Environmental Chemistry Letters

https://doi.org/10.1007/s10311-017-0695-2

ORIGINAL PAPER

Spongy Ni/Fe carbonate‑fluorapatite catalyst for efficient conversion

of cooking oil waste into biodiesel
Mostafa R. Abukhadra1,2 · Fatma M. Dardir3 · Mohamed Shaban1 · Ezzat A. Ahmed3 · Mamdouh F. Soliman3

Received: 3 August 2017 / Accepted: 14 December 2017

© Springer International Publishing AG, part of Springer Nature 2017

Abstract
Biodiesel produced from animal and plant fat oils is sustainable, but there is a need for efficient heterogeneous catalysts for
transesterification of crude oils into biodiesel. Here, spongy carbonate-fluorapatite loaded with nickel and iron was synthe-
sized and tested for conversion of waste cooking oil into biodiesel. The catalyst was synthesized by dissolution of phosphorite
in nitric acid, and then nickel chloride was dissolved in the filtrate. The catalyst was then precipitated with ammonia and
heated at 150 °C for 12 h, thus yielding a spongy porous solid containing about 8% iron and 3% nickel. Results show a 97.5%
biodiesel yield at 70 °C in 2 h using 10 wt% catalyst dose and 8:1 methanol/oil ratio. The final biodiesel product matches the
specification of ASTM D-6571 and most of EN 14214 biodiesel standards. This novel catalyst achieves better results than
normally used hydroxyapatite and other calcium-based catalysts.

Keywords Spongy · Apatite · Biodiesel

Introduction
The fast increase in the consumption of traditional fossil
fuels with their associated carbon dioxide pollution in the
contemporary world resulted in a critical demand to develop
new technologies for clean and environmental energy
resources (Nisar et al. 2017; Yi et al. 2015). Biodiesel pro-
duction utilizing oil and fats of plants and animals appeared
as a promising solution because of its environmental value,
non-toxicity, biodegradability and high flash point (Batista
et al. 2015; Chen et al. 2015). Also biodiesel is important
raw material in the production of valuable products as epox-
ides (Lehnen et al. 2014).
Recently, the use of heterogeneous catalysts in the trans-
esterification of oil into biodiesel attracted the attention of
several authors (Fan et al. 2014). This credited to their low
* Mostafa R. Abukhadra
Abukhadra89@Science.bsu.edu.eg
1
Nanophotonics and Applications Lab, Physics Department,
Faculty of Science, Beni-Suef University, Beni‑Suef 62514,
Egypt
2
Geology Department, Faculty of Science, Beni-Suef
University, Beni‑Suef, Egypt
3
Geology Department, Faculty of Science, Assiut University,
Assiut, Egypt
cost, lack of toxicity, easy separation and recovery, high sta-
bility at high temperatures and reusability for several runs
(Nisar et al. 2017). Several materials have been evaluated
for this target including alkaline earth, transitional metal
metals and oxides and noble elements (Liu et al. 2014).
However, the rate of transesterification reaction utilizing
heterogeneous catalyst is lesser as compared to using homo-
geneous catalyst (Nisar et al. 2017). Therefore, the use of
catalyst-supporting materials was investigated to minimize
the mass diffusion limitations, provide more active sites and
to enhance the specific surface area (Ma et al. 2017). The
commonly used materials as catalyst support in biodiesel
production are alumina oxide, zinc oxide, activated carbon,
bentonite, halloysite, MCM-41, apatite, zeolite and SBA-
15 (Zabeti et al. 2009). Other techniques have been used to
produce biodiesel from macroalgae through thermochemi-
cal liquefaction and utilizing supercritical carbon dioxide
(Aresta et al. 2005). Akalın et al. (2017) succeeded in the
production of biofuel from biomass through supercriti-
cal fluids extraction method. Also biodiesel was produced
through green chemistry methods such as intensification pro-
cess utilizing microwave and ultrasound techniques (Gude
and Martinez-Guerra 2017).
Apatite is a mineral of chemical formula X ­ 5(YO4)3(OH,
F, Cl), where X is metal cation, e.g., calcium, sodium
and barium. Y is the elements of phosphorous, arsenic or

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vanadium. There are four types of natural apatite: hydroxy-
lapatite, carbonate-fluorapatite, chlorapatite, and fluorapa-
tite. Porous hydroxylapatite is a common synthetic type that
is used widely as a catalyst support (Sandrine et al. 2007).
Hydroxyapatite was extensively synthesized either based on
chemical materials or based on natural materials (Liao et al.
2010; Hashimoto and Sato 2007). The type, structure and
porosity of the synthetic apatite are controlled by pH, reac-
tion temperature, reaction time and the nature of precursor
(Rhaiti et al. 2012). Thus, the nature of the starting natural
phosphate precursor can control the type of the synthetic
apatite and its structural properties.
Thus, in this study, spongy carbonate-fluorapatite was
synthesized for the first time and modified by Fe and Ni
metal to be used as a novel catalyst for efficient conversion
of waste cooking oil into biodiesel. The conversion process
was evaluated as a function of reaction time, catalyst dose,
methanol/oil molar ratio and the reaction temperature.
Experimental
Materials
Phosphorite samples were collected from Zug El Bohar
locality, Quseir area, Egypt. The average chemical com-
position of the sample is 46% CaO, 28% P ­ 2O5, 12% S
­ iO2,
2% ­Fe2O3, 2.8% F and 7% loss of ignition, in addition to
traces of A
­ l2O3 (0.8%), N
­ a2O (0.4%), MgO (0.5%) and K
­ 2O
(0.07%). Ammonium hydroxide (20%, Aldrich) and nickel
(II) chloride hexahydrate (Aldrich, 99.9%) were used in the
synthesis process. Waste oil samples from the surround-
ing environment (restaurants, houses, farms) and metha-
nol (Aldrich, 99.8%) were used in the transesterification
reaction.
Synthesis of the catalyst
The synthesis of spongy carbonate-fluorapatite was carried
out through dissolution–precipitation method. Fifty grams
of raw phosphorite was ground to be with size ranged from
10 to 100 µm and dissolved in 250 ml of 10 M nitric acid
under continuous stirring for 4 h at about 70 °C to obtain
high concentrations of C ­ a2+ and H
­ 3PO4. Then, the saturated
solution was separated by filtration for the precipitation step.
Five grams of nickel chloride hexahydrate was dissolved
in the filtrated solution as a source of nickel and stirred for
30 min. After that, the resulted solution was precipitated
using ammonium hydroxide solution (20%) and transferred
into Teflon-lined stainless steel autoclave and then heated for
12 h at 150 °C. After cooling, the solid was separated and
washed several times with hot distilled water and finally was
dried at 100 °C for 24 h.
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Environmental Chemistry Letters
Characterization
X-ray powder diffraction (XRD) patterns of raw phospho-
rite and the synthetic porous carbonate-fluorapatite were
obtained utilizing a Philips APD-3720 diffractometer. The
morphological properties and chemical composition of the
synthetic carbonate-fluorapatite were studied using scanning
electron microscopy (SEM) equipped with energy-dispersive
X-ray spectroscopy (EDX). The percentage of calcium ions
in the oil samples was determined using inductively coupled
plasma mass spectrometry (ICP).
Transesterification reaction
The transesterification reaction of waste oil in the pres-
ence of spongy Ni/Fe carbonate-fluorapatite as a catalyst
was done utilizing 3-neck flask (150 ml) attached with a
water-cooled condenser, magnetic stirrer with heater and
thermometer. Fifty grams of the studied oil was mixed with
methanol at different molar ratios (2:1–15:1) in the presence
of different amounts of the used catalyst (4–12 wt%) and at
different reaction temperatures (50–90 °C) for different time
intervals from 30 to 240 min. After that, the catalyst was
separated from the mixture by filtration and the filtrate was
kept in separating funnel for 24 h. The excess methanol in
the upper part of the funnel was removed through fan drying
for 24 h, and sodium sulfate was added to confirm complete
removal of any present water molecules.
Gas chromatography (Agilent 7890A) was used to deter-
mine the amount of produced fatty acids of methyl ester
(FAME). The percentage of biodiesel yield was estimated
based on Eq. 1 (Chen et al. 2015):
Biodiesel yield (% ) =
(Weight of biodiesel × %FAME)
× 100
Weight of oil
(1)
Results and discussion
Characterization of the catalyst
The characteristics X-ray diffraction (XRD) patterns of
the starting natural phosphorite and the synthetic Ni/Fe
apatite are shown in Fig. 1. The resulted XRD pattern of
natural raw phosphorite revealed the presence of carbon-
ate-fluorapatite (francolite) as the main phosphate-bearing
mineral in addition to other impurities of calcite, quartz,
and gypsum (Fig. 1a). The resulted X-ray diffraction pattern
after the conversion of phosphorite into the spongy apatite
shows complete disappearance of the associated impurities
and the formation of highly crystalline carbonate-fluorapa-
tite (Fig. 2b). Carbonate-fluorapatite phase was detected at
two-theta angles of 17.76°, 22.26°, 25.72°, 28.73°, 31.75°,
32.68°, 35.95°, 37.53°, 39.78°, 49.47° and 52.72° (Fig. 1b).
Environmental Chemistry Letters

Fig. 1  X-ray diffraction analysis

of natural phosphorite and the
synthetic spongy carbonate-
fluorapatite. Natural phos-
phorite completely converted
into carbonate-fluorapatite
after the synthesis process
(a), energy-dispersive X-ray
spectroscopy (EDX) analysis
revealed the presence of iron
and nickel within the structure
of spongy apatite (b), image
of hand specimen carbonate-
fluorapatite shows its spongy
structure which acquires it
high surface area (c), scanning
electron microscope images of
spongy carbonate-fluorapatite
reflected the presence of differ-
ent types of pores confirming its
novel spongy porous structure
(d–f). G gypsum, Q quartz, F
francolite, C calcite and A Ni/Fe
carbonate-fluorapatite

The average crystallite size (D) was estimated utilizing
Scherrer’s formula, and the value is 8.27 nm. The energy-
dispersive X-ray spectroscopy analysis (EDX) showed the
presence of oxygen, calcium, phosphorous, iron, carbon,
nickel and fluorine with mass% of 36.8, 30.03, 10.69, 8.54,
7.36, 3.34 and 3.26%, respectively. These results confirmed
the synthesis of Ni/Fe carbonate-fluorapatite.
The hand specimen of a sample of Ni/Fe carbonate-
fluorapatite appears to be spongy materials of numerous
disconnected macropores (Fig. 1c). Under the scanning
electron microscope, the sample appears as agglomerated
aggregates of micron size with different types of pores.
There is nano-pores distributed homogeneity throughout
the surface of carbonate-fluorapatite particles (Fig. 1d).
Additionally, the contact between the agglomerated par-
ticles resulted in secondary micropores with a size range
from 1 µm to about 3 1 µm (Fig. 1e). Other types of pores
were detected in the sample that can be classified as surfi-
cial pores (Fig. 1f). To the best of our knowledge, the
detected morphology has not been designated before for
any type of porous apatite.

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 Environmental Chemistry Letters

Fig. 2  Analyses of the effects

of reaction temperature on the
conversion efficiency; a effect
of temperature at different time
intervals indicated increasing
the efficiency with time until
equilibrium at 120 min and
the temperature until 70 °C
(120 min time at 70 °C tempera-
ture are the optimum values), b
the effect of methanol/oil ratio
curve exhibits increase in the
resulted biodiesel yield with
increasing the ratio till 8:1 and
then the value decreases again
achieving the best results as this
value, c effect of catalyst dose
on the biodiesel yield reflected
the increase in the efficiency
with increasing the dose to
10 wt% and above this value
the efficiency decreased again,
and d the reusability of catalyst
for several runs of conversion
indicated the decrease in the
efficiency with increasing the
number of runs from run 1 to
run 3

Conversion reactions
Reaction temperature
The effect of temperature at different reaction times was
evaluated at fixed catalyst dose 10 wt% and 8:1 methanol/
oil ratio (Fig. 2a). The biodiesel yield increased gradually
with increasing the temperature from 50 to 70 °C at all the
studied time intervals, and then, the yield value decreased
clearly with increasing the temperature above 70 °C. This
was assigned to the evaporation of methanol by raising
the reaction temperature which reduces the molar ratio of
methanol to oil (Samart et al. 2010). Thus, the optimum
reaction temperature is 70 °C. The interaction effect of the
reaction time with the temperature also plays a significant
role in the efficiency of the process. The biodiesel yield
increased significantly with increasing the reaction time till
reaching the equilibrium where the efficiency appears to be
fixed or slightly decreased. Transesterification reaction is a
reversible process, and increasing the time above the limit
decreases the biodiesel yield (Chen et al. 2015). At reac-
tion temperature 70 °C, the equilibrium was obtained after
120 min. Thus, reaction temperature 70 °C and reaction time
120 min are the optimum conditions for maximum biodiesel
yield (97.56%).
Methanol/oil ratio
The effect of methanol/oil molar ratio on the efficiency of
transesterification reactions was studied at different reac-
tion times and at fixed conditions of 10 wt% catalyst dose
and 70 °C temperature (Fig. 2b). At all the studied metha-
nol/oil ratios, the biodiesel yield increased with increasing
the reaction time till the equilibrium. However, the conver-
sion efficiency controlled mainly by methanol/oil ratio as
the biodiesel yield increased with increasing the ratio by
2:1, 4:1 and 8:1. Methanol/oil ratio of 8:1 is the optimum
ratio. Increasing the methanol/oil ratio above 8:1 resulted

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Environmental Chemistry Letters
in an apparent reduction in the conversion efficiency. This
credited to the effect of methanol ratio in promoting the
forward transesterification reaction, and it can promote
reversible reaction for the formed biodiesel (Chen et al.
2015). Also, this decreases the ratio of oil over the limit
which reduces the reaction rate and changes the trans-
esterification equilibrium. Moreover, excess volumes of
methanol can cause dilution or deactivation of the catalyst
which reduces the conversion efficiency (Viriya-empikul
et al. 2012).
Effect of catalyst dose
Effect of the dose was evaluated at the optimum condi-
tions of temperature (70 °C) and methanol/oil ratio (8:1)
for different reaction times (Fig. 2c). The biodiesel yield
shows continuous increasing with increasing the cata-
lyst dose by 4, 8 and 10 wt% achieving the best value at
10 wt% catalyst dose. Further increasing the amount of
Ni/Fe carbonate-fluorapatite catalyst causes considerable
decrease in the percentage of biodiesel yield. The previous
behavior might be related to the formation of a slurry of
high viscosity which reduces the adequate mixing between
the components of the system (Chen et al. 2015). The bio-
diesel yield curves utilizing different amounts of the cata-
lyst exhibit the same trend over the studied time intervals.
Stability of the catalyst
The reusability of the catalyst is critical for application
of the materials on the industrial scale. The stability was
evaluated through three runs of transesterification reac-
tions for different time intervals from 30 to 240 min
(Fig. 2d). The catalyst exhibits good conversion proper-
ties over the studied runs, and the efficiency decreased
from run 1 to run 3. The maximum biodiesel yield value
at run 1 is 97%, while at run 2 and run 3 it is 70 and
54%, respectively. The reduction in the catalytic efficiency
with the studied runs may be related to the decrease in the
­Ca2+ ions in the structure of carbonate-fluorapatite through
cation exchange process during the reactions and leach-
ing of them to the oil samples. This confirmed by induc-
tively coupled plasma mass spectrometry (ICP) for the oil
samples and energy-dispersive X-ray spectroscopy (EDX)
analysis of the catalyst after washing it several times. The
concentration of calcium ions increases gradually from
25 to 83 ppm with increasing the number of conversion
runs from run 1 to run 3 (Fig. 3). Energy-dispersive X-ray
spectroscopy (EDX) analysis indicated the decrease in the
calcium percentage from 30.03 to 24.67%, confirming the
leaching process for calcium ions.
Fig. 3  Analysis of calcium ions concentration within the oil sample
after the stability reaction runs. Calcium concentration increased
greatly from run 1 to run 3 indicating the release of calcium from
the catalyst structure which reduces the conversion efficiency with
increasing the number of transesterification runs
Physicochemical properties of the prepared biodiesel
The physicochemical properties of the obtained biodiesel
at the optimum conditions were investigated and are given
in Table 1 in comparison with the biodiesel international
standards set by European Committee for Standardization
(EN 14214) and American Section of the International Asso-
ciation for Testing Materials (ASTM D-6751). The final
product matches the specification of biodiesel set by ASTM
D-6571 biodiesel and most of the requirements set by EN
14214. The low calorific value of the obtained biodiesel as
compared to the standards might be credited to the presence
of methanol and unreacted triglyceride (Oliveira and Da
Silva 2013). Thus, refining of biodiesel through distillation
process is advisable to remove the associated impurities. The
obtained final results appear to be higher in efficiency than
the obtained results in the other studies such as Ma et al.
(2017), Chen et al. (2015), Viriya-empikul et al. (2012) and
Nisar et al. (2017).
Conclusion
Novel spongy structure from carbonate-fluorapatite loaded
by nickel and iron was synthesized via dissolution/precipita-
tion techniques from natural phosphorite. The product was
characterized by X-ray diffraction and scanning electron
microscope and used as a catalyst for efficient conversion of
waste cooking oil into biodiesel. The maximum biodiesel
yield 97.56 was obtained after reaction time 120 min, tem-
perature 70 °C, catalyst dose 10 wt% and 8:1 methanol/oil
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 Environmental Chemistry Letters

Table 1  Physicochemical properties of obtained biodiesel in comparison with international biodiesel standards

Contents Units American Section of the International Associa- European Committee for Biodiesel
tion for Testing Materials (ASTM D-6751) Standardization (EN 14214)

Ester % > 96.5 > 96.5 97.56

Viscosity mm2/s 1.9–6 3.5–5 4.3
Moisture content wt% < 0.05 < 0.05 0.012
Flash point °C > 120 > 120 153
Cloud point °C − 3 to 15 – 10.24
Pour point pp − 5 to 10 – 7.2
Cetane number 47–65 51–120 57.4
Density g/cm3 0.82–0.9 0.86–0.9 0.886
Calorific value MJ/kg 39.2 – 25.7
Acid number mg KOH/g < 0. 5 < 0.5 0.32
Oxidation stability (110 °C) h >3 >6 7.21

ratio. The final biodiesel product matches the specification of
ASTM D-6571 and most of EN 14214 biodiesel standards.
Acknowledegements The authors of this paper thank the Assiut Uni-
versity, Egypt, for funding the study as a research project of the M.Sc.
thesis of the second author (Fatma Dardir).
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