Journal of Molecular Liquids 279 (2019) 224–231

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Journal of Molecular Liquids

journal homepage: www.elsevier.com/locate/molliq

Diatomite supported by CaO/MgO nanocomposite as heterogeneous

catalyst for biodiesel production from waste cooking oil
Abdelrahman M. Rabie a,⁎, Mohamed Shaban b, Mostafa R. Abukhadra b,d, Rania Hosny b,c,
Sayed A. Ahmed e, Nabel A. Negm a,⁎
a
Petrochemical Department, Egyptian Petroleum Research Institute (EPRI), Cairo, 11727, Egypt
b
Nanophotonics and Applications Lab, Physics Department, Faculty of Science, Beni-Suef University, Beni-Suef 62514, Egypt
c
Chemistry Department, Faculty of Science, Beni-Suef University, Beni-Suef, Egypt
d
Geology Department, Faculty of Science, Beni-Suef University, Beni-Suef, Egypt
e
Chemistry Department (Organic Chemistry Division), Faculty of Science, Beni-Suef University, Beni-Suef, Egypt

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

Article history: Production of renewable, biodegradable, and non-toxic biodiesel by recycling waste cooking oil offers a profitable
Received 10 November 2018 way to reduce the raw materials of waste oil. Low-cost, efficient, reusable, and ecofriendly heterogeneous catalyst
Received in revised form 17 January 2019 is therefore obligatory for the massive and industrial production of biodiesel from used cooking oil. Here, a novel
Accepted 19 January 2019
basic heterogeneous catalyst was prepared from purified domestic diatomite supported by CaO/MgO composite.
Available online 23 January 2019
Different characterization techniques confirmed the loading of diatomite as catalyst support by CaO and MgO.
Keywords:
The catalyst casting by the porous structure of diatoms skeletons causing clear enhancing of the total porosity
Diatomite and surface area of the catalyst. The efficiency of diatomite@CaO/MgO catalyst for converting the waste cooking
Magnesium oxide oil into biodiesel was studied for different times, reaction temperatures, oil/methanol ratios, catalyst dosages, and
Calcium oxide reusability for several cycles of oil conversion. The maximum obtained biodiesel yield reaches 96.47% after
Nanocomposite 120 min at 90 °C using 6 wt% catalyst and 1:15 oil: methanol ratio. The produced biodiesel matched the standard
Transesterification biodiesel according to ASTM D-6571 and EN 14214 international biodiesel standards. Diatoms skeletons/CaO/
Biodiesel MgO composite is a promising basic heterogeneous catalyst for efficient, high throughput, and low-cost biodiesel
production.
© 2019 Elsevier B.V. All rights reserved.

1. Introduction introducing renewable and environmental fuels as an alternative source

Energy and environment are the most significant concerns of the
contemporary world and the greatest obsession of modern civilizations.
The conventional fossil fuels and their derivatives are the main sources
of energy for most of the industrial institutes and all the transportation
techniques [1–3]. The enormous consumption of such fuel resources
may cause enormous economic and environmental problems in the
coming decades [4]. Economically, the estimated reserves for the com-
mon fossil fuel resources will be exhausted within less than ten decades,
and the gradual increase in the fossil fuels demands continuously facing
the depletion of the related resources [3,5]. Environmentally, combus-
tion of the traditional fuels resulted in excessive emission of injurious
gases (COx, SOx, and NOx) and other air pollutants which resulted in sev-
eral problems for the environment, ecosystem and human health in ad-
dition to their major role in greenhouse effect [6–8]. Therefore,
⁎ Corresponding authors.
E-mail addresses: abdo3040@yahoo.com (A.M. Rabie), nabelnegm@hotmail.com
(N.A. Negm).
of energy is a critical demand for energy and environmental agencies.
Biodiesel was introduced as one of the best alternative energy
sources for the traditional diesel fuel [9]. Chemically, it is of alkyl methyl
esters with long chains of fatty acids that can be produced through es-
terification of fatty acids or transesterification of vegetable oils, animal
fats and cooking oil [1,10]. The reaction occurs in the existence of alco-
hol with a short chain and suitable homogenous or heterogeneous cat-
alyst [8,11]. The biodiesel is clean, eco-friendly, non-toxic and
biodegradable fuel [12]. Also, it is characterized by its high flash point,
low viscosity, high octane number, and high lubricant properties. More-
over, it can be used in the present engines without modifications [13]. In
the later period, transesterification production of biodiesel utilizing
suitable solid heterogeneous catalysts attracted the attention of numer-
ous researchers in this field [7]. This ascribed to several advantages; low
production cost, low corrosion properties, non-toxicity, high purity of
yielded biodiesel, easy separation and recovering of it from the reaction
system, high stability of such catalysts even at high temperatures and
their suitability to be used for several transformation cycles [14,15]. Sev-
eral natural and synthetic materials have been investigated as a hetero-
geneous catalyst for efficient conversion of fatty acid and vegetable oils

https://doi.org/10.1016/j.molliq.2019.01.096
0167-7322/© 2019 Elsevier B.V. All rights reserved.
 A.M. Rabie et al. / Journal of Molecular Liquids 279 (2019) 224–231
into biodiesel [16]. CaO and MgO received interest in the
transesterification reactions the production of biodiesel [7,17].
Supporting of the heterogeneous catalysts on suitable materials was
studied to minimize the disadvantages of heterogeneous catalysts
[14]. However, little work focus on introducing cheap, efficient and
available natural porous silica as an alternative catalyst supports in bio-
diesel production. The use of available porous natural materials will give
a more realistic view of the applicability of using the final product on the
industrial scale.
Diatomaceous earth or diatomite is a natural fine-grained siliceous
rock composed of micronized amorphous silica particulates with amaz-
ing porous structure from the skeletons of single-celled algae known as
diatoms [18–20]. Diatomite exhibits unique physical properties such as
low bulk density, high porosity, high surface area, insulating ability, and
relative inertness. Such properties give the diatomite deposits great eco-
nomic and industrial value [21,22]. From the previous literature survey,
the application of diatomite as catalyst support in biodiesel production
was investigated [22]. Modiba et al., used diatomite impregnated in
KOH and achieved 90% biodiesel yield from vegetable oil after reaction
time 4 h at reaction temperature 75 °C using 30% methanol/oil ratio
and 5% catalyst/oil ratio [22]. Shan et al., applied diatomite supported
by CaO in the production of biodiesel from vegetable oil achieving
92.4% conversion percentage [23].
Here, a hybrid system composed of purified diatomite supported by
CaO/MgO composite was synthesized as a basic heterogeneous catalyst.
The synthetic catalyst was applied for the first time in the
transesterification of waste cooking oil into biodiesel as a function of re-
action time, catalyst dose, reaction temperature, catalyst/methanol
ratio, and reusability of the used catalyst for several conversion cycles.
2. Experimental work
2.1. Materials
Waste oil samples from the surrounding environment (restaurants,
houses, farms) and methanol (99.8%, Sigma Aldrich) were used in the
transesterification reaction. Purified diatomite represented to El-
Fayoum area, Egypt was delivered from Central Metallurgical and De-
velopment, Egypt as a catalyst support. The chemical composition of
the purified diatomite sample is 97.87% SiO2, 1.79% Al2O3 and 0.34%
L.O.I. Sodium hydroxide pellets (N98%, Sigma Aldrich), magnesium ni-
trate hexahydrate (N98%, Sigma Aldrich) and calcium nitrate
tetrahydrate (N98%, Sigma Aldrich) were used in the synthesis of CaO
and MgO catalyst. All these reagents are of AR grade and used without
further purification.
2.2. Preparation of the catalyst
2.2.1. Synthesis of diatomite supported by Ca(OH)2 (CaOH/diatomite)
Synthesis of Ca(OH)2/diatomite was performed through a conven-
tional impregnation method. In a typical procedure, 5 g of pure diato-
mite was dispersed in calcium nitrate solution (100 mL, 30%) and
stirred for 10 h at 50 °C. Then the solid was separated, washed by dis-
tilled water and dried at 120 °C for 12 h.
2.2.2. Synthesis of diatomite supported by CaO/MgO composite (DCM)
Loading of MgO trough out the porous structure of pre-synthetic Ca
(OH)2/diatomite was accomplished through chemical precipitation
method [24]. Typically, 5 g of the synthesized Ca(OH)2/diatomite were
dispersed in magnesium nitrate hexahydrate solution (100 mL, 0.5 M)
and stirred for 30 min at 800 rpm until homogeneous mixture of
suspended Ca(OH)2/diatomite particles was obtained. Then, sodium hy-
droxide solution (50 mL, 1 M) was added suddenly to the reaction me-
dium under ultrasonic stirring 85 °C till a thick white gel is formed. The
formed gel then transferred into a Teflon lined stainless steel autoclave
and heated at 150 °C for 12 h. Then, the obtained solid fractions were
225
centrifuged and washed several times using deionized water to remove
the excess sodium hydroxide and magnesium nitrate. The obtained
product was dried at 120 °C for 24 h and powdered, then calcinated
for 3 h at 800 °C to complete the conversion of magnesium hydroxide
into magnesium oxide.
2.3. Characterization of the catalyst
X-ray diffraction (XRD) charts of diatomite, Ca(OH)2/diatomite and
diatomite@CaO/MgO were obtained by scanning the compounds from
20 to 70o using PANalytical empyrean diffractometer with Cu (Kα) (λ
= 0.15406 nm) at scanning increment of 0.02° and accelerating voltage
of 40 kV and current intensity of 35 mA. High-resolution Scanning elec-
tron microscope (SEM; Gemini, Zeiss-Ultra 55) was used to investigate
the morphologies of the different compounds. Fourier Transform Infra-
red spectrometer (FTIR; Bruker, Vertex 70 FTIR-FT Raman) was used to
identify the different function groups of the compounds. Brunauer–
Emmett–Teller (BET) method was used to estimate the specific surface
area of the samples. Also, Pore-size distribution was measured from the
adsorption branches of the isotherms using the Barrett–Joyner–Halenda
(BJH) method.
2.4. Procedures of transesterification reaction of waste cooking oil
The transesterification reaction of the waste cooking oil using diato-
mite@CaO/MgO as an alkaline heterogeneous catalyst was performed
using three necked flask (250 mL) connected with a magnetic stirrer,
digital heater, and a water-cooling condenser. Waste cooking oil
(50 g) was stirred with different amounts of the prepared catalyst
(1–8 wt%) for different reaction time intervals (0.5–5 h) at different
temperatures (40 °C to 120 °C) and using different oil/methanol ratios
of 1:3, 1:6, 1:9, 1:12, 1:15 and 1:18. Each reaction condition, including
reactants amounts, reaction time and temperature and time were re-
peated three times. After each experiment, the catalyst was removed
from the reaction medium by centrifugation and the residual liquid
was retained in separating funnel overnight. Excess methanol was
stripped out under reduced pressure at 40 °C to obtain the
transesterification product of biodiesel. The efficiency of conversion re-
action (biodiesel yield %) was estimated from the amount of the re-
sulted fatty acids methyl esters (FAMEs) which obtained from the Gas
chromatography (Agilent 7890A) analysis of the products [12,25]
using Eq. (1):
ðWeight of biodiesel x%FAMEÞ
Biodiesel yield ð%Þ ¼  100: ð1Þ
Weight of oil
3. Results and discussion
3.1. Catalyst characterization
3.1.1. Samples structures
The structural features of used diatomite support and the synthetic
CaO and MgO catalysts were investigated based on XRD analysis
(Fig. 1). The XRD pattern of the purified diatomite sample exhibits a
broad peak around 2θ of 22° which assigned to amorphous silica
(Fig. 1A). The XRD pattern of diatomite impregnated in calcium solution
shows the presences of calcium carbonate (JCPDS card: No. 86-0174)
and calcium hydroxide (JCPDS card No. 01-073-5492) as the main
formed crystalline calcium based phases in addition to the reduced
broad peak of amorphous silica related to the original diatomite support
(Fig. 1B). The presences of calcium carbonate assigned to the rapid at-
mospheric carbonation of Ca(OH)2 by CO2 during washing and drying
[25].
The XRD pattern of the final prepared catalyst confirmed loading of
diatomite by of CaO and MgO as composite material; and the formation
226 A.M. Rabie et al. / Journal of Molecular Liquids 279 (2019) 224–231
Fig. 1. XRD patterns of purified diatomite (A), diatomite impregnated with calcium
solution (B) and the prepared diatomite supported by CaO/MgO (C).
of cristobalite (JCPDS card No. 89-3606 and 89-3434) as high-
temperature polymorph of silica after calcination diatomite at 800 °C
[26] (Fig. 1C). Additionally, small peaks were detected for the formation
of calcium silicate phase represented by Ca2SiO4 at 2θ of 34.3° (JCPDS
card No. 31-0302). MgO diffraction peaks were detected at 2θ of 43.2°
and 74.7° which are corresponding to crystallographic planes (200)
and (311), respectively (JCPDS; Cubic No. 01-077-2364). This is related
to cubic MgO with crystal lattice parameters of ?? = ?? = ?? = 4.213 Å
and space group Fm − 3 m (225). The crystallite size of the synthetic
MgO was determined based on the Scherrer equation and the obtained
value is about 81.6 nm. Several diffraction peaks were detected for CaO
at 2θ of 32.23°, 37.6°, 55.4° and 67.14°, which were assigned to the crys-
tallographic planes of (111), (200), (202) and (222) of cubic CaO crystal
with lattice parameters of ?? = ?? =?? = 4.8105 Å (JCPDS card No. 00-
004-0777). The average crystallite size of CaO in CaO/MgO composite
was found to be 63.3 nm.
3.1.2. Chemical functional groups
The change in the chemical functional groups with loading of diato-
mite by CaO and MgO was followed using FTIR spectroscopy of raw di-
atomite, Ca(OH)2/diatomite, and diatomite@CaO/MgO nanocomposite
(DCM) (Fig. 2). FTIR spectra of raw diatomite show the existence of
Fig. 2. FTIR spectra of raw diatomite, Ca(OH)2/diatomite, and diatomite@CaO/MgO
composite.
the following absorption bands at: 3437, 1638, 1092, 799 and
465 cm−1 (Fig. 2A). The two broad bands at 3437 cm−1 and
1638 cm−1 were assigned to the characteristic surficial silanol group
(SiO\\H) of diatomite silica skeletons and the H\\O\\H vibration of
the adsorbed water molecules, respectively [27,28]. The presence of
asymmetric stretching of Si\\O\\Si siloxane group was confirmed by
the absorption bands at 1092 cm−1 and 465 cm−1, while the symmetric
stretching of Si\\O\\Si was confirmed by the absorption band at
799 cm−1 [29].
Loaded Ca(OH)2/diatomite and the associated carbonized product
(Calcite) was pointed in the FTIR spectrum (Fig. 2B). Loading of diato-
mite by Ca(OH)2 caused apparent reduction in the intensity of the char-
acteristic absorption bands of raw diatomite, e.g., absorption bands of
asymmetric vibration Si\\O\\Si group and SiO\\H group. Also, this re-
sulted in a disappearance of the absorption bands of symmetrical
Si\\O\\Si and H\\O\\H groups. The formation of the loaded phases
were confirmed by the appearance of new absorption band at
1465 cm−1 assigned for CO32– groups which produced from the carbon-
ation of calcium hydroxide to calcium carbonate [23].
The prepared diatomite@CaO/MgO catalyst showed new absorption
bands related to the loaded oxides (Fig. 2C). Shifting the absorption
band located at 465 cm−1 to 443 cm−1 indicated the formation Ca\\O
bond [3]. The observed spectrum band around 867 cm−1 was assigned
to the Mg\\O\\Mg interaction or C\\O bond [30]. The absorption
band of CO32– showed significant increases in the intensity and the
width of it which attributed to surface adsorption of CO2 from the atmo-
sphere by the synthetic CaO or formation of magnesium carbonate [11].
3.1.3. Morphological properties
The changes in the morphological features of diatomite with the
loading of it by CaO and MgO catalyst were studied through SEM images
in Fig. 3. Raw diatomite sample appears with its characteristic shapes
and its amazing nanoporous structure (Fig. 3A). Penates type diatom's
skeletons are the dominant type in the purified sample as shown in
the magnified SEM images. The average pores width is ~224 nm, and
the average cell wall thickness is ~604 nm. After loading by calcium hy-
droxide and carbonization to calcium carbonate (calcite), diatom skele-
tons appear to be thoroughly coated with calcium hydroxide and
calcium carbonate particles (Fig. 3B). The porous morphology of diatom
skeletons was not destructed after the modification, but it was partially
closed by the deposited calcium-based materials. The coated particles
present in two main features represented by nanofibrous grains distrib-
uted throughout the porous structure of diatoms (Fig. 3C) and
nanoflakes or plated partially covered some parts of the diatomite
grains surfaces (Fig. 3D). The pores diameters were reduced to
b25 nm as shown in the insets magnified images of Fig. 3C. After MgO
coating, the diatomite surface was entirely covered by the studied
oxide (Fig. 3E). The diameter of the pores was reduced to b10 nm as
shown in the inset of Fig. 3E. The precipitated MgO has cast the porous
structure of diatomite, (inset of Fig. 3E), which enhanced the total sur-
face area and the overall porosity of the prepared diatomite@CaO/
MgO catalyst.
3.1.4. Textural properties
The textural properties of raw diatomite and the modified products
are described numerically in Table 1. The specific surface area of the raw
diatomite was increased significantly from 117 m2/g to 167 m2/g after
impregnation with calcium hydroxide to form Ca(OH)2/diatomite. This
can be attributed to the fibrous morphology of the loaded calcium hy-
droxide and its carbonated products. However, the loading of diatomite
by Ca(OH)2 cause blocking of some of the raw diatomite pores which
was associated with an increase in the pore volume from 0.09 cc/g to
0.168 cc/g. This was assigned to the formation of secondary pores due
to the interlocking between the fibrous particles of calcium hydroxide
and calcium carbonate. In addition, the average pore diameter was de-
creased from 16.57 nm of raw diatomite to 15.84 nm after loading of
 A.M. Rabie et al. / Journal of Molecular Liquids 279 (2019) 224–231 227

Fig. 3. SEM images of: (A) raw diatomite, (B) diatomite loaded by Ca(OH)2 and CaCO3 particles (C) nanofibrous grains structures of diatomite loaded by CaCO3, (D) nanoflakes or plated
structures of diatomite loaded by CaCO3, (E) diatomite loaded by CaO/MgO.

it by calcium hydroxide. i.e., both samples can be defined as mesoporous
materials. Reducing the average pore diameter can be related to the par-
tial filling of raw diatomite pores by calcium hydroxide and calcium
carbonate.
The synthetic diatomite@CaO/MgO catalyst exhibits higher surface
area of 134.85 m2/g than raw diatomite but lower than loaded Ca(OH)
2/diatomite. That can be commented to the blocking of raw diatomite
pores after modification by MgO. This also was resulted in an apparent
reduction in the average pore diameter and pore volume to be
0.137 cc/g and 11.57 m2/g, respectively.
3.2.1. Effect of methanol to oil ratio
The studying of transesterification reactions of waste cooking oil was
performed using different methanol to oil ratios (3:1, 6:1, 9:1, 12:1,
15:1, and 18:1) in the presence of 5% by weight of the synthesized diat-
omite@CaO/MgO catalyst for 180 min at 60 °C. The yield % of the ob-
tained biodiesel was determined at each ratio, Fig. 4. It is clear from
data in Fig. 4 that a gradual increase in the biodiesel yield percentage

3.2. Transesterification reaction

The transesterification reaction of waste cooking oil with methanol

to obtain the corresponding biodiesel was studied using the prepared
diatomite@CaO/MgO catalyst by studying the reaction parameters.
The studied parameters were: methanol to oil ratio, temperature, cata-
lyst amount, and the effect of time on the reaction.

Table 1
Textural properties of raw purified diatomite and its modified products.

Material BET surface area Average pore diameter Pore volume

(m2/g) (nm) (cc/g)

Raw diatomite 117.7 16.57 0.09

Ca(OH)2/diatomite 167.99 15.84 0.168
Fig. 4. Influence of oil to methanol ratio on the conversion percent of waste cooking oil into
Diatomite@CaO/MgO 134.85 11.57 0.137
biodiesel.
228 A.M. Rabie et al. / Journal of Molecular Liquids 279 (2019) 224–231
Fig. 5. Influence of reaction time on the conversion of waste cooking oil into biodiesel.
was observed by increasing the methanol to oil ratio from 3:1 to 15:1.
The yield percentage increased by 80.5%, 88.5%%, 90.9%, 92.3%, 92.7%
with increasing the ratio by 3, 6, 9, 12 and 15, respectively. Increasing
the methanol to oil ratio has no positive effect on expanding the interfa-
cial area between the present immiscible liquid which might be resulted
in higher frequency passage for the used heterogeneous catalyst
through it. This phenomenon resulted in increasing the exposed surface
area of the used catalyst and in turn a noticeable enhancing in the con-
version rate of waste cooking oil into biodiesel [31].
The biodiesel yield percentage was started to decrease with increas-
ing the ratio at 18:1. Increasing the methanol to oil ratio beyond 15 to
18, the biodiesel yield percentage decreased to 91.7%. This behavior
can be related to the deactivating role of excess methanol in dilution
of the components in the transesterification system, which reduces
the conversion rate [32]. Additionally, this is commonly associated
with difficulty in separation of the obtained biodiesel from the excess
methanol and increase in the solubility of glycerol by-product in the
used system which shifts the conversion reactions backsides [33].
3.2.2. Effect of reaction temperature
It was reported that increasing the transesterification reaction tem-
perature has a direct reflection on the transesterification reaction subse-
quently the conversion of the oil into biodiesel [34]. Consequently, the
experiments using diatomite@CaO/MgO catalyst were carried out at a
Fig. 6. Influence of amount of catalyst (%) by weight on the transesterification reaction of
waste cooking oil into biodiesel.
Fig. 7. Influence of reaction time on the conversion of cooking oil into biodiesel.
temperature range from 40 to 120 °C using 5% by weight of the synthe-
sized catalyst for 180 min at 1:15 oil to methanol ratio (Fig. 5). This fig-
ure showed a clear enhancement in the conversion reaction efficiency
by increasing the reaction temperature from 40 to 90 °C. Then, the con-
version efficiency decreased after increasing the temperature above 90
°C. The biodiesel yield percentage through the transesterification pro-
cess using diatomite@Cao/MgO as a catalyst was achieved at the maxi-
mum of 96.2% at 90 °C. This result was reported [35–37] and was
related to the gradual increase in the activation energy of the reaction
and the reaction rate by increasing the temperature of the
transesterification reaction of vegetable oils. The increase of the reaction
rate is resulted in more collisions between the used methanol and the
present triglyceride molecules which in turn promote the conversion
reaction and become faster at high temperatures [36].
Increasing the reaction temperature to 100–120 °C resulted in de-
creasing the conversion efficiency by 96.1%, 95.88%, and 95.67%, respec-
tively. This can be attributed to the evaporation of the methanol by
increasing the temperature which can reduce the methanol: oil molar
ratio during the conversion reaction and also due to the reverse behav-
ior of the transesterification reaction [34].
3.2.3. Effect of the catalyst amount
The effect of diatomite@CaO/MgO composite amount used on the
transesterification reaction of waste cooking oil was investigated using
catalyst amount of 1–6% by weight for 180 min at 90 °C and 1:15 oil
to methanol ratio (Fig. 6). The biodiesel yield percentage was increased
with increasing the catalyst weight from 1% to 6%. However, raising the
Fig. 8. Stability of diatomite@CaO/MgO for seven runs of transesterification of waste
cooking oil into biodiesel.
 A.M. Rabie et al. / Journal of Molecular Liquids 279 (2019) 224–231 229

Table 2 biodiesel yield showed a gradual increase with increasing the

Physicochemical properties of the obtained biodiesel in comparison with international transesterification time from 30 to 210 min. Then, the conversion effi-
biodiesel standards.
ciency was slightly decreased with increasing the reaction time from
Contents Unit ASTM EN Prepared Literature 210 to 280 min. The biodiesel yield was increased by 79.7%, 83.3%,
D-6751 14214 biodiesel values 86.6%, 91.3%, 94.2%, 96.5% and 96.4% with increasing the
Viscosity mm2/s 1.9–6 3.5–5 3.12 3.20–3.22 transesterification time by 30, 60, 90, 120, 150, 180, and 210 min,
[40] respectively.
Moisture wt.(%) b0.05 b0.05 0.022 0.015 [40]
Enhancing the conversion efficiency of waste cooking oil with in-
content
Flash point °C N120 N120 133 129–131 [41] creasing the time can be assigned to the immiscibility of the oil and
Cloud point °C −3 to 15 – 3 3–4 [41] methanol at the initial stages of the reaction [38]. While reversing of
Pour point °C −5 to 10 – 3 0–2 [43] the behavior after a specific reaction time can be attributed to the re-
Cetane number – 47–65 51 to 120 51.4 46–49 [34] versible nature of the conversion reaction of oils into biodiesel [32].
Density g/cm3 0.82–0.9 0.86–0.9 0.876 0.869 [34]
Calorific value MJ/kg – 32.9 38.431 –
Thus, the reaction time of 210 min is the optimum time for the best con-
version of waste cooking oil into biodiesel using diatomite@CaO/MgO
composite catalyst.
catalyst amount N6% resulted in a gradual decrease in the obtained bio-
diesel yield %. The increment of the catalyst amount by 1–6% was re-
sulted in biodiesel yield of 88.7%, 93.1%, 95.3%, 96.2% and 96.47%, 3.2.5. Catalyst stability
respectively. This can be assigned to the increase in the present active The stability of the prepared catalyst during the transesterification
catalytic sites of the catalyst with increasing the amount [36]. reaction of waste cooking oil was determined at the optimum reaction
Further increase in the catalyst amount to 7–10% decreased the con- conditions for several runs of the reaction using the same catalyst. The
version efficiency to 96.3%, 95.8%, and 95.2%, respectively. This can be used catalyst after each run washed several times with a mixture of
referred to the increase in the viscosity of the reaction medium under methyl alcohol and n-hexane (1:1 V:V), then re-activated at 800 °C for
the formation of dense slurry from the catalyst powder and the used 3 h. The suitability of diatomite@CaO/MgO composite for several runs
oil, which resulted in a difficulty in the homogenous mixing of the reac- of transesterification of waste cooking oil into biodiesel was represented
tants and consequently decreases in the interaction between the cata- in Fig. 8, for seven runs at the pre-estimated optimum reaction condi-
lyst and reaction component [37]. tions (210 min, 1:15 oil to methanol ratio, 6% catalyst amount, 90 °C).
The catalytic activity of the synthetic catalyst decreased with increasing
the conversion runs. This is closely related to the decreasing of the active
3.2.4. Effect of conversion time catalytic sites under the sequential use of the catalyst due to the precip-
Fig. 7 showed the effect of the reaction time on the conversion of itation of the insoluble by-products on its surface, e.g., glycerol [39]. The
waste cooking oil into biodiesel. At fixed conditions of 1:15 oil to meth- biodiesel yield was decreased by 96.4%, 94.3%, 90.2%, 87.45%, 78.23%,
anol ratio, 90 °C reaction temperature, and 6% catalyst amount, the 65.45% and 50.4% with reusing the catalyst from 7 runs.

Fig. 9. Mechanism of alkaline transesterification reaction of waste cooking oil and methanol in the presence of the prepared catalyst.
230 A.M. Rabie et al. / Journal of Molecular Liquids 279 (2019) 224–231
3.3. Biodiesel properties
The properties of the obtained biodiesel from the transesterification
reaction of waste cooking oil at the determined optimum reaction con-
ditions was characterized based on the physicochemical specifications
of the international standards of EN-14214 and ASTM D-6751
(Table 2). It is clear from the data in Table 2 that the specification re-
quirements of the obtained biodiesel are in accordance with the ASTM
D-6571 and EN 14214 limits. The obtained values of the produced bio-
diesel including viscosity, moisture content, flash point, cloud point,
pour point, cetane number and density were compared by the recently
published data [34,40,41,43]. Table 2 showed that the comparison com-
prised the comparable properties between the obtained biodiesel and
its validity for the use as alternative, environmentally and cheap fuel.
3.4. Mechanism of diatomite@CaO/MgO nanocomposite
transesterification reaction
The transesterification reaction between vegetable oils and metha-
nol are complicated reaction involves two main steps. The first is the
cracking of ester bonds in the triglyceride molecules and the second is
the substitution of the short chain alcohols in the molecules to produce
the desired biodiesel [41]. The prepared catalyst is characterized by the
presence of highly alkaline catalytic sites which play an important role
in the cleavage steps of the triglycerides and the alcohol molecules.
The alkaline catalytic sites in the catalyst are the metal oxide cores of
MgO and CaO. The presence of the Ca and Mg oxides in the chemical
structure of the catalyst has a high influence on its alkalinity [42,43].
That is due to the presence of Ca and Mg metal ions as the first two el-
ements in the alkaline earth metal series increases the negative charges
on the oxygen atoms. That increases their catalytic action in the alkaline
hydrolytic mechanisms [44]. Also increases the stability of the polarized
molecules in the form of calcium or magnesium methoxide and fatty
acid salts. The first catalytic step of the reaction involves polarization
of the ester group of the triglycerides in the C\\O bond between the
fatty acid moieties and the glycerol molecule [45]. Furthermore, a polar-
ization occurred for the methanol molecules due to the interaction by
the different alkaline sites in the catalyst, Fig. 9. The second step of the
reaction is the cracking of the triglyceride and methanol molecules
which accompanied by combination of the formed methoxy group
and the alkyl chains of the different fatty acids [46]. The interaction be-
tween the formed intermediates during the transeterification reaction
produces methyl esters of the different fatty acid moieties in the used
oil (biodiesel) and the glycerol as a bi-product of the process.
4. Conclusion
Diatomite supported by CaO/MgO composite was synthesized and
characterized as a novel basic heterogeneous catalyst for
transesterification of waste cooking oil into biodiesel. CaO/MgO com-
posite was successfully loaded into the porous structure of diatoms skel-
eton. The suitability of diatomite@CaO/MgO as a heterogeneous catalyst
in the transesterification reactions was addressed according to the com-
monly used conversion parameters. The catalyst achieves high catalytic
activity represented by maximum biodiesel yield percentage about
96.5%. This result was obtained after conversion time 120 min using
6 wt% catalyst at 1:15 oil/methanol ratio and a reaction temperature
of 90 °C. The qualifications of the final biodiesel product at the optimum
conditions match the specifications of the international standards bio-
diesel (ASTM D-6571 and most of EN 14214). Therefore, supporting of
diatoms skeletons by CaO/MgO composite is promising basic heteroge-
neous catalyst in the transesterification reactions and can be used as an
efficient, cheap and available catalyst support rather than the com-
monly study synthetic silica porous materials.
Acknowledgement
The Egyptian Academy for Scientific Research & Technology partially
supports this work (ASRT/SNG/E/2014-5).
References
[1] D.Y. Leung, X. Wu, M. Leung, A review on biodiesel production using catalyzed
transesterification, Appl. Energy 87 (2010) 1083–1095.
[2] A.M. Rabie, M.A. Betiha, S.E. Park, Direct synthesis of acetic acid by simultaneous co-
activation of methane and CO2 over Cu-exchanged ZSM-5 catalysts, Appl. Catal. B
Environ. 215 (2017) 50–59.
[3] N.A. Negm, M.A. Shaalan, G.S. El Barouty, M.Y. Mohamed, Preparation and evalua-
tion of biodiesel from Egyptian castor oil from semi-treated industrial wastewater,
J. Taiwan Inst. Chem. Eng. 63 (2016) 151–156.
[4] A. Elfadly, I. Zeid, F. Yehia, A. Rabie, S.E. Park, Highly selective BTX from catalytic fast
pyrolysis of lignin over supported mesoporous silica, Int. J. Biol. Macromol. 91
(2016) 278–293.
[5] S. Lee, D. Posarac, N. Ellis, Process simulation and economic analysis of biodiesel pro-
duction processes using fresh and waste vegetable oil and supercritical methanol,
in
Chem. Eng. Res. Des. 89 (2011) 2626–2642.
[6] A. Silitonga, H. Masjuki, H.C. Ong, T. Mahlia, F. Kusumo, Optimization of extraction of
lipid from Isochrysis galbana microalgae species for biodiesel synthesis, Energy
Sources, Part A 39 (2017) 1167–1175.
[7] A. Silitonga, T. Mahlia, H.C. Ong, T. Riayatsyah, F. Kusumo, H. Ibrahim, S. Dharma, D.
Gumilang, A comparative study of biodiesel production methods for Reutealis
trisperma biodiesel, Energy Sources, Part A 39 (2017) 2006–2014.
[8] F. Kusumo, A. Silitonga, H.C. Ong, H. Masjuki, T. Mahlia, A comparative study of ultra-
sound and infrared transesterification of Sterculia foetida oil for biodiesel production,
Energy Sources, Part A 39 (2017) 1339–1346.
[9] T.H. Dang, B.H. Chen, D.J. Lee, Optimization of biodiesel production from
transesterification of triolein using zeolite LTA catalysts synthesized from kaolin
clay, J. Taiwan Inst. Chem. Eng. 79 (2017) 14–22.
[10] A. Endut, S.H.Y.S. Abdullah, N.H.M. Hanapi, S.H.A. Hamid, F. Lananan, M.K.A.
Kamarudin, R. Umar, H. Juahir, H. Khatoon, Optimization of biodiesel production
by solid acid catalyst derived from coconut shell via response surface methodology,
Int. Biodeterior. Biodegrad. 124 (2017) 250–257.
[11] N.A. Negm, A.M. Rabie, E.A. Mohammed, Molecular interaction of heterogeneous
catalyst in catalytic cracking process of vegetable oils: chromatographic and biofuel
performance investigation, Appl. Catal. B Environ. 239 (2018) 36–45.
[12] G. Chen, R. Shan, J. Shi, C. Liu, B. Yan, Biodiesel production from palm oil using active
and stable K doped hydroxyapatite catalysts, Energy Convers. Manag. 98 (2015)
463–469.
[13] M. Zabeti, W.M.A.W. Daud, M.K. Aroua, Activity of solid catalysts for biodiesel pro-
duction: a review, Fuel Process. Technol. 90 (2009) 770–777.
[14] Y. Ma, Q. Wang, X. Sun, C. Wu, Z. Gao, Kinetics studies of biodiesel production from
waste cooking oil using FeCl3-modified resin as heterogeneous catalyst, Renew. En-
ergy 107 (2017) 522–530.
[15] A. Silitonga, T. Mahlia, F. Kusumo, S. Dharma, A. Sebayang, R. Sembiring, A.
Shamsuddin, Intensification of reutealis trisperma biodiesel production using infra-
red radiation: simulation, optimization and validation, Renew. Energy 133 (2019)
520–527.
[16] J. Milano, H.C. Ong, H. Masjuki, A. Silitonga, W.H. Chen, F. Kusumo, S. Dharma, A.
Sebayang, Optimization of biodiesel production by microwave irradiation-assisted
transesterification for waste cooking oil-Calophyllum inophyllum oil via response
surface methodology, Energy Convers. Manag. 158 (2018) 400–415.
[17] J. Milano, H.C. Ong, H. Masjuki, A. Silitonga, F. Kusumo, S. Dharma, A. Sebayang, M.Y.
Cheah, C.T. Wang, Physicochemical property enhancement of biodiesel synthesis
from hybrid feedstocks of waste cooking vegetable oil and beauty leaf oil through
optimized alkaline-catalysed transesterification, Waste Manag. 80 (2018) 435–449.
[18] J.A. Melero, J. Iglesias, G. Morales, Heterogeneous acid catalysts for biodiesel produc-
tion: current status and future challenges, Green Chem. 11 (2009) 1285–1308.
[19] S.S. Ibrahim, A.Q. Selim, Evaluation of Egyptian diatomite for filter aid applications,
Physicochemical Problems of Mineral Processing, 47, 2011, pp. 113–122.
[20] M. Hassan, I. Ibrahim, I. Ismael, Diatomaceous deposits of Fayium, Egypt; character-
ization and evaluation for industrial application, Chin. J. Geochem. 18 (1999)
233–241.
[21] H.A. Alyosef, S. Ibrahim, J. Welscher, A. Inayat, A. Eilert, R. Denecke, W. Schwieger, T.
Münster, G. Kloess, W.D. Einicke, Effect of acid treatment on the chemical composition
and the structure of Egyptian diatomite, Int. J. Miner. Process. 132 (2014) 17–25.
[22] N. Damanik, H.C. Ong, W. Chong, A. Silitonga, Biodiesel production from
Calophyllum inophyllum−palm mixed oil, Energy Sources, Part A 39 (2017)
1283–1289.
[[23] E. Modiba, C. Enweremadu, H. Rutto, Production of biodiesel from waste vegetable
oil using impregnated diatomite as heterogeneous catalyst, Chin. J. Chem. Eng. 23
(2015) 281–289.
[24] W. Jindapon, S. Jaiyen, C. Ngamcharussrivichai, Al2O3-supported mixed Ca and Zn
compounds prepared from waste seashells for synthesis of palm fatty acid methyl
esters, Chem. Eng. Commun. 202 (2015) 1591–1599.
[25] A.R. Ibrahim, J.B. Vuningoma, Y. Huang, H. Wang, J. Li, Rapid carbonation for calcite
from a solid-liquid-gas system with an imidazolium-based ionic liquid, Int. J. Mol.
Sci. 15 (2014) 11350–11363.
[26] S. Zheng, C. Bai, R. Gao, Preparation and photocatalytic property of/diatomite-based
porous ceramics composite materials, Int. J. Photoenergy 2012 (2012).
 A.M. Rabie et al. / Journal of Molecular Liquids 279 (2019) 224–231
[27] J.F. Mukerabigwi, S. Lei, L. Fan, H. Wang, S. Luo, X. Ma, J. Qin, X. Huang, Y. Cao, Eco-
friendly nano-hybrid superabsorbent composite from hydroxyethyl cellulose and
diatomite, RSC Adv. 6 (2016) 31607–31618.
[28] J.F. Mukerabigwi, S. Lei, H. Wang, S. Luo, X. Ma, J. Qin, X. Huang, Y. Cao, Synthesis and
properties of a novel ecofriendly superabsorbent hydrogel nanocomposite based on
xyloglucan-graft-poly (acrylic acid)/diatomite, RSC Adv. 5 (2015) 83732–83742.
[29] S. Zhang, A new nano-sized calcium hydroxide photocatalytic material for the
photodegradation of organic dyes, RSC Adv. 4 (2014) 15835–15840.
[30] P. Devaraja, D. Avadhani, S. Prashantha, H. Nagabhushana, S. Sharma, B.
Nagabhushana, H. Nagaswarupa, Synthesis, structural and luminescence studies of
magnesium oxide nanopowder, Spectrochim. Acta A Mol. Biomol. Spectrosc. 118
(2014) 847–851.
[31] D.M. Marinković, J.M. Avramović, M.V. Stanković, O.S. Stamenković, D.M. Jovanović,
V.B. Veljković, Synthesis and characterization of spherically-shaped CaO/γ-Al2O3
catalyst and its application in biodiesel production, Energy Convers. Manag. 144
(2017) 399–413.
[32] M.R. Abukhadra, F.M. Dardir, M. Shaban, E.A. Ahmed, M.F. Soliman, Spongy Ni/Fe
carbonate-fluorapatite catalyst for efficient conversion of cooking oil waste into bio-
diesel, Environ. Chem. Lett. 16 (2018) 665–670.
[33] D. Zeng, L. Yang, T. Fang, Process optimization, kinetic and thermodynamic studies
on biodiesel production by supercritical methanol transesterification with
CH3ONa catalyst, Fuel 203 (2017) 739–748.
[34] N.A. Negm, M.K. Zahran, M.R. Abd Elshafy, I.A. Aiad, Transformation of Jatropha oil to
biofuel using transition metal salts as heterogeneous catalysts, J. Mol. Liq. 256
(2018) 16–21.
[35] M. Feyzi, Z. Shahbazi, Preparation, kinetic and thermodynamic studies of Al–Sr
nanocatalysts for biodiesel production, J. Taiwan Inst. Chem. Eng. 71 (2017)
145–155.
[36] N.A. Negm, G.H. Sayed, F.Z. Yehia, O.I. Habib, E.A. Mohamed, Biodiesel production
from one-step heterogeneous catalyzed process of Castor oil and Jatropha oil
231
using novel sulphonated phenyl silane montmorillonite catalyst, J. Mol. Liq. 234
(2017) 157–163.
[37] N.A. Negm, G.H. Sayed, O.I. Habib, F.Z. Yehia, E.A. Mohamed, Heterogeneous catalytic
transformation of vegetable oils into biodiesel in one-step reaction using super
acidic sulfonated modified mica catalyst, J. Mol. Liq. 237 (2017) 38–45.
[38] M. Feyzi, N. Hosseini, N. Yaghobi, R. Ezzati, Preparation, characterization, kinetic and
thermodynamic studies of MgO-La2O3 nanocatalysts for biodiesel production from
sunflower oil, Chem. Phys. Lett. 677 (2017) 19–29.
[39] X. Niu, C. Xing, W. Jiang, Y. Dong, F. Yuan, Y. Zhu, Activity and stability of solid base
KF/La2O3 catalysts for transesterification of tributyrin with methanol, React. Kinet.
Mech. Catal. 109 (2013) 167–179.
[40] A.M. Rabie, E.A. Mohammed, N.A. Negm, Feasibility of modified bentonite as acidic
heterogeneous catalyst in low temperature catalytic cracking process of biofuel pro-
duction from nonedible vegetable oils, J. Mol. Liq. 254 (2018) 260–266.
[41] A.W. Schwab, M.O. Baghy, B. Freedman, Preparation and properties of diesel fuels
from vegetable oils, Fuel 66 (1987) 1372–1378.
[42] D.M. Marinkovic, J.M. Avramovic, M.V. Stankovic, O.S. Stamenkovic, D.M. Jovanovic,
V.B. Veljkovic, Synthesis and characterization of spherically-shaped CaO/γ-Al2O3
catalyst and its application in biodiesel production, Energy Convers. Manag. 144
(2017) 399–413.
[43] J.P. Gomes, J.B. Puna, J.M. Bordado, M.N. Correia, A.S. Dias, Status of biodiesel produc-
tion using heterogeneous alkaline catalysts, Int. J. Environ. Stud. 69 (2012) 635–653.
[44] I.S. Resck, Polyaminophosphazenes as super bases nitrogenadas, Quim. Nova 17
(1994) 317–321.
[45] P. Chand, C.V. Reddy, J.G. Verkade, T. Wang, D. Grewell, Thermogravimetric quanti-
fication of biodiesel produced via alkali catalyzed transesterification of soybean oil,
Energy Fuel 23 (2009) 989–992.
[46] I.A.W. Mohamad, O.A. Ali, Evaluation of the transesterification of waste palm oil into
biodiesel, Bioresour. Technol. 85 (2002) 251–256.