluting method was used for reducing the nitrogenate
content of the product. The method was based on the fact that all

2.2.5. Product analysis

For liquid product analysis, the GC-MS technique (HP/Agilent
6890) was used. The GC column was HP-5MS made of fused silica
with length, internal diameter, and film thickness of 30 m,
0.25 mm, and 0.25 mm, respectively. It was equipped with an MS
detector (5973N. MSD). Helium (99.999%) was carrier gas, and the
temperatures of injection port and detector were 250
C and
230
C. The temperature program of the column was first heating at
60
C for 1 min, then rising temperature to 250
C with 10
C.min1
rate, and finally, heating at this temperature for 10 min.
The gas products were determined by GC-TCD (HP/Agilent
5890) with Porapak Q packed column made of stainless steel with
length and the internal diameter of 3 m and 2.1 mm, respectively.
Helium (99.999%) was carrier gas, and the temperatures of injection
port and detector were 120
C and 380
C. The temperature pro-
gram of the column was first heating at 40
C for 5 min, then rising
temperature to 70
C with 2
C.min1 rate, and finally, heating at
this temperature for 20 min.

Table 2
Elemental analysis of sesame cake by CHNSO technique.

Element Content (wt. %)

Carbon 50.32
Hydrogen 8.05
Fig. 1. Thermal process setup; (1) Molten salts mixture bath, (2) Tubular reactor, (3)
Nitrogen 7.26
Heating element, (4) Thermocouple, (5) Pressure gauge (scale, up to 40 MPa), (6 and 7)
Sulfur 0.54
Valves (operating pressure scale, up to 30 MPa), (8) Pressure gauge (scale, up to
Oxygen 30.26
0.5 MPa), (9) Valve (operating pressure scale, up to 2.5 MPa), and (10) Septum.

966
T. Nematian, M. Fatehi, M. Hosseinpour et al.
nitrogenate compounds exhibited in the mixture have alkaline
properties. The processes with no catalyst and in the presence of
each catalyst were performed five times. After centrifuge and
liquid-liquid extraction, the products of each five runs were
collected, mixed with 75 mL deionized water, and transferred to a
250 mL two-neck round-bottom flask. The flask was equipped with
a Soxhlet apparatus, and a CO2 gas flow. The content of the flask was
heated to 70
C and stirred moderately for 24 h. The high purity
silica gel powder (2 g) was placed in the bottom of the absorption
tube. Fig. 2 shows a schematic view of the setup and the appearance
of the crude and upgraded product of MgeAl. In this method, the
CO2 is slightly dissolved in H2O, which is distributed continuously
in organic phase, and forms H2CO3. Because of the nitrogenates
presence, mixing organic and aqueous phases makes an alkaline
medium. The alkaline medium helps carbonic acid dissociate to Hþ
and HCO3. The Hþ reacts with R3N (that is in the organic phase) in
a reversible reaction and forms [R3NHþ] [HCO3]. The created
material is salt and soluble in the water, so nitrogenate migrates
from n-hexane to water. On the other hand, the mixture temper-
ature is over n-hexane boiling point, so the evaporation is per-
formed, continuously. The vapor phase may be a mixture of n-
hexane, water, and some dissolved components including [R3NHþ]
[HCO3]. The aqueous phase is the minor part of the vapor because
the temperature is below water boiling point. The vapor is
condensed and fall into the absorption tube and the aqueous phase
is located at the bottom and absorbed by silica gel, slowly. A key
role was considered for silica gel. It reduces the [R3NHþ] [HCO3]
content of the round-bottom flask. As a result, the reversible re-
action in the organic phase shifts to the right and more HNR3þ
species are produced and enter the aqueous phase. The aqueous
phase evaporates, distillates, and is absorbed by silica gel in the
adsorption tube. This process is repeated many times during 24 h.
Finally, the mixture of the flask was transferred to a decanting
funnel to separate two phases. The upper layer (Organic phase) was
injected to GC-MS. The amounts of the components in the upgra-
ded product were compared with crude ones.
2.2.8. Statistical analysis
The Statistical analysis was performed by SPSS Statistics V. 17.01
(SPSS Inc., Chicago, USA). The ANOVA and LSD post-hoc tests were
used for analyzing data. P-values<0.05 were considered significant.
The uncertainties were ±0.2
C for temperature measurements,
Fig. 2. (a) Schematic of the process for reducing nitrogen content, (b) crude product
from MgeAl catalyst of, and (c) upgraded product from MgeAl catalyst.
967
Renewable Energy 170 (2021) 964e973
±0.1 mL for volume measurements, ±0.1 MPa for pressure mea-
surements, and ±0.001 g for mass measurements.
3. Results and discussion
3.1. The characterization of catalysts
The ICP-OES technique was used for the determination of CaO
and MgO amounts that impregnate on g-Al support. The results are
reported in Table 3. As shown in this table, values of impregnated
metals were very close to expected ones.
Fig. 3 shows TEM micrographs of g-Al, CaeAl, and MgeAl that
approved the porous structure of g-Al and good distribution of
particles in the support pores.
The XRD patterns of g-Al, CaeAl, and MgeAl are illustrated in
Fig. 4. Peaks at 2W ¼ 38, 45, 67 are attributed to g-Al2O3. Peaks at
2W ¼ 39 and 30 are related to CaO and MgO, respectively. Table 4
shows the results of surface morphology characterization for g-Al,
CaeAl, and MgeAl. The results showed the reduction of SBET, mean
pore diameter, and pore volume by incorporation of the metal
oxides to g-Al. The support pore blockage by CaO and MgO is a
reason for their lower textural properties compare with g-Al. The
SBET, pore volume, and mean pore diameter of CaeAl catalyst were
founded to be smaller than MgeAl. It can be related to the fact that
calcium atoms occupy the larger volume than magnesium because
of the higher atomic radius.
The CaO is one of the catalysts that has been used repeatedly in
the production of biodiesel. There are recent interesting reports
about the SBET of this transesterification catalyst. Studies have
shown that the surface area of CaO depends on its precursor and
how it is prepared. In a study with double treatment and calcina-
tion of eggshell, the surface area increased up to 12-fold, and the
pore volume increased up to 10.5 times. At best, however, the SBET
value has been reported 23.30 m2 g1 [20]. In another study, CaO
nanoparticles have been used as catalysts for the transesterification
reaction. A very effective method has been used to produce these
nanoparticles. In this method, calcination has been performed at
900
C. The SBET of this catalyst was 659.3303 m2 g1, which is an
excellent value for a metal oxide catalyst [21].
In this study the textural properties of the catalyst are highly
dependent on the properties of the support and the percentage of
the metal oxides. Since g-alumina has a porous structure, the
addition of metal oxides on its surface reduces the SBET, pore vol-
ume, and the mean pore diameter.
3.2. Products analysis
3.2.1. Gaseous products
The gas mixtures compositions consist of H2, CO2, CO, CH4, and
some alkanes and alkenes (light hydrocarbons) were detected us-
ing GC-TCD. Fig. 5 shows H2, CO2, CO, and light hydrocarbons
amounts produced in the presence of g-Al, CaeAl, and MgeAl
catalysts as well as the produced gas in the reaction with No Cat.
Results showed that Ca and Mg oxides had the significant effect on
the total gas production. As shown in the picture, the process had
the highest hydrogen, carbon monoxide, and carbon dioxide pro-
duction with MgeAl. The trends of H2 and CO2 production can be
related to the cogeneration of these two gases in the methanol
steam reforming reaction that is the main reaction in this process
(Re. 1). Carbon monoxide can be produced from biomass feedstock
in this process. Therefore, the increase in carbon monoxide pro-
duction in the presence of these metal oxides is a reason for the
performance of CaO and MgO in the gasification of cellulosic
biomass. The production of methane as the main component of
light hydrocarbons showed no significant increase by using the
T. Nematian, M. Fatehi, M. Hosseinpour et al. Renewable Energy 170 (2021) 964e973

Table 3
The ICP-OES results for the catalysts.

Catalyst Matal Expected values for metal oxide (wt%) ICP result for metal oxide (wt%)

CaeAl Ca 10 9.82
MgeAl Mg 10 9.66

Table 4
The textural properties of g-Al, CaeAl, and MgeAl.

Catalyst SBET (m2.g1) Pore volume (cm3.g1) Mean pore diameter (nm)

g-Al 212.40 0.6653 14.50

MgeAl 143.13 0.3921 11.18
CaeAl 98.77 0.2568 10.40

describe using Re. 2 and Re. 3 that show the conversion of methanol
to CH4, CO2, and H2O.

CH3OH þ H2O / CO2 þ 3H2 Re. 1

4CH3OH / CO2 þ 2H2O þ 3CH4 Re. 2

CH3OH þ H2 / CH4 þ H2O Re. 3

Fig. 3. The TEM micrographs of (A) g-Al, (B) CaeAl, and (C) MgeAl.
catalyst in the process. The type of catalyst also had no significant
difference in methane production. The methane production can
The result reveals that g-Al, MgeAl and, CaeAl have a negligible
effect on light hydrocarbons production in the supercritical
methanol-hot water medium.
Results of statistical analysis showed that for all products (H2,
CO, CO2, and light hydrocarbons), there were significant differences
between all catalytic and non-catalytic processes except in two
cases. There were no significant differences between non-catalytic
process and the process in the presence of g-Al in the case of light
hydrocarbons and carbon monoxide productions. This confirms
that for light hydrocarbons and CO production in such conditions,
using g-Al is unnecessary. However, as shown in Fig. 5, in the case
of H2 and CO2 production, there is a significant difference between
non-catalytic process and the process in the presence of g-Al. These

Fig. 4. The XRD patterns of g-Al, CaeAl, and MgeAl. The characteristic peaks for g-Al2O3 (*), CaO (-), and MgO (C).

968
T. Nematian, M. Fatehi, M. Hosseinpour et al.
Fig. 5. Comparing of the produced gas composition for reaction with no catalyst and with g-Al, CaeAl, and MgeAl catalysts; a: P-value< 0.05 vs. group No. Cat.; b: P-value<0.05 vs.
group g-Al; c: P-value< 0.05 vs. group CaeAl; d: P-value< 0.05 vs. group MgeAl.
results reveal that g-Al has the catalytic effect on reactions 1, 2, and
4, which are main reactions for CO2 and H2 production.
3.2.2. Liquid products
Table 5 shows the products detected by GC-MS in the liquid
product after non-catalytic and catalytic processes. For a better
description of the processes, the products were classified as fatty
acid methyl esters, oxygenates (except methanol), hydrocarbons
(except n-hexane), and nitrogenates. The hexadecanoic and octa-
decanoic acid methyl esters were two FAMEs in the liquid products.
The triglycerides are converted to FAMEs through the trans-
esterification reaction. The cyclic and non-cyclic oxygenates may
produce from carbohydrates such as cellulose, starch, and sugars
[5]. These chemical structures are deformed in high temperatures
and form ethers and ketones and other oxygenates. As plants
immobilize the nitrogen using biomolecules such as proteins, the
precursor of the produced nitrogenates can be these biomolecules.
The hydrocarbons which were detected in the products all are
linear and saturated. Alkanes and alkenes are naturally available in
the sesame structure. Alkanes passed the high temperature and
pressure processes with no reaction, but it seems that alkenes
reacted with the produced H2 and produced saturated hydrocar-
bons (alkanes).
The production of FAMEs, oxygenates, nitrogenates, and
969
Renewable Energy 170 (2021) 964e973
hydrocarbons were compared for each process (Fig. 6). As shown,
FAMEs were the main product of the processes. They were pro-
duced even in the reaction with no catalyst. The process in the
presence of CaeAl shows the best performance for biodiesel
production.
The lower FAMEs production of MgeAl catalyzed reaction can
be related to more alkaline nature of CaO compare with MgO. In the
case of oxygenates, hydrocarbons, and nitrogenates, there is a slight
difference between two nanocatalysts. It may be due to this fact
that the production of these components is related to the harsh
condition of the process. High temperatures extract alkanes and
alkenes from biomass, and subsequently, hydrogenation of alkenes
occurs. Also, in this condition, proteins and carbohydrates are
destructed, and form oxygenates and nitrogenates. As shown in this
figure, no significant differences indicated for hydrocarbons and
nitrogenates production. This result indicates that for decreasing
the nitrogenate content of the product, changing catalysts from CaO
to MgO cannot be helpful.
Supercritical methanol for biodiesel production in the present
CaO and MgO has been reported in the literature. The palm oil has
been converted to FAMEs in sub- and supercritical methanol in the
presence of CaO/KI/g-Al2O3. The preparation method of the catalyst
was precipitation and impregnation. The 95% conversion has been
reported as the highest yield [22]. A no-glycerol FAMEs production
T. Nematian, M. Fatehi, M. Hosseinpour et al. Renewable Energy 170 (2021) 964e973

Table 5
The product components detected for non-catalytic and catalytic processes.

Compound Formula Products (Wt.%)

No. Cat. Y-Al CaeAl MgeAl

Methanol 19.38 14.22 8.03 10.32

n-Hexane 53.94 46.41 30.706 39.67

n-Octane 1.8 2.713 6.06 4.67

n-Heptanol No. Pro. No. Pro. 0.59 0.32

4-Methyl-3-penten-2-one No. Pro. 1.24 1.73 1.62

p-Xylene 2.2 4.13 5.48 5.59

m-Xylene 0.35 0.56 0.78 1.01

4-methoxy-4-methyl-2-pentanone No. Pro. 0.07 0.15 0.11

3-ethyl-2,4,5-trimethyl-1H-Pyrrole 1.24 1.55 2.09 1.98

2-ethyl-3-methylpyrazine 0.85 1 1.08 1.11

1-hydroxy-1-phenylacetone No. Pro. No. Pro. 1.19 0.79

2,2,6,6-Tetramethyl-4-piperidinone 4.73 5.47 6.27 6.16

3-methyl-1,2,4-cyclopentanetrione No. Pro. No. Pro. 0.21 0.19

Tetradecane 0.07 0.12 0.16 0.2

Pentadecane 0.05 0.08 0.12 0.18

Hexadecanoic acid, methyl ester 1.46 2.16 4.24 3.23

Octadecanoic acid, methyl ester 13.91 20.27 31.11 22.83

has been performed from transesterification of rapeseed oil in su-
percritical dimethyl carbonate in the presence of CaO. The pro-
duction yield of 92.6% has been reported [23]. In an interesting
work, CaO/Al2O3 has been used in form of aerogel for biodiesel
production catalyzing. No phase change has been occurred during
calcination at 700
C. The best specific surface area of CaO/Al2O3
aerogel was 44 m2 g1, and the maximum biodiesel yield was 89.9%
[24]. The MgO has also been used as catalyst for biodiesel pro-
duction. The Madhuca indica oil has been converted to FAMEs in
supercritical methanol in the presence of MgO. This metal oxide has
the best performance in competition with others, including Mn3O4,
and has performed up to 100% conversion [25].
3.3. Reduction of nitrogenate content
The liquid biofuel N-content reducing idea was based on the
alkaline nature of the produced nitrogenates. Fig. 7 shows the
970
interactions between two phases that may happened. The com-
parison of nitrogenates in crude and upgraded products, and the
reduction percentages for non-catalytic and catalytic processes
were shown in Fig. 8. Results showed that 65.2, 64.3, 60.2, and 61.9%
of liquid products’ N-content removed after the upgrading for No
Cat., g-Al, CaeAl, and MgeAl, respectively. Also, the percentages of
other components increased because of decreasing nitrogenates in
the mixtures. The interesting result was the significant differences
among N-content reduction percentages of four groups of the
experiment. Since the upgrading processes were performed under
the same conditions, no significant difference was predicted.
However, the results show that the performance of the N-content
reduction process depends on the type of the catalyst. It can be
related to the fact that some metal oxide catalysts such as CaO are
dissolved in supercritical methanol [26]. The metal oxides dissolved
in the organic phase makes the medium alkaline, when aqueous
and organic phases are being mixed. The alkaline medium
T. Nematian, M. Fatehi, M. Hosseinpour et al.
Fig. 6. The FAMEs, oxygenates, nitrogenates, and hydrocarbons production comparison; a: P-value< 0.05 vs. group No. Cat.; b: P-value<0.05 vs. group g-Al; c: P-value< 0.05 vs.
group CaeAl; d: P-value< 0.05 vs. group MgeAl.
Fig. 7. Possible reaction mechanism for nitrogen removal from the product; A nitro-
genate sample (2,2,6,6-Tetramethyl-4-piperidinone).
consumes some Hþ created from CO2 dissolving in the aqueous
phase. Therefore, compare with No Cat. and g-Al, less Hþ species
succeed to react with N-contain molecules in the liquid products
from CaeAl and MgeAl. So, it may be a reason for the lower per-
formance of the upgrading process for these nanocatalytic pro-
duced biofuels. On the other hand, the N-content reduction
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Renewable Energy 170 (2021) 964e973
percentage for CaeAl product was less than MgeAl. The CaO makes
medium more alkaline compare with MgO, so the medium in the
presence of MgO contains more Hþ species, and subsequently, more
NR3 molecules are converted to HNRþ 3.
4. Conclusion
Hydrogen and biodiesel with low-content nitrogen as fuels were
produced from sesame cake where supercritical methanol and
water co-solvent was nominated as the reaction medium. The re-
action was performed in the presence of g-Al, CaeAl, and MgeAl
catalysts and the results were compared with the same condition,
but in the absence of catalysts. The main components in the gas
product include H2, CO, CO2, and CH4, where MgeAl catalyst
showed the best performance in the production of hydrogen as a
green fuel. In the liquid, however, the main products were fatty acid
methyl esters with the highest FAMEs production obtained by
CaeAl. Besides, some other compounds were detected in the liquid
products which classify as oxygenates, hydrocarbons, and nitro-
genates. The presence of oxygenates including ketones, ethers, and
alcohols is advantageous since the higher oxygen content in liquid
fuels encompass the higher quality during combustion which
T. Nematian, M. Fatehi, M. Hosseinpour et al.
Fig. 8. The comparison of N-content weight percentages before and after upgrading
(A), [a: P-value< 0.05 vs. group No. Cat.; b: P-value<0.05 vs. group g-Al; c: P-value<
0.05 vs. group CaeAl; d: P-value< 0.05 vs. group MgeAl]. The reduction percentage of
N-content after upgrading (B).
deduce to the lower release of air pollutant to the atmosphere.
In order to decrease the N-content of the biodiesel, which
crucially unfavorable, CO2 gas flow was used to increase medium
acidity and form [R3NHþ][HCO 3 ] with the considerable solubility in
the aqueous phase followed by absorbing water from the distillant
in the absorption tube by silica gel. Beside the efficiency of this
approach, increased by introducing catalyst which attributed to the
trace dissolving of the CaO and MgO in the biodiesel mixtures, and
subsequent increasing in the medium pH. It is an alkaline medium
that consumes Hþ released by CO2 dissolving.
CRediT authorship contribution statement
Tahereh Nematian: Conceptualization, Data curation, Writing -
original draft, Writing - review & editing. Milad Fatehi: Data
curation, Writing - original draft. Morteza Hosseinpour: Concep-
tualization, Methodology, Writing - review & editing. Mohammad
Barati: Supervision, Conceptualization, Methodology, Software,
Writing - review & editing.
Declaration of competing interest
The authors declare that they have no known competing
972
Renewable Energy 170 (2021) 964e973
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Acknowledgment
The authors are thankful to the Iran National Science Foundation
(INSF) and University of Kashan for their financial supports.
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