Fuel 265 (2020) 117019

Contents lists available at ScienceDirect

Fuel
journal homepage: www.elsevier.com/locate/fuel

Full Length Article

Application of Cu impregnated TiO2 as a heterogeneous nanocatalyst for the T

production of biodiesel from palm oil
⁎
Arghyadeep De, Siddhartha Sankar Boxi
Department of Chemical Engineering, Haldia Institute of Technology, Haldia 721657, West Bengal, India

A R T I C LE I N FO A B S T R A C T

Keywords: Biodiesel is gaining more research interest in recent years as an alternative fuel which is sustainable and en-
Biodiesel vironment friendly over the conventional fossil fuels. Here in heterogeneous based nanocatalysts have received
TiO2 considerable attention for the biodiesel production to simplify the process and to reduce the purification cost. In
Copper this study pure TiO2 and Cu impregnated TiO2 were used as the heterogeneous catalyst for the production of
Palm oil
biodiesel from palm oil. The particle size of the TiO2 was found to be 80 – 150 nm. The transesterification
Transesterification
reaction was carried out under different parametric conditions such as catalyst dose, % of Cu impregnation, time,
Yield
temperature, methanol to oil ratio. Maximum yield of biodiesel was obtained at 90.93% under optimal condi-
tions. The performance of the catalyst showed maximum at 45 °C temperature with methanol to oil ratio of 20:1.
The reaction was completed in 45 min. Density, viscosity, flash point, fire point, aniline point, diesel index, and
cetane number of the obtained biodiesel were tested for the quality determination. Composition of the biodiesel
was determined by gas chromatography-mass spectrometry (GC-MS) analysis.

1. Introduction in the biodiesel production in improving economical feasibility of the

The demand of sustainable and renewable energy resources has
become most significant in present era because of the environmental
issues in the fossil based fuels. Biodiesel is reported to be one of the
most renewable fuel source and possesses nontoxic and biodegradable
properties with less emission of greenhouse gases like NOx, SOx, CO,
CO2, etc [1,2]. Biodiesel is nothing but the lower alkyl ester of long
chain fatty acids produced due to the transesterification reaction.
Transesterification is the reaction of oil or fat with alcohol to form alkyl
esters and glycerol [3,4]. However, biodiesel is not getting so much
popularity like traditional petroleum diesel because of its high pro-
duction cost and non availability of the raw materials [5]. Conventional
transesterification reaction was carried out based on homogeneous
based catalyst such as NaOH or KOH. In this method the production
yield was high but the separation and purification of the product was
time consuming and costly [3,6]. To overcome this problem research
has been focused on the heterogeneous based catalyst in recent years.
The heterogeneous catalysts are insoluble and recyclable. It eliminates
the separation and purification steps in the biodiesel production, which
results the reduction in synthesis cost of biodiesel and environmental
pollution. Moreover the biodiesel produced by this method is highly
pure in quality [7,8]. Selection of feed stock is an important parameter
product. Feed stocks such as soybean oil [9,10], waste cooking oil [11],
jatropha oil [12,13], canola oil [14], Mustard oil [15], sunflower oil
[16], palm oil [17], rubber seed oil [18], Chinese tallow seed oil [19],
etc. were used for the production of biodiesel. Till date different het-
erogeneous catalysts have been developed in the transesterification
process, such as silica [20], Al2O3 supported Cao & MgO [21], NKC-9
cation-exchange resin [22], calcium manganese oxide [23], Co-Zn/
HZSM-5 [24], KF/ZnO [10], etc. Some other solid catalysts such as egg
shell [25], calcium containing silicate mixed oxide [26], snail shell
[27], waste capiz (amusium cristatum) shell [28], etc. were also been
used as the heterogeneous catalyst. Nanomaterials, which exhibit ex-
traordinary properties such as insolubility, recyclability, stability, were
also been utilized for the production of biodiesel. Moreover, because of
lower particle size and higher surface area, nanomaterials were re-
ported to be more active in transesterification reaction. Some nanoca-
talyst such as lithium ion impregnated calcium oxide [29], KF/CaO-
Fe3O4 [30], bimetallic gold-silver core-shell nanoparticles [31], etc.
were applied as the heterogeneous catalyst. Apart from these catalysts
TiO2 is reported to have some additional properties compared to other
conventional nanomaterials such as durability, antifungal, environ-
mental friendly, and cheap [32]. But, very few literatures are available
on the TiO2 based heterogeneous catalyst for biodiesel production.

⁎
Corresponding author.
E-mail address: ssboxich@gmail.com (S.S. Boxi).

https://doi.org/10.1016/j.fuel.2020.117019
Received 14 August 2019; Received in revised form 30 October 2019; Accepted 2 January 2020
0016-2361/ © 2020 Elsevier Ltd. All rights reserved.
A. De and S.S. Boxi
TiO2-ZnO mixed oxide nanocatalyst was investigated for palm oil
transesterification process for biodiesel production [33]. Recently Li
impregnated TiO2 was used as a heterogeneous catalyst for the pro-
duction of biodiesel and it was reported the product yield of 98% [2].
However, a very few works have been done on metal impregnated TiO2
as a heterogeneous catalyst for the production of biodiesel.
This experimental work involves the use of TiO2 as heterogeneous
catalyst along with impregnation of copper for the production of bio-
diesel. The palm oil was chosen as the feedstock. Experiments were
conducted under various reaction conditions, such as catalyst dose,
time, temperature, methanol to oil ratio in order to optimize the bio-
diesel yield.
2. Experimental
2.1. Materials
Titanium dioxide (TiO2) was obtained from Loba Chemie, Mumbai,
India. Cupric sulphate (CuSO4·5H2O) was taken from S. D. Fine-Chem
Limited, Mumbai, India. Palm oil was purchased from the market and
was used without further purification. Methanol (CH3OH) was supplied
by Finar Chemicals Limited, Ahmedabad, India. Aniline (C6H5NH2) was
bought from Ranbaxy Laboratories Limited. All the chemicals were
used as it was received without any further purification.
2.2. Preparation of Cu impregnated TiO2
The Cu impregnated TiO2 nanoparticles were synthesized by wet
impregnation method [34]. Initially TiO2 nanoparticles were suspended
in distilled water. Aqueous solution of cupric sulphate (according to the
desired concentration) was then added to the slurry. Then it was stirred
for 30 min. The resultant slurry was kept in an oven at 60 °C for
overnight. The dried powder was calcined at 450 °C for 2 hr. A series of
Cu impregnated TiO2 nanoparticles were synthesized with varying
copper concentrations of 0.5–20% of TiO2.
2.3. Characterization of nanoparticles
Size and shape of the TiO2 nanoparticles were characterized by field
emission scanning electron microscope (FE-SEM) (JEOL JSM 6510LV).
The elemental compositions of the nanoparticles were analyzed by
energy-dispersive X-ray spectroscopy (EDX) attached to the FE-SEM.
2.4. Transesterification reaction
Transesterification reaction was performed in a 500 ml flat bottom
flask with three necks. The reactor was equipped with a magnetic
stirrer, water cooled condenser, a septum for sample collection, and a
thermometer. Initially the catalyst (0.5–10% for TiO2) was placed to the
reactor followed by the addition of methanol (5:1, 10:1, 16.5:1, 20:1,
25:1, and 30:1 ratio), then the feed stock (palm oil) was added to the
reaction media. Throughout the reaction the media was maintained
Fig. 1. (a) FE-SEM image and (b) EDX pattern of the TiO2 nanoparticles.
2
Fuel 265 (2020) 117019
under continuous stirring condition (800 rpm). The reaction tempera-
ture was maintained at 32, 45, 58, 65, 70, and 73 °C. The reaction was
conducted for different time such as 10, 20, 30, 45, 60, 120, and
240 min. After the completion of transesterification reaction the bio-
diesel was separated using separating funnel. Yield of the produced
biodiesel from the palm oil was calculated by the Eq. (1) given by Leung
et al. [35].
Weight of biodiesel produced
Yield of biodiesel(%) = × 100
Weight of palmoil (1)
2.5. Characterization of biodiesel
The composition of the produced biodiesel was analyzed by gas
chromatography-mass spectrometry (GC-MS) (Shimadzu, QP2010
Plus). The viscosity of the obtained biodiesel was tested by redwood
viscometer (Usha Instruments and Chemicals). The specific gravity or
relative density of the biodiesel was measured by density hydrometer
(Leimco). The density of the biodiesel is further presented in °API. The
°API was calculated based on the Eq. (2) [36]. The Flash point and fire
point of the diesel were determined by a Pensky-Martens apparatus
closed-cup tester (Test master). Aniline point of the biodiesel was
measured as the temperature at which equal volume of anhydrous
aniline and the biodiesel mixed together. Diesel index and cetane
number were calculated based on aniline point data by using the Eqs.
(3) and (4), respectively [37].
°API 141.5
= − 131.5
Sp.Gr60/ °60F (2)
Diesel index = (Aniline point in °F×API)/100 (3)
Cetane number = 0.72 × Diesel index + 10 (4)
3. Results and discussion
3.1. Characterization of nanoparticles by FE-SEM and EDX
The field emission scanning electron microscopy (FE-SEM) image of
the TiO2 nanoparticles is shown in Fig. 1(a). The image indicates that
TiO2 nanoparticles are mostly spherical in shape. The size of the par-
ticle are lies in the range of about 80–150 nm. The energy-dispersive X-
ray spectroscopy (EDX) pattern of the TiO2 is shown in Fig. 1(b). It
clearly indicates the presence of titanium and oxygen atoms.
3.2. Optimization of TiO2 catalyst
The transesterification reactions of palm oil were performed in the
presence of TiO2 catalyst by varying its concentration from 0.5 to 10%
in order to find out the optimum concentration of TiO2. Fig. 2 shows the
% yield of biodiesel plotted against different concentration of TiO2. It
has been seen that with increasing the TiO2 concentration the yield of
biodiesel increases up to 3%. After 3% TiO2 concentration there is
A. De and S.S. Boxi Fuel 265 (2020) 117019

100 100

90
% Yield 90
80

70
80
% Yield

% Yield
60

50 70 % Yield

40
60
30

20
0 1 2 3 4 5 6 7 8 9 10 11 50
0 50 100 150 200 250
% TiO2
Time (min)
Fig. 2. Influence of Quantity of TiO2 on biodiesel yield. Fig. 4. Influence of time on biodiesel yield.

decrease in yield of the biodiesel. The decrease in yield at higher con-
centration of TiO2 might be because of increase in viscosity of the re-
action mixture [38]. Similar kind of the behavior was also found in the
study of synthesis of biodiesel from waste frying oil using a hetero-
geneous catalyst derived from snail shell by Birla et al. [27]. This result
suggests that the optimum concentration of TiO2 for this transester-
ification reaction was 3%. The maximum yield was obtained as 84.5%.
3.3. Optimization of Cu content with TiO2
The transesterification reaction was also conducted in the presence
of Cu impregnated TiO2. The catalyst dose was maintained at 3% and
the Cu concentration was varied from 0.5 to 20% of catalyst (TiO2)
dose. The results are shown in Fig. 3. It shows that there is a significant
effect of Cu impregnation with TiO2 on the yield of biodiesel produc-
tion. The maximum yield was obtained at 2% Cu impregnation, which
was 89.09%. So, there is 4.59% increase in the yield of the product after
Cu impregnation with TiO2. Further increase in concentration of Cu
leads to decrease in yield of the product. This result indicates that the
optimum level of the Cu impregnation was 2%. At higher concentration
of Cu there is decrease in yield of the biodiesel production. This might
be because of destroying the lattice structure of the TiO2 at higher Cu
concentration due to the serious lattice mismatching and the loss of
stoichiometry. The lattice mismatching further leads to quantum tun-
nelling and structural instability in the material [39]. Because of this
change in the material structure the catalytic properties of the material
also hampered, which directly effect on the yield of the biodiesel pro-
duction.
3.4. Optimization of time
Time is one important variable for transesterification reaction as it
is an equilibrium reaction. The transesterification reaction was con-
ducted for different time to optimize the time for completion of the
reaction. The reaction was conducted for 10, 20, 30, 45, 60, 120, and
240 min. The time vs. yield of the product is plotted in Fig. 4. From the
graph it can be seen that with increasing time there is increase in the
yield of the biodiesel production up to 45 min, and after that there is no
further increase in the yield with further increase in time. The results
indicate that the reaction was completed by about 45 min.
3.5. Optimization of temperature
The transesterification reaction was also conducted at different
temperatures such as 32, 45, 58, 65, 70, and 73 °C to evaluate the effect
of temperature on the reaction. The results are shown in Fig. 5. The
yield of biodiesel increases gradually with increasing the temperature
up to 45 °C. Further increase in temperature leads to the decrease in the
yield of biodiesel. The reduction in yield at higher temperature is
mainly because of the evaporation of methanol, which results in the
methanol deficiencies in the reaction media.
3.6. Optimization of methanol to oil ratio
Methanol to oil ratio is an important parameter in the transester-
ification reaction to get the maximum yield of biodiesel. Since trans-
esterification of triglyceride is a reversible reaction, the excess

100 100
% Yield % Yield
90
90
80

80 70
% Yield

% Yield

60
70
50

40
60
30
50 20
0 2 4 6 8 10 12 14 16 18 20 22 25 30 35 40 45 50 55 60 65 70 75 80 85
% Cu with TiO2 Temperature (°C)
Fig. 3. Influence of Cu impregnation with TiO2 on biodiesel yield. Fig. 5. Influence of temperature on biodiesel yield.

3
A. De and S.S. Boxi Fuel 265 (2020) 117019

100
90
80
70
60
% Yield

50
40
% Yield
30
20
10
0 (d) diesel (using Cu-TiO2).
5:1 10:1 16.5:1 20:1 25:1 30:1
Methanol to Oil Ratio
Fig. 6. Influence of methanol to oil ratio on biodiesel yield.
methanol is expected to shift the equilibrium in forward direction to get
the maximum yield [29]. To determine the optimum methanol to oil
ratio, the reaction was conducted at different ratios, such as 5:1, 10:1,
16.5:1, 20:1, 25:1, and 30:1. Fig. 6 presents the % yield at different
methanol to oil ratio. At low methanol to oil ratio (5:1) the yield was
about 14.4%, then with increasing the ratio the yield was also in-
creased. The maximum yield was obtained 90.93% at 20:1 methanol to
oil ratio.
From the overall parameters studies it is obvious that the optimum
values of the parameters are: Catalyst (TiO2) loading 3%, Cu impreg-
nation 2%, time 45 min, temperature 45 °C, and methanol to oil ratio
20:1. At these optimum conditions the maximum yield was obtained
90.93%.
3.7. Properties of biodiesel
The fuel properties such as density and viscosity of the biodiesel
were determined. To compare the properties (density, viscosity) of the
biodiesel obtained from heterogeneous catalyst, the transesterification
reaction was also conducted in the presence of homogeneous catalyst
(NaOH). The density and kinematic viscosity of the produced biodiesel
for different catalyst (NaOH, TiO2, Cu-TiO2) are listed in Table 1. The
density of the biodiesel is lowest (775 kg/m3) for Cu-TiO2 catalyst and
maximum (847 kg/m3) for NaOH. The density of the biodiesel is further
presented in °API. The results are presented in Table 1. Kinematic
viscosity of the biodiesel was 0.0114, 0.0124, and 0.0211 m2/s for Cu-
TiO2, TiO2, and NaOH catalyst. The Changes of kinematic viscosity of
the biodiesel with temperature for three different catalysts are pre-
sented in Figs. S1, S2, and S3, Supporting Information. The kinematic
viscosities gradually reduced with increasing the temperature. In pre-
sence of Cu impregnation to TiO2 it was seen that the kinematic visc-
osity of the produced biodiesel reduced compared to the biodiesel ob-
tained by pure TiO2 catalyst. It is because of the performance of the
individual catalyst. When Cu is impregnated to TiO2 it penetrates
through the surface and combined with TiO2, and subsequently it helps
to increase the surface area of the catalyst [40]. The higher surface area
enhances the conversion of palm oil to bio-diesel as well as improves
the quality of biodiesel. In addition the presence of Cu with TiO2
Fig. 7. Image of (a) palm oil, (b) diesel (using NaOH), (c) diesel (using TiO2),
influences on the band gap energy of base material (TiO2) [41], which
might have also impacted on activity of the TiO2 catalyst. Some other
properties of the produced biodiesel such as flash point, fire point, and
aniline point were also tested. The details results are presented in
Table 1. The physical appearance of the biodiesel obtained by three
different catalysts (NaOH, TiO2, Cu-TiO2) are shown in Fig. 7.
The composition of biodiesel was determined by gas chromato-
graphy-mass spectrometry (GC-MS) analysis. The chromatogram of the
biodiesel is shown in Fig. 8. The detail summaries of GC-MS analysis are
presented in Table 2. The prominent peaks correspond to hexadecanoic
acid, methyl ester (peak 1) with the retention time of 24.349 and the
composition of 35.19%, n-hexadecanoic acid (peak 2) with the reten-
tion time of 24.715 and the composition of 2.5%, 9,12-octadecadienoic
acid, methyl ester (peak 3) with the retention time of 25.924 and the
composition of 7.76%, 9-octadecenoic acid, methyl ester (peak 4) with
the retention time of 25.98 and the composition of 28.47%, 9-octade-
cenoic acid, (E)- (peak 5) with the retention time of 26.291 and the
composition of 3.22%, hexadecanoic acid, 2-hydroxy-1-(hydro-
xymethyl)ethyl ester (peak 6) with the retention time of 28.89 and the
composition of 6%, 9-Octadecenoic acid (Z)-, 2,3-dihydroxypropyl ester
(peak 7) with the retention time of 30.1 and the composition of 16.86%.
Quite similar compounds were also found in the GC-MS studies of
biodiesel obtained from industrial liquid waste of crude palm oil pro-
cessing as reported by Maulidiyah et al. [42].
4. Conclusions
Production of biodiesel through transesterification reaction was
investigated based on heterogeneous nanocatalyst. Palm oil was taken
as feed stock for the reaction and TiO2 and Cu-TiO2 as the hetero-
geneous catalyst. The reaction was carried out in different parametric
conditions. The optimum TiO2 concentration was 3% and Cu con-
centration was 2% to get maximum yield of the product. Time taken to
complete the overall reaction was found to be 45 min. Highest yield was
obtained at temperature 45 °C with methanol to oil ratio of 20:1. The
maximum yield of biodiesel was seen to be 90.93%. The physico-
chemical properties of the obtained biodiesel were also studied and
were found to be satisfactory for a good quality biodiesel. From the
overall results it can be pointed out that the Cu impregnated TiO2 can
be applied as the heterogeneous nanocatalyst for production of bio-
diesel from cheaper feed stocks like palm oil.

Table 1
. Density, kinematic viscosity, flash point, fire point, aniline point, diesel index, and cetane number of the biodiesel for different catalyst.
Catalyst Density, kg/m3 °API Kinematic Viscosity, m2/s Flash point (°C) Fire point (°C) Aniline point (°C) Diesel index Cetane number

NaOH 847 35.56 0.0211 60 68 34 33.14 33.86

TiO2 817 41.69 0.0124 69 76 32 37.35 36.89
Cu-TiO2 775 51.08 0.0114 67 75 35 48.53 44.94

4
A. De and S.S. Boxi Fuel 265 (2020) 117019

Fig. 8. GC-MS Chromatogram of the biodiesel obtained from palm oil.

Table 2 catalysts. Bioresour Technol 2011;102:2151–61.

. Composition of biodiesel according to the results of GC-MS analysis. [9] Kouzu M, Kasuno T, Tajika M, Sugimoto Y, Yamanaka S, Hidaka J. Calcium oxide as
a solid base catalyst for transesterification of soybean oil and its application to
Peak R.Time Area Area% Name biodiesel production. Fuel 2008;87:2798–806.
[10] Xie W, Huang X. Synthesis of biodiesel from soybean oil using heterogeneous KF/
1 24.349 1,885,260 35.19 Hexadecanoic acid, methyl ester ZnO catalyst. Catal Lett 2006;107:53–9.
2 24.715 133,899 2.50 n-Hexadecanoic acid [11] Jacobson K, Gopinath R, Meher LC, Dalai AK. Solid acid catalyzed biodiesel pro-
3 25.924 415,597 7.76 9, 12-Octadecadienoic acid, methyl ester duction from waste cooking oil. Appl Catal B: Environ 2008;85:86–91.
4 25.980 1,525,358 28.47 9-Octadecenoic acid, methyl ester [12] Deng X, Fang Z, Liu Y-H, Yu C-L. Production of biodiesel from jatropha oil catalyzed
5 26.291 172,271 3.22 9-Octadecenoic acid, (E)- by nanosized solid basic catalyst. Energy 2011;36:777–84.
[13] Anr R, Saleh AA, Islam S, Hamdan S, Maleque A. Biodiesel production from crude
6 28.890 321,330 6.00 Hexadecanoic acid, 2-hydroxy-1-
jatropha oil using a highly active heterogeneous nano–catalyst by optimizing
(hydroxymethyl)ethyl ester
transesterification reaction parameters. Energ Fuel 2016;30:334–43.
7 30.100 903,476 16.86 9-Octadecenoic acid (Z)-, 2,3- [14] D’Cruz A, Kulkarni MG, Meher LC, Dalai AK. Synthesis of biodiesel from canola oil
dihydroxypropyl ester using heterogeneous base catalyst. J Am Oil Chem Soc 2007;84:937–43.
[15] Boro J, Thakur AJ, Deka D. Solid oxide derived from waste shells of turbonilla
striatula as a renewable catalyst for biodiesel production. Fuel Process Technol
Declaration of Competing Interest 2011;92:2061–7.
[16] Borges ME, Díaz L, Alvarez-Galván MC, Brito A. High performance heterogeneous
catalyst for biodiesel production from vegetal and waste oil at low temperature.
The authors declare that they have no known competing financial Appl Catal B: Environ 2011;102:310–5.
interests or personal relationships that could have appeared to influ- [17] Baroutian S, Aroua MK, Raman AAA, Sulaiman NMN. A packed bed membrane
reactor for production of biodiesel using activated carbon supported catalyst.
ence the work reported in this paper. Bioresour Technol 2011;102:1095–102.
[18] Yang R, Su M, Zhang J, Jin F, Zha C, Li M, et al. Biodiesel production from rubber
Acknowledgments seed oil using poly (sodium acrylate) supporting NaOH as a water-resistant catalyst.
Bioresour Technol 2011;102:2665–71.
[19] Wen L, Wang Y, Lu D, Hu S, Han H. Preparation of KF/CaO nanocatalyst and its
Authors are grateful to Thapar Institute of Engineering and application in biodiesel production from Chinese tallow seed oil. Fuel
Technology, Punjab, India, for providing their FE-SEM facility. Authors 2010;89:2267–71.
[20] Kazemian H, Turowec B, Siddiquee MN, Rohani S. Biodiesel production using ce-
also acknowledge the West Bengal Waste Management Limited (A di-
sium modified mesoporous ordered silica as heterogeneous base catalyst. Fuel
vision of RAMKY Enviro Engineers Limited), Haldia, India, for giving 2013;103:719–24.
the opportunity to access their GC-MS facility. [21] Umdu ES, Tuncer M, Seker E. Transesterification of nannochloropsis oculata mi-
croalga’s lipid to biodiesel on Al2O3 supported CaO and MgO catalysts. Bioresour
Technol 2009;100:2828–31.
Appendix A. Supplementary data [22] Feng Y, Zhang A, Li J, He B. A continuous process for biodiesel production in a fixed
bed reactor packed with cation-exchange resin as heterogeneous catalyst. Bioresour
Supplementary data to this article can be found online at https:// Technol 2011;102:3607–9.
[23] Dias JM, Alvim-Ferraz MCM, Almeida MF, Díaz JDM, Polo MS, Utrilla JR. Biodiesel
doi.org/10.1016/j.fuel.2020.117019. production using calcium manganese oxide as catalyst and different raw materials.
Energy Convers Manag 2013;65:647–53.
References [24] Cheng S, Wei L, Julson J, Muthukumarappan K, Kharel PR. Upgrading pyrolysis bio-
oil to biofuel over bifunctional Co-Zn/HZSM-5 catalyst in supercritical methanol.
Energy Convers Manag 2017;147:19–28.
[1] Saba T, Estephane J, Khoury BE, Khoury ME, Khazma M, Zakhem HE, et al. [25] Wei Z, Xu C, Li B. Application of waste eggshell as low-cost solid catalyst for bio-
Biodiesel production from refined sunflower vegetable oil over KOH/ZSM5 cata- diesel production. Bioresour Technol 2009;100:2883–5.
lysts. Renew Energy 2016;90:301–6. [26] Hsin T-M, Chen S, Guo E, Tsai C-H, Pruski M, Lin VSY. Calcium containing silicate
[2] Alsharifi M, Znad H, Hena SF, Ang M. Biodiesel production from canola oil using mixed oxide-based heterogeneous catalysts for biodiesel production. Top Catal
novel Li/TiO2 as a heterogeneous catalyst prepared via impregnation method. 2010;53:746–54.
Renew Energy 2017;114:1077–89. [27] Birla A, Singh B, Upadhyay SN, Sharma YC. Kinetics studies of synthesis of biodiesel
[3] Ma F, Hanna MA. Biodiesel production: a review. Bioresour Technol 1999;70:1–15. from waste frying oil using a heterogeneous catalyst derived from snail shell.
[4] Chouhan APS, Sarma AK. Modern heterogeneous catalysts for biodiesel production: Bioresour Technol 2012;106:95–100.
a comprehensive review. Renew Sust Energ Rev 2011;15:4378–99. [28] Suryaputra W, Winata I, Indraswati N, Ismadji S. Waste capiz (Amusium cristatum)
[5] Kulkarni MG, Dalai AK. Waste cooking oilan economical source for biodiesel: a shell as a new heterogeneous catalyst for biodiesel production. Renew Energy
review. Ind Eng Chem Res 2006;45:2901–13. 2013;50:795–9.
[6] Demirbas A. Progress and recent trends in biodiesel fuels. Energ Convers Manage [29] Kaur M, Ali A. Lithium ion impregnated calcium oxide as nano catalyst for the
2009;50:14–34. biodiesel production from karanja and jatropha oils. Renew Energy
[7] Bet-Moushoul E, Farhadi K, Mansourpanah Y, Nikbakht AM, Molaei R, Forough M. 2011;36:2866–71.
Application of CaO-based/Au nanoparticles as heterogeneous nanocatalysts in [30] Hu S, Guan Y, Wang Y, Han H. Nano-magnetic catalyst KF/CaO–Fe3O4 for biodiesel
biodiesel production. Fuel 2016;164:119–27. production. Appl Energ 2011;88:2685–90.
[8] Semwal S, Arora AK, Badoni RP, Tuli DK. Biodiesel production using heterogeneous [31] Banerjee M, Dey B, Talukdar J, Kalita MC. Production of biodiesel from sunflower

5
A. De and S.S. Boxi Fuel 265 (2020) 117019

oil using highly catalytic bimetallic gold-silver core-shell nanoparticle. Energy
2014;69:695–9.
[32] Fujishima A, Rao TN, Tryk DA. Titanium dioxide photocatalysis. J Photoch Phobio
C 2000;1:1–21.
[33] Madhuvilakku R, Piraman S. Biodiesel synthesis by TiO2–ZnO mixed oxide nano-
catalyst catalyzed palm oil transesterification process. Bioresour Technol
2013;150:55–9.
[34] Sun J, Niu W, Taguchi A, Abe T, Yoneyama Y, Tsubaki N. Combining wet im-
pregnation and dry sputtering to prepare highly-active CoPd/H-ZSM5 ternary cat-
alysts applied for tandem catalytic synthesis of isoparaffins. Catal Sci Technol
2014;4:1260–7.
[35] Leung DYC, Guo Y. Transesterification of neat and used frying oil: optimization for
biodiesel production. Fuel Process Technol 2006;87:883–90.
[36] Owolabi RU, Osiyemi NA, Amosa MK, Ojewumi ME. Biodiesel from household/
restaurant waste cooking oil (WCO). J Chem Eng Process Technol 2011;2:4.
1000112.
[37] Haldar SK, Nag A. Utilization of three non-edible vegetable oils for the production
of biodiesel catalysed by enzyme. Open Chem Eng J 2008;2:79–83.
[38] Zhang L, Sheng B, Xin Z, Liu Q, Sun S. Kinetics of transesterification of palm oil and
dimethyl carbonate for biodiesel production at the catalysis of heterogeneous base
catalyst. Bioresour Technol 2010;101:8144–50.
[39] Boxi SS, Paria S. Effect of silver doping on TiO2, CdS, and ZnS nanoparticles for the
photocatalytic degradation of metronidazole under visible light. RSC Adv
2014;4:37752–60.
[40] Yu X, Wena Z, Li H, Tu S, Yan J. Transesterification of Pistacia chinensis oil for
biodiesel catalyzed by CaO-CeO2 mixed oxides. Fuel 2011;90:1868–74.
[41] Tayade RJ, Kulkarni RG, Jasra RV. Transition metal ion impregnated mesoporous
TiO2 for photocatalytic degradation of organic contaminants in water. Ind Eng
Chem Res 2006;45:5231–8.
[42] Maulidiyah, Nurdin M, Fatma F, Natsir M, Wibowo D. Characterization of methyl
ester compound of biodiesel from industrial liquid waste of crude palm oil pro-
cessing. Anal Chem Res 2017;12:1–9.