Renewable and Sustainable Energy Reviews 72 (2017) 746760

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Renewable and Sustainable Energy Reviews

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Application of nano CaObased catalysts in biodiesel synthesis MARK

Ivana B. BankoviIli, Marija R. Miladinovi, Olivera S. Stamenkovi, Vlada B. Veljkovi
Faculty of Technology, University of Ni, Bulevar osloboenja 124, 16000 Leskovac, Serbia

A R T I C L E I N F O A BS T RAC T

Keywords: Calcium oxide (CaO) itself, as cheap, highly active and easily available, is one of the most used solid catalysts for
Biodiesel transesterication reaction of dierent oils and fats to biodiesel. A way to improve its catalytic activity is to
Nano calcium oxide, preparation methods increase its specic surface by preparing it in the nanoform. This paper gives an overview of the preparation of
Reusability nanosized CaObased catalysts and their application in the biodiesel production. Various forms of nanosized
CaObased catalysts have been employed in the biodiesel production like neat, doped and loaded CaO as well as
waste material containing CaO. The modern technology based on the use of nano CaObased catalysts aiming at
high biodiesel yields will have further positive implications like simplicity, safety, economy and eciency of
biodiesel production. This overview proves the promising potentiality of nano CaObased catalysts as solid
catalysts in biodiesel production.

1. Introduction
The major source of energy comes from fossil fuels which satisfy
more than 90% of the world energy demand. Because of the excessive
consumption of fossil fuels that results in greenhouse gas emissions,
the mankind is faced with global warming. The current global problem
is also limited fossil fuels sources. The experts predict that available
sources of fossil fuels will run out by 2050 because their consumption is
105 faster than their natural production [1,2] while the world energy
demand will reach 30 TW [3]. Therefore, the renewable energy sources
gain more attention. According to expectations their use will provide
the 50% of global energy by 2040 and reduce the greenhouse gas
emissions up to 70% [4].
Among the renewable fuels, biodiesel has a signicant position. Not
only it can be produced from widespread biosources, such as vegetable
oils, animal fats and algal lipids, but also it is nontoxic and biodegrad-
able and has high ash point, good lubricant properties and low gas
emission with no sulfur and cancerogenic compounds during combus-
tion [5,6]. In addition, used and waste oils and fats from households,
restaurants and food industry can also be used as raw materials, which
contribute to the reduction of biodiesel production cost and help
solving the waste disposal [7,8]. Biodiesel can be used as additives to
fossil fuel and as a 100% fuel. Its application as an additive does not
require any modication of the existing diesel engine while as a 100%
fuel does but not signicant. According to the standard, biodiesel is a
mixture of fatty acid methyl esters obtained by the catalyzed or
uncatalyzed reaction between triacylglycerols (TAGs) or free fatty acids
(FFAs) and a short chain alcohol (mainly methanol or ethanol), which
satisfy the prescribed quality specications. For the catalyzed reaction,
the dierent type of catalyst can be employed homogeneous or
heterogeneous catalysts. The currently implemented technologies for
biodiesel production are based mostly on homogeneous base catalysis.
The noncorrosive and environmentally friendly nature of heteroge-
neous catalysts and the possibility to be easily separated from products
and reused with or without regeneration make them more convenient
for the biodiesel production compared to homogeneous catalysts.
However, there are some limitations for their commercial application
like the complex methods for their synthesis and diculties in handling
during application on large scale plants.
Calcium oxide (CaO) itself, as cheap, easily available, noncorrosive,
environmentally friendly, easy to handle material with low solubility
and high basicity that can be regenerated and reused, is one of the most
used solid catalyst for transesterication reaction of dierent feed-
stocks to biodiesel, which has been already proved as a highly ecient
catalyst for biodiesel synthesis [912]. All these advantages draw the
attention of many researchers for further investigations of CaO aiming
at the improvement of its overall properties. A way to improve the
catalytic activity of CaO is to increase its specic surface by preparing it
in the nanoform.
The use of nanocatalysts has recently been the focus of numerous
researches related to biodiesel synthesis. Nanocatalysts represent the
nanomaterials or nanocrystals with the particle size in the range of 1
100 nm [13]. The particularly large specic surface area and high
catalytic activity are their favorable properties for application in

Corresponding author.
E-mail address: veljkovicvb@yahoo.com (V.B. Veljkovi).

http://dx.doi.org/10.1016/j.rser.2017.01.076

Available online 21 January 2017

1364-0321/ 2017 Elsevier Ltd. All rights reserved.
I.B. BankoviIli et al.
heterogeneouslycatalyzed biodiesel synthesis. Many researchers have
tested nano CaO as a catalyst for biodiesel synthesis [1420].
This paper gives an overview of the preparation of nanosized
CaObased catalysts and their application in the biodiesel production
as heterogeneous catalysts. In line with this, the paper summarizes the
current status of nano CaObased catalysts, indicates their promising
capability in biodiesel production and identies the future opportu-
nities in this research area. The main aim of this paper is to estimate
the possibility of performing the heterogeneously catalyzed oil alcoho-
lysis by nano CaObased catalysts through the analysis of the inuence
of dierent operating conditions (water and FFA contents in raw
materials, catalyst amount, type and concentration of impregnated ion,
reaction temperature, type of alcohol, molar ratio of methanol to oil
and use of cosolvents) on biodiesel yield. First, the importance of the
application of nanomaterials in the catalytic processes is shortly
described. After presenting the benets and drawbacks of biodiesel
synthesis over nanosized CaObased catalysts, their preparation and
activation are discussed. Then, the application of dierent forms of
nano CaO catalysts (neat, doped, loaded and waste) in the conversion
of various oily feedstocks into biodiesel and the inuence of dierent
reaction conditions on biodiesel yield are explained. Finally, the
possibility of multiple utilization of nano CaObased catalysts, as well
as the kinetics and statistical optimization of transesterication reac-
tions conducted in the presence of these catalysts are considered.
2. Nanocatalysts
In the last decades, scientists have been searching for new
advanced, functional and costeective nanomaterials, which include
carbon nanotubes, nanobers, nanoclays, nanocomposites, nanoporous
materials, nanowires and nanoparticles, for dierent applications.
These nanomaterials have at least one geometrical dimension less than
100 nm. Nanoparticles, as spherical (or quasispherical) particles
having a diameter less than 100 nm, may have important roles in
numerous catalysis processes, which is one of the oldest application of
nanotechnology.
The processes (physical or chemical) of nanoparticles synthesis
used mostly in laboratories are energy dependent. Physical methods
often require large capital costs with reduced environmental impact,
while chemical methods are somewhat cheaper because of reduced
energy input. Usually, the synthesis methods consist of ve process
steps. Following the clustering and complexation steps, the nucleation
process takes place leading to the formation of nuclei with uniform or
nonuniform size distribution. These nuclei give rise to nanoparticles
following a diusional growth process. The obtained nanoparticles
could be monodisperse, polydisperse or aggregates. Nanoparticles size
and molecular structure are two properties that can be controlled using
the nanotechnology [13].
The role of nanoparticles in catalytic processes is important from
the environmental, social, technological and scientic points of view
because of their relevant characteristics such as activity, selectivity,
durability and recoverability. Understanding of the catalysis processes,
especially the relationship between the structure and composition of
catalyst surface and the catalytic properties, has fundamental impor-
tance in nanoparticles applications. The most important characteristics
that nanocatalysts should satisfy relate to 100% selectivity, extremely
high activity, low energy consumption and long lifetime. This is possible
using precisely controlling the size, shape, spatial distribution, surface
composition and electronic structure, as well as thermal and chemical
nanocomponent stability [21]. Expected advantages of nanocatalysis
applying in chemical industries can be specied as improved economy,
energy eciency, reduced global warming, optimum feedstock utiliza-
tion, safer catalysts and reagents and minimum chemical waste [22].
The active surface, as the most important property of catalysts,
increases when the catalyst size is decreased. So, with smaller particles,
the surface to volume ratio and the reaction eciency are greater and
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Renewable and Sustainable Energy Reviews 72 (2017) 746760
the required amount of catalyst for reaction decreases. The second
relevant property is the spatial organization of the active sites in a
catalyst. A high degree of catalyst selectivity, i.e. the geometrical and
electronic structures, plays an important role in catalyst processes. This
makes heterogeneous catalysis as a prime energy saving technology
[23]. According to Filliponni [23], a typical heterogeneous catalyst
consists of few nanoparticles dispersed on a highly porous support
material having surface areas up to 250 m2 per gram.
Because of a number of favorable nanoparticles catalytic properties,
which are especially related to very high activity, surface reactivity,
large pore size and large surface area compared to macroscopic
catalysts, they are attractive candidates as catalysts for production
environmentally friendly fuels, such as biodiesel. However, although
many advantages of nanocatalysts application are proven, there are a
few drawbacks due to which nanocatalyzed biodiesel productions have
not yet been commercialized. Generally, the problems related to the use
of nanocatalysts can be specied as dicult separation from the
reaction mixture, dicult handling due to the formation of pulverulent
materials, the high pressure drop and leaching of the solid phase.
Dierent solid catalysts in nanoform have been tested in biodiesel
synthesis, such as amorphous alumina powder [24], K2O/Al2O3 [25],
hydrotalcite particles [26], mixed oxide SiO2/ZrO2 [27], Fe3O4 [28],
amino silane modied Fe3O4 [29], Ca/Al/Fe3O4 [30], KF/Al2O3 [31],
potassium bitartrate on zirconia support [32], CsCa/SiO2TiO2 [33],
K2CO3/AlCa [34], etc. Among them, Cabased compounds are very
attractive as catalysts for the use in nanoform for transesterication of
dierent oily feedstocks. In addition, they require mild reaction
conditions and produce high biodiesel yield [9,10]. Advantages and
disadvantages of biodiesel synthesis over nanosized CaOcatalysts in
neat, doped or loaded forms are presented in Table 1.
3. Nano CaO as catalyst in biodiesel synthesis
Unlike many other solid catalysts, nanosized CaO can be prepared
without much eort. The synthesis of nano CaO catalysts is usually
conducted in two main steps: preparation and activation of nanopar-
ticles. The rst step includes dierent methods such as thermal
decomposition, impregnation, mixing and precipitation, while the
second step is most frequently the calcination of the produced
nanoparticles in order to achieve the specic catalytic activity. In this
way, the specic surface area of nano CaO catalysts increases, so that
they can be employed for the transesterication of a variety of raw
materials. Table 2 illustrates an overview on the preparation and
characterization of dierent nano CaObased catalysts.
3.1. Preparation of nano CaO catalysts
3.1.1. Thermal decomposition
Thermal decomposition of fresh raw material, as calcite, involves
the pretreatment at a high temperature in order to decompose the raw
material and to increase the number of active sites at the surface of
catalyst particles. In general, the eciency of the catalyst depends on
the availability of basic sites for catalysis. When CaO is in contact with
air, chemisorption of carbon dioxide and water on the basic sites
occurs, thus reducing the number of active sites for catalysis. The
nature of basic sites on the surface of solid particles depends on the
calcination conditions, temperature primarily. The increase of the
calcination temperature inuences the desorption of molecules, which
blocks active sites, and also the readjustment of the catalyst atoms on
the particle surface [47]. The shape and basicity of obtained CaO
nanoparticles depend on the precursor. For instance, CaO catalyst
derived by calcining Ca(OH)2 shows a higher activity in the transester-
ication reaction than those obtained from CaCO3 or Ca(NO3)24H2O
[48].
As precursors of CaO in nano form, Bai et al. [36] and Yoosuk et al.
[38] used CaCO3 in the form of mineral calcite as an environmentally
I.B. BankoviIli et al. Renewable and Sustainable Energy Reviews 72 (2017) 746760

Table 1
Advantages and disadvantages of biodiesel synthesis over nano-sized CaO catalysts.

Type of catalysts Chemical composition Advantages Disadvantages Reference

Neat CaO Pure CaO Room temperature for reaction Shorter reaction time in the [19]
presence of a co-solvent
Granular form of catalyst give better recyclability
compared to powder form
Pelletized form of catalyst would be more attractive in
commercialization due to easy handling
Much higher conversion rate with nano CaO than with Water present in methanol cannot improve [35]
powder CaO the conversion rate catalyzed by nano CaO
Simple and low-cost route of catalyst synthesis [36]
Reusability of catalyst [19,37]
Reusability of catalyst without re-calcination [38]

Doped CaO LiC/CaO Complete conversion of non-edible oil having a higher [18]
amount of moisture and/or FFAs into biodiesel
Li+/CaO Complete conversion of non-edible oils Catalyst non-recyclability [14])

K+/CaO High tolerance of catalyst to FFA and moisture contents [17]

Reusability of catalyst

KF/CaO Reusability of catalyst [20]

Good anti-acidic ability of catalyst
Superior activity and stability of catalyst
Higher activity and greater tolerance to FFA poisoning
compared to pure CaO

KF/CaO No need for wet washing of biodiesel, so no environmental [39]

pollution
Continuous process with automatic glycerol separation
and cyclic utilization of methanol
Long lifetime and good stability of catalyst, thus reducing
the production cost

K2CO3/CaO High activity of catalyst [40]

Reusability of catalyst

Zn/CaO Reusability of catalyst [41]

Complete conversion of waste and non-edible oils with
high FFA content
High catalyst tolerance to the FFA and moisture contents
Short reaction time

Zr/CaO Reusability of catalyst [15]

High catalyst tolerance to the FFA and moisture contents
KF/(CaO/NiO) Reusability of catalyst [16]

KF/(CaO/MgO) Higher catalyst activity, better resistance to saponification Difficult catalyst separation [42]
and better acidoresistance, compared to CaO and KF/CaO
catalysts

Cheap and environmentally benign material for catalyst Complex recycling

preparation
Reusability of catalyst

KF/(CaO/Fe3O4) High activity of catalyst Ferromagnetic catalyst with no more [43]

Adding water ( < 2.7 wt%) increases reaction rate and significant activity compared to KF/CaO
biodiesel yield in a short time catalyst
Good durability and high recovery of catalyst

Loaded CaO CaO/graphite oxide Excellent activity of catalyst [44]

Easily regeneration of catalyst by simple heat-treatment
High surface area of catalyst

CaO/Fe3O4 Higher activity of the magnetic catalyst than that of pure [45]
CaO
Reusability of catalyst

Ca-aluminate/ Fe3O4 Easily recycling of catalyst with a little loss by magnetic field [30]
Higher catalyst activity and better recovery compared to
catalyst without magnetic property
Reusability of catalyst
Low-cost material Musa balbisiana Colla Very low production cost of catalyst [46]
containing CaO underground stem ash

748
 Table 2
Preparation and characterization of nano CaO catalysts.

Catalyst Catalyst preparation Morphology Diameter (nm) Diameter Surface Basic strength Reusability Reference
(precursor) (nm)/volume area (m2/ (H-)a /basicity
Synthesis Calcination of pore (cm3/ g) (mmol HCl/g)
g)
I.B. BankoviIli et al.

CaO Unknown, commercial product Powder, pellets and 20, 40 90, 20 Powder/pellets (20 nm): 8/4; [19]
granules containing powder (40 nm): 3; granules
crystallites with well- (40 nm): 5
defined edges
CaO powder, 98% Unknown, commercial product < 160 [35]
CaO (moderate Unknown, commercial product 37.3 22.25 9.3 < H- < 15 / 10 (insignificant decrease in [37]
surface area) 13.95 activity)
CaO (high surface Unknown, commercial product 27.3 92/0.2 89.52 15 < H- < 18 / 10 (insignificant decrease in
area) 17.2 activity)
CaO, 97.2 (calcit) Thermally decomposition of fresh 600 C, 3 h Very rough and highly 42.2c - / 0.25 25 12.2 < H- < 15 / 5 (slightly lowered activity after [38]
calcite (CaCO3). Hydration (60 C, 6 h), textured particlesb 1532.4d the second repetition)
ltration, heating (120 C) overnight
CaO Mixing CaCl2 with Na2CO3 (30 s, room 1000 C, 2 h Large and irregular 15100/0.0249 5.3 [36]
(calcit) temperature), centrifugation of CaCO3 crystalsb
precipitate, washing with pure water
and acetone (3 times), drying
LiC/CaO Wet impregnation of Li2CO3 from Hexagonal and oval shaped 4000e, 50f (70c) 15 < H- < 18.4 [18]
aqueous solution, stirring (2 h), clasterse of smaller
evaporation to dry, heating (120 C, particlesb,c
24 h)
Li+/CaO Wet impregnation of LiNO3 from Hexagonal and oval shaped 2000e, 5070f 95.02/0.004 1.7 15 < H- < 18.4 [14]
aqueous solution, stirring (2 h), clasterse of smaller (40c)

749
evaporation to dry, heating (120 C, particlesb,c
24 h)
K/CaO Wet impregnation of KOH from Hexagonal and irregular 20005000e, 50f 5.84 11.1 < H- < 15 3 (recovering by filtration, [17]
aqueous solution, stirring (3 h), drying shaped clusterse of (40c) washing with hexane and drying)
(180 C, 24 h) hexagonal shaped particlesf with partial loss of activity
KF/CaO Impregnation KF from aqueous solution 600 C, 3 h Evenly distributed granules 30100b,c,f 97/- 109 15 < H- < 18.4 / 16 (biodiesel yield at the end: [20,39]
(1 h), backing (105 C, 46 h) and abundant large pores 0.94 91%)
K2CO3/CaO Impregnation via incipient wetness 500 C, 3 h Rounded particlesb 50100 12.85 9.8 < H- < 15 / 5 (recovering by catalyst [40]
method: dropwise addition of K2CO3 0.96 separation, washing with
solution onto CaO, drying (120 C, 16 h) methanol and n-hexane, drying);
insignificant decrease in activity
Zn/CaO Chemical method: 550 C, 12 h Hexagonal, cubic and 20005000b, 13f 10.95 15 < H- < 18.4 5 (recovering by filtration, [41]
Impregnation Zn(CH3COO)2 from irregular-shaped clastersb (23c) washing with hexane and
aqueous solution, stirring (3 h), air- smaller particlesf calcination)
drying
Zr/CaO (-) Wet impregnation of ZrOCl28H2O from 700 C Irregular shaped clusterse 5002000b, 30f 1.86 11.1 < H- < 15 / 4 (recovering by filtration, [15]
aqueous solution, stirring (4 h), of further smaller quasi- (28.5c) 20.21 washing with hexane and
evaporation to dry, heating (120 C, spherical particles calcination at 700 C); FAME
24 h) (monoclinic crystallite)c,f yield: > 99% (second run), 80%
(third run) and 40% (fourth run)
KF/(CaO/NiO) Support preparation: Suspension of NiO 700 C Clastersb with rhombus 1800b, 150f 0.9 15 < H- < 18.4 / 4 (recovering by filtration, [16]
in water and adding Ca(NO3), stirring of shaped particlesf (41.7c) 6.11 washing with hexane and drying
slurry (5 h), drying (120 C, 24 h); (20 C; no decrease in activity);
calcination to mixed oxide CaO/NiO 50% conversion after fth run
(500 C). Wet impregnation of KF from
aqueous solution CaO/NiO, stirring
(4 h), drying (120 C, 24 h)
KF/(CaO/Fe3O4) Magnetic core preparation by co- 600 C, 3 h Particles with a unique 50f 42 20.8 14 (recovering by catalyst [43]
precipitation: dropwise addition of NH3 porous structuref separation from permanent
(continued on next page)
Renewable and Sustainable Energy Reviews 72 (2017) 746760
 Table 2 (continued)

Catalyst Catalyst preparation Morphology Diameter (nm) Diameter Surface Basic strength Reusability Reference
(precursor) (nm)/volume area (m2/ (H-)a /basicity
Synthesis Calcination of pore (cm3/ g) (mmol HCl/g)
g)
I.B. BankoviIli et al.

H2O in solution of FeSO47H2O and magnet, washing with anhydrous

Fe2(SO4)37H2O, stirring (0.5 h), aging methanol, drying), 10% decrease
(1 h), water washing, drying (60 C, in activity
24 h), precipitate pulverization. Mixing
Fe3O4 with CaO, impregnation of KF
from aqueous solution, drying (105 C,
24 h)

KF/(CaO/MgO) Support preparation via coprecipitation: 600 C, 3 h Grains mesoporous 100300f, 35c 34 113.8 6 (FAME yield: 90%) [49]
dropwise addition of solution of CaCl2 structuref
and MgCl2 in solution of Na2CO3 and
NaOH, aging (60 C, 6 h), ltration,
water washing, drying, calcination
(800 C, 4 h). Isochoric impregnation by
KF.

CaO/graphite oxide Mixing aqueous solution of Ca(NO)3 800 C, 1 h Grains 27c, 24c,g 10.7, 10.0g 437, 439g 4 (regeneration at 600 C); 2g [44]
and graphite oxide, stirring (2 h), (FAME yield: 18.6% after 4 h)
evaporation (80 C, atmospheric
pressure)
CaO/Fe3O4 Magnetic core preparation: dropwise 800 C, 8 h Cuboid particlesb 49.76c 3.72 4 (no decrease in activity). FAME [45]
addition of NH3 in solution of FeSO4 yield: > 90% (fifth run), 70%
7H2O and Fe2(SO4)37H2O, stirring), (tenth run)

750
aging (1 h), water washing. Adding
magnetic core in CaCl2 solution.
Titration by NaOH or Na2CO3 under
stirring, aging (65 C, 18 h),
precipitation in magnetic eld, washing,
vacuum drying (12 h, 80 C)
(Ca/Al)/Fe3O4 Calcination of CaCO3 to CaO (1000 C, 600 C, 6 h Particles with low 31.51c 25.89 5 (FAME yield: 93.53%) [30]
10 h), that was hydrated to Ca(OH)2. agglomerationb
Addition Al-sheet in NaOH solution to
obtain Na-meta-aluminate solution.
Addition nano-Fe3O4 in mixed solution
of NaOH and Ca(OH)2, stirring (80 C,
5 h). Powders washing, dehydration
using alcohol, vacuum drying (12 h).
Musa balbisiana Cuting into thin pieces, drying, burning Particles like bricksf 702015f. 2.187/0.042 38.71 9.3 < H- < 15 2 (no decrease in activity). 20% [46]
Colla under- to ashes, drying (550 C, 2 h) Length: < 100f activity reduction in the third run
ground stem ash
(10% CaO)

a
Hammett indicator,
b
SEM,
c
XRD,
d
mol CO2/g,
e
FESEM,
f
TEM,
g
Calcination in argon ow.
Renewable and Sustainable Energy Reviews 72 (2017) 746760
I.B. BankoviIli et al.
friendly material of low toxicity and price and high basicity. Bai et al.
[36] developed a simple and lowcost route for preparing the CaO
catalyst with a new morphology and a high catalytic activity. The
catalyst was synthesized by the thermal decomposition of spherical
CaCO3 precursor, which was previously obtained by mixing CaCl2 with
Na2CO3. After the spherical CaCO3 was calcined at 1000 C, CaCO3
nanoparticles were decomposed into large and irregular CaO nano-
crystals. Yoosuk et al. [38] reported that neat and/or modied CaO
obtained by the calcination of calcite could be successful used as a solid
catalyst in the biodiesel synthesis, but it was less eective than
homogeneous catalysts, due to its less basicity and surface activity.
Therefore, a technique combining the thermal decomposition of
natural calcite and the hydrationdehydration method was recom-
mended, which could improve the activity, basicity and specic surface
area of the catalyst in nano form. This technique generated a new CaO
in nano form with excellent textural properties and a large number of
basic sites, which could be suitable as a solid catalyst in the biodiesel
production. During the catalyst preparation, the carbonate decom-
posed into CaO, which were further hydrated to form Brnsted basic
sites. The decomposedhydrated calcined calcite had a higher activity
than the decomposed natural calcite.
3.1.2. Impregnation
The impregnation method of an active catalyst precursor was
usually used to obtain doped CaO catalysts. The basic strength of
CaO catalysts is enhanced when alkali metal ions are impregnated onto
nano CaO particles. In a typical preparation, CaO solid carrier is rst
suspended in water, then the aqueous solution of the precursor is
added and nally, the catalyst is calcined at the temperature between
500 C and 900 C in order to transform the precursor to the active
form [1418,20,39,42,43]. High calcination temperature favors the
interaction between the carrier and the active component to form new
crystals, i.e. new active sites, but overheating results in the surface
sintering and the reduction of the specic surface area, i.e. the catalytic
activity [20].
The activity of a doped CaO catalyst depends on the type of metal
ion, available basic sites of CaO and interaction between metal ions and
CaO. Ions of alkali metals (Li+, K+ and Na+) with various concentration
are used as an impregnation precursor. Kumar and Ali [18] reported
that nano CaO impregnated with alkali metal ions showed a high
specic surface area, compared to neat CaO; the highest specic surface
area was found in the case of lithiumimpregnated CaO. The basic
strength of the alkali metal ion impregnating CaO and the catalytic
activity toward transesterication decreases with increasing the ion
size. The amount of Li+ ions impregnated onto CaO that provides the
best catalytic activity is 1.5% [18] or 1.75% (related to carrier amount)
[14], while the best amount of impregnated K+ ions is 3.5% (related to
carrier amount) [17], i.e. 3% (related to oil amount) [40]. But, Kumar
and Ali [41] reported that alkali metal doped nano CaO showed
poor stability and suered from leaching of active species into the
reaction medium. Therefore, they tried the use transitionmetal ions,
such as Mn, Fe, Co, Cu, Ni, Zn and Cd, for the CaO activation and
demonstrated that the Zn/CaO catalyst showed the best activity
toward transesterication under the optimized reaction conditions
among the prepared catalysts due to its highest basic strength.
Moreover, the nanoZn/CaO catalyst showed better resistance
toward moisture unlike neat CaO, even after exposure to atmospheric
moisture. It was found that the Zn/CaO catalyst activity could be
enhanced when the Zn2+ concentration increased up to 1.5%; a
further increase in the ion concentration had no inuence on the
activity of the catalyst. Further, when Zr2+ ion was applied for the
preparation of a Zr/CaO nanocatalyst, the zirconium concentration was
15% [15].
Also, Kaur and Ali [16] and Hu et al. [43] rst prepared the mixed
oxides CaO/NiO and CaO/Fe3O4, respectively which were then im-
pregnated with KF to improve the catalytic activity of CaO. Metal mixed
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Renewable and Sustainable Energy Reviews 72 (2017) 746760
oxides usually possess a higher catalytic activity than corresponding
neat oxides, as their active centers could be either oxygen atoms or the
dopant itself [16]. The catalysts having 20 wt% [16] or 25 wt% [43] of
the impregnated K+ showed the best catalytic activity. When the K+
amount was higher than the indicated one, the catalyst basicity did not
increase because KF covered the active centers and the required time
for the complete TAG conversion was not shorter. The increase in the
KF concentration during the impregnation led to the formation of
KCaF3 as a new phase, which could inuence the catalyst activity and
stability [16,20,43].
3.1.3. Mixing
The method of physical mixing is often used for obtaining the
catalyst consisting of a metal oxides mixture when it is possible to apply
a larger amount of the active component on the oxide with the carrier
role. In this way, the catalyst with a smaller specic area and thereby a
smaller concentration of basic active sites is obtained [49]. For
instance, Kaur and Ali [16] used this physical method for the
preparation of a CaO/NiO mixed oxide catalyst serving as a carrier,
which was then impregnated with KF in order to obtain the nanoca-
talyst for the complete conversion of waste cottonseed oil by the
methanolysis reaction.
3.1.4. Coprecipitation
The coprecipitation method was applied for the preparation of
catalysts with a higher basicity. Using this method, Wang et al. [42]
prepared a twocomponent complex carrier (CaO/MgO), which was
isochorically impregnated by KF in order to obtain the mesoporous
nanosized catalyst with a large surface area and a relatively big size.
The authors mentioned that this catalyst with mesoporous structure
could more easily be separated from the product, compared to the
nanosize catalyst. Liu et al. [45] prepared a nanomagnetic catalyst by
loading CaO onto Fe3O4 using aqueous solutions of NaOH or Na2CO3
as a precipitator. It was referred that the catalysts obtained by
calcinating Ca(OH)2 on Fe3O4 had a higher catalytic activity than that
obtained by calcinating CaCO3 on Fe3O4. The catalyst characterization
proved a new kind of cuboid crystalloid with high activity, Ca2Fe2O5,
which was formed by calcinating the precursors and some of the neat
CaO attached on the surface of the cuboids. The best proportion
Ca2+:Fe3O4 for achieving the highest biodiesel yield was 7:1. At higher
value than 10:1, there was more the pure CaO on the particle surface
which prevented the contact between the reagents and the catalyst. But,
at a lower value (5:1) there were less active crystalloids formed.
3.2. Activation of CaO catalysts
Generally, the activated form of nano CaObased particles can be
obtained by the method of calcination at enhanced temperatures in the
two main cases:
1) the calcination of CaO precursor, after washing and drying in air
[36], or afterwards using the hydration method [38], and
2) the calcination of CaO in neat [38], doped or loaded forms after
dierent preparation methods, such as wet impregnation
[15,16,20,39], chemical [41], incipient wetness [40] or mixing
method [16].
3.3. Forms of nano CaO catalysts used in biodiesel synthesis
Various compounds are used as heterogeneous catalysts in many
reported investigations of biodiesel synthesis. Their catalytic activity
depends on the nature, size and specic surface of catalyst particles and
the applied reaction conditions. The most of the previous researches
refer to the use of the alkaline earth metal oxides and hydroxides,
whereby their basic strength increase in the order of Mg < Ca < Sr < Ba.
Among them, CaO shows the greatest potential in the transesterica-
I.B. BankoviIli et al.
tion reaction, because of its already mentioned favorable properties.
However, due to low activity of commercial CaO toward transester-
ication reaction, CaO prepared in nanocrystalline form has occupied a
more attention in the last time. The diverse forms of nano CaO, such as
neat, doped, loaded or waste, are presented in the literature as catalysts
in biodiesel synthesis from dierent feedstocks. Neat CaO particles
easily form hydrogen bonds with methanol or glycerol, thus complicat-
ing the posttreatment and phase separation and increasing the total
production costs. The solution of the problems related to neat CaO can
be overcome by using doped and loaded CaObased catalysts in nano
form.
3.3.1. Neat CaO
Reddy et al. [19] rst investigated the methanolysis of soybean oil
and poultry fat in the presence of nanocrystalline CaO as a solid
catalyst in the form of powder, pellets and granules at room tempera-
ture. They found that the high biodiesel yield could be obtained (about
100%) with both feedstocks. The high methanol/oil molar ratio (27:1)
for the reaction was needed, but the higher surface area associated with
the small crystallite size enhanced the nano CaO reactivity and the
reaction kinetics. It was found that the granular form of catalyst gave
better recyclability than the powdered form. Also, the pelletized form of
catalyst would be more attractive in commercialization because of easy
handling. Additionally, tetrahydrofuran as a cosolvent accelerating the
miscibility of oil and methanol as reactants played an important role in
shortening the reaction time for twice. However, the production of
biodiesel under the same conditions, without cosolvent, in the presence
of commercial laboratorygrade CaO was unsuccessful, indicating by a
very low TAG conversion degree (only 2%). Also, Reddy et al. [19]
investigated the eciency of a series of nanocrystalline metal oxides for
the oil transesterication, such as Mg, Zn, Al, Ti and Ce oxides. Except
for powder of MgO, when only 6% conversion was achieved, no
observable reaction occurred in the presence of the other nanooxide
catalysts.
Comparing the catalytic eects of the two forms of CaO (powder
and nano) on the biodiesel synthesis assisted by microwave irradiation,
Hsiao et al. [37] found that after the 30 min reaction, the conversion
rate was signicantly higher (about 30 times) when nano CaO was
used. This was attributed to the larger contact surface of the nanoca-
talyst particles.
Yoosuk et al. [38] reported a simple and exible method to increase
the activity of calcined natural calcite, which might contribute to the
development of better solid catalysts for the biodiesel synthesis. The
authors compared catalytic activities of a commercial CaO powder and
a nano CaO form obtained by the calcination and hydrationdehydra-
tion of fresh calcite. It was found that the Cacarbonated form (fresh
calcite) did not have enough basicity to catalyze the reaction and to
produce the appropriate esters. But, after the calcination of calcite at
800 C, the nano CaO was formed. Its catalytic activity was proved by
achieving 75.5% ester yield within 1 h. The hydrated form of the
obtained catalyst possessed lower activity (3.5% ester yield), while after
the dehydration of the same nanocatalyst and recalcination at 600 C,
the greatest activity was observed (93.9% ester content in 1 h). Also,
these research group conrmed that commercial CaO had a lower
activity to catalyze transesterication reaction at the same conditions
than the nano CaO.
Zhao et al. [37] investigated the activity and stability of two types of
commercial nano CaO catalysts with various specic surface areas for
the biodiesel production. The both nanocatalysts exhibited high activity
but the catalyst with larger surface area and higher basic strength
resulted in a 10 fold decrease in the catalyst amount required to reach
high biodiesel yield. Also, the both nanocatalysts had higher activity
than the laboratorygrade CaO. This can be explained by the sig-
nicantly reduced internal diusion limitation because of shorter paths
that molecules should pass to access active sites and the larger surface
area that increases the availability of the basic sites for the reaction. In
752
Renewable and Sustainable Energy Reviews 72 (2017) 746760
other words, the catalyst activity is determined by both the basic
strength and the number of accessible active sites.
Teo et al. [50] did not suggest neat CaO for industrial application
because of calcium leaching and the formation of calcium diglyceroxide
reducing the reusability and environmental sustainability of the
catalyst. Hence, they recommended the use of calcium metoxide in
nano form, which was prepared by the dispersion of neat CaO in
dehydrated methanol, followed by methanol evaporation and drying.
Because of its eciency, low toxicity, cost eectivity and easy prepara-
tion, nano calcium methoxide is indicated as a green catalyst.
3.3.2. Doped CaO
In order to increase the basic strength of the neat CaO catalyst,
doping of some catalytically active species onto a CaO carrier is
recommended. For this purpose, the most frequently used loaded
materials are oxides of alkali and alkaline earth metals. They are
prepared from corresponding precursors, thermally nonstable porous
substances, by calcination at high temperatures. Applying the impreg-
nation method for the preparation of a catalyst in nano form, numerous
researchers have used these doped CaObased catalysts for the
transesterication of feedstocks containing FFAs [1418,20,3943].
These investigations deal with the inuence of type and concentration
of the impregnated ion, concentration of catalyst, reaction temperature,
alcohol/oil molar ratio as well as moisture and FFA contents on the
ester production.
By testing the inuence of dierent alkali metal ions, such as Li+, K+
and Na+, on the catalyst activity, Kumar and Ali [18] found the highest
basic strength in the case of LiCdoped CaO, probably because of the
formation of strong basic sites on the CaO surface. The authors proved
that the LiC/CaO catalyst showed the highest activity in the transester-
ication reaction of vegetable oil that resulted in the complete oil
conversion in only 45 min at 65 C, and within 6 h at 35 C. Thus, this
nanocatalyst has a potential for converting the cheap feedstocks
containing higher moisture and FFA contents to biodiesel with the
reduced production cost. Another research group found that the Li
impregnated CaO catalyst had a higher specic surface area in
comparison with neat CaO [14,18]. Similarly, the doping of K+ions
on CaO produces a catalyst eective in the transesterication of various
feedstocks such as soybean, cotton, castor, karanja and jatropha oils,
mutton fat [17], Chinese tallow seed oil [20] and rapeseed oil [39].
Also, K2CO3 doped on CaO oers the advantages of easy impregnation,
lower cost and environmental inertness [40]. The complete conversion
of waste oil over Zn/CaO [41] and nonedible oils over Zr/CaO [15]
were achieved at 35 C and 65 C, respectively.
CaO also has a potential to mix with other oxides such as NiO, MgO
or Fe3O4. For instance, Kaur and Ali [16] demonstrated the complete
transesterication of waste cottonseed oil over KFdoped CaO/NiO
mixed oxide in nano form. Also, Wang et al. [42] used the KF/(CaO/
MgO) nanocatalyst for obtaining the 95%ester yield from rapeseed
oil. Higher catalyst activity, cheap and environmentally benign material
for catalyst preparation, better resistance to saponication and better
acid resistance, compared to CaO and KF/CaO catalysts, represents
important advantages of this catalyst. Hu et al. [43] compared the
catalytic activity of a series of nanomagnetic solid base catalysts such
as KF/(CaO/Fe3O4), KF/(MgO/Fe3O4) and KF/(SrO/Fe3O4). The cat-
alytic activity was in accordance with its specic surface area. Hence,
the nanoKF/(CaO/Fe3O4) catalyst showed the best activity, which was
proved by the highest ester yield (higher by about 10%), compared to
other two catalysts. However, the magnetic core had a little eect on
the catalytic activity of the nanoKF/(CaO/Fe3O4) catalyst, compared
to nanoKF/CaO, since the ester yields obtained with the two catalysts
were approximately the same.
3.3.3. Loaded CaO
Several studies have reported the immobilization of CaO on
dierent carriers to get socalled the loaded CaO form which is shown
I.B. BankoviIli et al.
as an active catalyst for transesterication reactions. Graphite oxide
produced by the controlled oxidation of graphite [44] and magnetic
Fe3O4 [32,45] are used in the form of nanoparticles as carriers for the
loaded CaO. The graphite oxide loaded CaO nanocatalyst with high
surface area exposes excellent activity and is easily regenerated by
simple heattreatment. The groups containing oxygen (i.e. hydroxyl,
epoxide, carboxyl) on the graphite oxide carrier surface probably act as
eective anchoring centers for the active phase (CaO), thus resulting in
the formation of an active and stable catalyst. A high biodiesel yield
(98%) was achieved by the methanolysis of soybean oil in the presence
of the CaO/graphite oxide catalyst [44]. Magnetic solid base nanoca-
talysts combine the advantages of base homogeneous (the high specic
area) and heterogeneous (easily separation from reagents) catalysts
[45], thus preventing the catalyst loss and reducing the overall
production costs. In the methanolysis of jatropha oil, CaO loaded on
Fe3O4 magnetic core, gave 99% conversion within 4 h. It was proved to
be more ecient than neat CaO. Tang et al. [30] developed a magnetic
composite catalyst by loading calcium aluminate onto magnetic Fe3O4
nanoparticles (Ca/Al/Fe3O4) to improve the catalytic activity and
recovery. The biodiesel yield of 98.7% was achieved from rapeseed
oil under the optimum reaction conditions. The comparison of the two
nanocatalysts, with and without magnetic properties, showed the
former catalyst had smaller size and higher specic surface area.
3.3.4. Waste CaO
The use of wastes as raw materials in the preparation of a
nanocatalyst for biodiesel synthesis was reported only in the study of
Sarma et al. [46]. They investigated the preparation, structure,
composition and use of the ash obtained from underground stems of
a banana tree (Musa balbisiana Colla) as the nanocatalyst for the
transesterication of jatropha oil having a high percentage of FFAs. The
catalyst with 10% of CaO was very eective during the jatropha oil
methanolysis under high pressure (4.2 MPa) and temperature (275 C)
as a high ester yield (98%) was obtained. The main advantage of this
catalyst is a very low cost of its production from priceless waste
underground stems.
4. The eect of operating conditions on biodiesel yield in the
presence of nano CaO
Previous investigations of the use of nano CaO catalysts in biodiesel
production include the inuence of dierent operating conditions on
the biodiesel yield, such as: contents of moisture and FFAs in raw
feedstocks, type and concentration of impregnated ion on CaO carrier,
catalyst amount, calcination and reaction temperatures, alcohol type,
alcohol/oil molar ratio, presence of cosolvent and catalyst reuse. A
review of the reaction conditions applied so far in biodiesel synthesis
over nano CaObased catalysts is given in Table 3.
4.1. Calcination temperature and time
In order to remove the adsorbed moisture and carbondioxide
molecules from the catalyst surface, the catalyst particles must be
calcined at a higher temperature in a certain period of time. By
calcination, the catalyst activity can be restored and even improved.
The calcination temperature and time are crucial for the generation of
active sites on the catalyst particle surface and the structural and
catalytic properties of catalysts. Hence, there have been a few attempts
to optimize both temperature and time duration of calcination of
various nano CaObased catalysts [51]. The values of optimal tem-
peratures of calcination for dierent nano CaObased catalysts are
given in Table 2.
The eect of the calcination temperature and time on the biodiesel
yield was investigated for dierent nano CaOdoped catalysts such as
KF/(CaO/MgO), KF/(CaO/Fe3O4) and Zn/CaO by Wang et al. [42], Hu
et al. [43] and Kumar and Ali [41], respectively. Generally, with the
753
Renewable and Sustainable Energy Reviews 72 (2017) 746760
increase of the calcination temperature and time the biodiesel yield
with the nano KF/(CaO/MgO) catalyst increases to a maximum yield
value and then decreases [4143]. At the optimal calcination tempera-
ture, the active centers are well developed, contributing to the favorable
eciency of the catalyst. However, the number of catalyst active sites
decreases at temperatures higher than the optimal one and with a
prolonged calcination because of surface sintering and the reduction of
specic surface area. A similar observation was reported for the loaded
(Ca/Al)/Fe3O4 composite magnetic nanocatalyst by Tang et al. [30],
who suggested that the increase in the biodiesel yield with the increase
of the calcination temperature was due to the gradual development of
stable catalyst crystals with a high specic surface area. After achieving
the ester yield maximum, a part of the active component of the catalyst
may be lost and catalyst agglomeration will happen at higher calcina-
tion temperatures, thus resulting in decreasing the ester yield.
4.2. Water and FFA contents
In the case of homogeneous catalysts, the presence of > 0.3 wt%
water and/or > 0.5 wt% FFA in the starting reaction mixture leads to
the saponication instead transesterication reaction [52]. For the
heterogeneous catalysts in nano form, the upper limits for water and
FFA contents for achieving the complete transesterication depends on
the type of nano CaObased catalyst (Table 4). For instance, for
complete transesterication of waste cottonseed oil the limit moisture
content is 10.3 wt% for K/CaO [17], 15 wt% for nano LiC/CaO [18],
6 wt% for Zr/CaO [15] and 4.3 wt% for Zn/CaO [41]. The smaller
activity of doped catalysts in the presence of high water amount in the
reaction mixture is the consequence of the reaction between water and
the catalyst carrier (CaO), which converts stronger Lewis basic (O)
sites back into weaker Brnsted basic (OH) sites [15,41].
The eect of water content in methanol on the biodiesel yield
during the microwaveassisted soybean oil methanolysis using a nano
CaO powdered catalyst was analyzed by Hsiao et al. [37], who found
that the conversion rate and the biodiesel yield increased with
increasing the water content up to 2 wt%. Hu et al. [43] found the
increase of the biodiesel yield with increasing the water content up to
2.7 wt% in the conversion of Stillingia oil catalyzed by a nano
magnetic KF/CaO/Fe3O4 catalyst. The observed phenomenon can be
explained by the adsorption of water molecules on the catalyst surface
forming OH groups, which after that abstract proton from methanol
molecule and generate active CH3O anion. Also, the catalyst can
behave in a similar way. However, OH ion is more easily adsorbed on
the catalyst surface than methoxide anion. Consequently, the addition
of a small amount of water accelerates the reaction and increases the
biodiesel yield. If too much water (higher than the limit) is added to
methanol, the biodiesel yield decreases with the increase of water
content because of deterioration of the catalyst and the ester hydro-
lysis.
Kumar and Ali [18] found that the maximum water content in
waste cottonseed oil must be less than 15 wt%. Also, they studied the
combined eect of moisture and FFA contents on the activity of the
nano LiC/CaO catalyst. The complete oil conversion to biodiesel was
achieved for 4 h with 5 wt% of water and 2 wt% of FFA. The further
increase of either moisture or FFA amount led to the saponication
reaction.
Under the optimal reaction conditions, the K/CaO and Zn/CaO
nanocatalysts contributed to the complete conversion of waste cotton-
seed and jatropha oils having up to 8.4 wt% FFAs, respectively [17,41].
In order to determine the maximum tolerance of nanocatalysts on
FFA content in starting oil, some authors [14,16,18] added palmitic
acid in the reaction mixture. For the complete transesterication of
waste cottonseed oil over the nano LiC/CaO catalyst, the FFA content
must not be higher than 6 wt% [18]. The nanoLi/CaO catalyst was
eective for the complete conversion of karanja and jatropha oils when
the maximum FFAs content was 6.4 wt% and 10.3 wt%, respectively
I.B. BankoviIli et al. Renewable and Sustainable Energy Reviews 72 (2017) 746760

(continued on next page)

[14]. The nano KF/CaO/NiO catalyst was resistant to the presence of

Reference
maximally 3 wt% of added palmitic acid while the further increase in
the FFA content deactivated the catalyst and only partial conversion of

[19]

[35]

[38]

[36]
[37]

[18]

[14]

[17]
waste cottonseed oil was realized within 14 h [16].

4.3. Type and concentration of impregnated metal ions

Kumar and Ali [18] analyzed the eect of dierent alkali metal ions

(Conversion),
(Li+, K+ and Na+) on the catalyst activity during the transesterication

%/Time, h
Optimal reaction conditions

(100)/0.75

> 99/1.25
95.7/0.75
of waste cottonseed oil. The basic strength and activity were reduced

(96.6)d/1

> 99/2.5
98.72/ 3
99.85/2
(99)/24

(100)/6
(99)b/6

> 99/2
(99)/1
(99)/2
100/1
Yield
with the increase of alkali metal ion size. The highest activity was found
for the nanoLi/CaO catalyst. In order to determine the optimal
amount of the impregnated metal ion on CaO surface, a series of

12:1; 7.5%; 65 C
9:1; 0.3%; 65 C

12:1; 5%; 65 C

12:1; 5%; 65 C
catalysts with dierent concentration of metal ions have been prepared

7:1; 3%; 65 C

9:1; 3%; 65 C
conditions
and applied in the oil transesterication at various operating conditions

Reaction
[1418,20]. The optimal concentration of Li+ ion was found to be 1.5%
[18] or 1.75% [14]. However, the optimal concentration of K+ ion was
in a wide range, depending on the type of feedstock and the type of
nanocatalyst: 3.5% with waste cottonseed oil and K/CaO [17], 20%
with waste cottonseed oil and KF/(CaO/NiO) [16] and 25% with

Tempe-
rature,

5065

6065
6065

3565

3565

3565
Chinese tallow seed oil and KF/CaO [20]. When the amount of doped

room
C

60

65
metal ion was higher than the optimal, the basic strength and activity of
the nanocatalyst stayed constant and the reaction time needed for the

Catalyst/amount (wt% to
complete conversion of oil decreased to a minimum value which did
not change further. When Zr4+ was used for doping of the nano CaO
catalyst, the maximum basic strength was achieved with 15 wt% of Zr

K/CaO/2.512.5
[15].

Li+/CaO/110
LiC/CaO/18
CaOf/0.10.5
Mixed oxides with higher activity than corresponding neat oxides

CaO/1 mmol
CaO/0.056g

CaOe/24
CaO/1.13
can be satisfactory applied as catalysts in oil transesterication reaction.

CaO/13
the oil)

CaO/7

CaO/3
For instance, the basic strength of mixed oxides CaO/NiO [16], CaO/
Fe3O4 [43] and CaO/MgO [42] impregnated by KF increases with
increasing the K+ concentration, due to the formation of KCaF3 and
Alcohol: oil molar

KMgF3 compounds. After achieving the optimal ion concentration of

ratio, mol/mol

20 wt% [16] or 25 wt% [42,43], the catalyst activity decreases due to

covering the active sites and the decrease of the active surface for catalysis. 6:110:1

6:112:1

3:118:1

3:112:1

6:121:1
15:5a
10:3c
27:1

15:1
4.4. Catalyst concentration
9:1
The review of the reaction conditions applied for biodiesel synthesis in the presence of nano CaO catalysts.

The strong basic catalysts can accelerate the transesterication

reaction of oily feedstocks even at small catalyst concentrations
Methanol

Methanol

Methanol

Methanol
Methanol

Methanol

Methanol

Methanol
Type of
alcohol

[53,54]. The increase of the catalyst concentration increases the ester

yield due to the increase of the available active sites for the reaction
[37]. However, there is an optimal amount of the catalyst that depends
Three neck flask, 250/electromagnetic,
Type of stirrer, stirring intensity,

Three neck flask, 100/magnetic, 600

on the used feedstock and the applied reaction conditions [14

Round-bottom flask, 200/ magnetic,
Type, volume of reactor, cm3/

18,20,37,40]. For the catalyst concentration higher than the optimal,

the ester yield does not increase signicantly, due to the higher
Two neck flask/ magnetic, -
Centrifuge tube/magnetic, -

viscosity of the threephase reaction mixture and the mass transfer

Three neck flask, 250/ -

resistance [15] or the initiation of the saponication reaction [37].

Two neck flask/-

Two neck flask/-

4.5. Reaction temperature

The rate of transesterication in the presence of nano CaObased

rpm

catalysts signicantly increases with the rise of the reaction tempera-

350

500

ture [20]. The most researchers have shown that the optimal tempera-
Waste cottonseed

ture for the oil methanolysis is the boiling point of methanol (65 C) at
Used cottonseed

the atmospheric pressure. Higher temperatures than the optimal one

Jatropha oil

Jatropha oil
Feedstock

Soybean oil
Soybean oil

Soybean oil

Soybean oil

Karanja oil

Karanja oil
Palm olein
Poultry fat

Canola oil

neither decrease the reaction time nor increase the conversion rate
[1418,20,37]. When the reaction temperature exceeds the boiling
oil

oil

point of methanol, it begins to evaporate, the contact time between

methanol and oil is reduced and the biodiesel yield is lower [20,37].
Although the nano CaObased catalyst is very eective at 65 C, the
Type of catalyst

complete oil conversion into biodiesel can also be observed at lower

Doped CaO

temperatures (35 C) but in a longer reaction time [15,16,41]. Also,

Neat CaO

Reddy et al. [19] reported that, when the reaction was performed at
Table 3

room temperature, approximately 24 h was needed to complete the

conversion of soybean oil using the nano CaO as a catalyst (Table 3).

754
 I.B. BankoviIli et al.

Table 3 (continued)

Type of catalyst Feedstock Type, volume of reactor, cm3/ Type of Alcohol: oil molar Catalyst/amount (wt% to Tempe- Optimal reaction conditions Reference
Type of stirrer, stirring intensity, alcohol ratio, mol/mol the oil) rature,
rpm C Reaction Yield
conditions (Conversion),
%/Time, h

Chinese tallow Three neck flask, 250 / - Methanol 6:112:1 KF/CaO/15 5070 12:1; 4%; 65 C 96/2 [20]
seed oil
Rapeseeed oil Continuous reactor (diameter 6 cm, Methanol KF/CaO 7090 81.5 C 93.7/- [39]
length 65 cm) lled with glass beads vaporg
Waste cottonseed Two-neck flask, 100 /magnetic, 500 Methanol 3:118:1 Zn/CaO /110 3565 9:1, 5%, 65 C 99 / 0.75 [41]
oil
Jatropha oil Two neck flask, 50/ magnetic, 500 Methanol 3:118:1 Zr/CaO/16 3565 15:1; 5%; 65 C 99/1.83 [15]
Ethanol 3:124:1 4575 21:1; 5%; 75 C 99/7.1
Canola oil Batch reactor, 1000/ magnetic, 600 Methanol 6:118:1 K2CO3/CaO/17 2565 9:1; 3%; 65 C 97.67/8 [40]
Waste cottonseed Two neck flask, 250/ magnetic, - Methanol 3:118:1 KF/(CaO/NiO)/ 3575 15:1; 5%; 65 C 99/4 [16]
oil 16
Rapeseed oil Glass reactor, 100/ magnetic, - Methanol 12:1 KF/(CaO/MgO)/3 70 C 95/3 [42]
Stillingia oil Glass reactor, 100/ mechanical, - Methanol 12:1 65 95/3 [43]

755
KF/(CaO/Fe3O4)h/1

Loaded CaO Soybean oil Three neck flask, 50 /- Methanol 0.83:1 CaO/graphite oxide /8 60 98.3/ 2 [44]
97.8i/2
Jatropha oil Three neck flask, - / - Methanol 15:1 CaO/ Fe3O4h/2 70 (99)/4 [45]
Rapeseed oil Round-bottom flask, 250/magnetic, Methanol 15:1 (Ca/Al)/Fe3O4h/6 65 98.71/3 [30]
270

Low-cost material Jatropha oil Batch reactor, 1800 /-, 650 Methanol 9:1 Musa balbisiana Colla 60275 275 C 98/1 [46]
containing CaO underground stem ash (10%
CaO)/5

a
mL/mL.
b
THF as co-solvent.
c
mL/g.
d
Microwave irradiation (2.45 GHz, 300 W).
e
moderate surface area.
f
high surface area.
g
Countercurrent phases ow, ow rates (mL/min): oil 18, methanol 1620.
h
Magnetic properties.
i
Catalyst preparation in inert atmosphere of Ar.
Renewable and Sustainable Energy Reviews 72 (2017) 746760
I.B. BankoviIli et al. Renewable and Sustainable Energy Reviews 72 (2017) 746760

Table 4
The limits of water and FFAs contents in the starting feedstock and the optimal impregnated ion content needed for complete conversion.

Feedstock (oil) Catalyst Water/FFA contents (wt% of oil) Optimal impregnated ion content (wt% to CaO) Reference

Soybean CaO 2a/- [35]

Waste cottonseed LiC/CaO 15/6 1.5 [18]

Karanja Li+/CaO -/6.4 1.75 [14]

Jatropha -/10.3
Waste cottonseed K/CaO 10.3/8.4 3.5 [17]
Chinese tallow seed KF/CaO 25 [20]
Waste cottonseed Zn/CaO 4.3/- 1.5 [41]
Jatropha Zn/CaO -/8.4 1.5
Jatropha Zr/CaO 6/15 15 [15]
Canola K2CO3/CaO 3 [40]
Waste cottonseed KF/(CaO/NiO) -/3 20 [16]
Rapeseed KF/(CaO/MgO) 25 [42]
Stillingia KF/(CaO/Fe3O4) 2.7/- 25 [43]

a
- wt% of methanol.

The positive eect of increasing the reaction temperature on the
reaction rate and the biodiesel yield was observed by Sarma et al.
[46], who used the ash of underground stems of Musa balbisiana Colla
with 10% of CaO as a nanomaterial for the catalysis of jatropha oil
methanolysis under high pressure. The same result was obtained when
methanol was replaced with ethanol. The optimal temperature for the
ethanolysis of jatropha oil under atmospheric pressure is the boiling
point of ethanol (75 C) [15].
4.7. The eect of cosolvent
Reddy et al. [19] added a cosolvent (tetrahydrofuran) to the
reaction mixture (soybean oil/methanol/neat nano CaO) in order to
promote the phases miscibility, to enhance the contact between the
system components and to accelerate the reaction rate. The 99%
conversion of soybean oil to biodiesel was achieved for a twice shorter
reaction time under the same other reaction conditions, compared to
the reaction in the absence of the cosolvent.

4.8. The eect of microwave irradiation

4.6. Type of alcohol and alcohol/oil molar ratio
Kumar and Ali [41] rst used a nano CaObased catalyst (Zn/CaO)
in the transesterication of waste cottonseed oil with a variety of
alcohols. They found the same ester yield (99%) in the methanolysis
and ethanolysis of waste cottonseed oil catalyzed by the nanoZn/CaO
catalyst, but the reaction time in the former (45 min) was shorter than
in the latter (60 min). To investigate further the inuence of the
inherent carbon chain length of the alcohol on the catalyst activity,
the authors tested a series of aliphatic alcohols and observed the
increase of the reaction time with the increase of the carbon chain
length from 1 to 8. A further increase in the carbon chain length (912)
did not inuence the catalytic activity signicantly. The changes in the
catalyst activity can be caused by the reduction in the acidic alcohol
strength and the change in the alcohol solubility.
Also, Kaur and Ali [15] performed the transesterication of
jatropha oil with methanol and ethanol over the nano Zr/CaO catalyst
(5%). The same high biodiesel yield (99%) was achieved with both
alcohols, but in a much longer reaction time (about 4 times) and at a
higher alcohol/oil molar ratio with ethanol than with methanol.
Although the theoretical minimal alcohol/oil molar ratio, necessary
for achieving the complete oil conversion is the stoichiometric one
(3:1), the transesterication reaction is usually performed with an
excess of methanol. For heterogeneous catalysis, a high methanol/oil
molar ratio is needed not only to shift the equilibrium toward the
forward direction and to obtain the maximum biodiesel yield, but also
to wash the product molecules from the catalyst surface and to
regenerate the active sites [16].
The rate of the transesterication reaction increases with increasing
the alcohol/oil molar ratio to a limit above which the reaction time is
not signicantly reduced [1418,20,37,40,41]. This limit is the opti-
mum alcohol/oil molar ratio, which depends on the applied reaction
conditions (Table 3). The decrease of the conversion rate above the
optimum alcohol/oil molar ratio is attributed to the dicult separation
of the phases [37].
Hsiao et al. [37] investigated the eciency of the transesterication
of soybean oil over nano CaO catalyst in the absence and the presence
of microwave irradiation. The conversion degree achieved in the same
reaction time (30 min) was about twice higher if the reaction mixture
was irradiated with microwaves.
4.9. Continuousow integration process
Currently, when nano CaO catalysts were used for biodiesel
production, the onestep batch transesterication processes were
mainly applied. Only Hu et al. [39] created a new continuousow
integration process based on the countercurrent ow of gas (methanol
vapor) and liquid (rapeseed oil) phases, the separation of glycerol on
line and the cyclic utilization of methanol. The average yield of
triplicate experiments with a nano microporous solid base KF/CaO
catalyst was 93.7%. Hence, the continuous process might be a good
potential in the biodiesel production.
5. Regeneration, reusability and leaching of nano CaObased
catalysts
The possibility of their multiple utilization in the transesterication
reaction, after or without regeneration of their activity, is one of the
important advantages of heterogeneous catalysts, compared to homo-
geneous catalysts, for the biodiesel production at commercial scale. The
catalyst activity and deactivation can be reduced with the repeated or
prolonged use from various reasons. In the case of nano CaO catalyst,
deactivation can be associated with the presence of organic impurities
or adventitious moisture and the formation of enolate anion by the
deprotonation of the alpha carbon of the carboxyl group in TAG or
ester [19].
The investigations related to the reusability of the neat nano CaO
catalyst have showed that it can be applied in three cycles with poultry
fat and in eight cycles with soybean oil as the feedstock in the
methanolysis reaction with no signicant decrease in its catalyst

756
I.B. BankoviIli et al.
activity [19]. For reasons that are not clear, a granular form of nano
CaO has better recyclability compared to the powder form in the
transesterication of soybean oil at room temperature. Reddy et al.[19]
conrmed that fresh powder form of the nano CaO catalyst consisted of
numerous crystallites with welldened edges, while the partially
deactivated form after several cycles of use, had formed aggregates of
polycrystals with less welldened edges. When the authors prepared
biodiesel from waste poultry fat with higher concentrations of impu-
rities, compared to soybean oil, the nanocrystalline CaO catalyst
showed a lower recyclability.
In the methanolysis of palm olein, a nano CaO catalyst maintained
the sustained activity for 5 cycles, with a slightly lowered level of its
activity after the second repetition [38]. The reason for the decrease in
the catalyst activity might be the blockage of active sites by the
adsorbed intermediates or products (mono and diacylglycerols,
glycerol) and the contamination by oxygen, water and carbon dioxide
from the air. The leaching of active species into the reaction mixture
also contributes to the decrease of catalyst activity.
The study of Zhao et al. [37] showed that two nano CaO catalysts
with moderate and high specic surface area had a good activity and
stability for the rst 10 cycles proved by a steady ester yield of about
90%. The signicant decrease in the catalysts activity were observed
when the yield dropped to around 70% after 15th cycle due to the
changes in the physical properties of the catalyst during the reaction,
the adsorbed CO2 on the catalyst surface and the loss of catalyst surface
area because of combination eects of particle aggregation and the
formation of Ca(OCH3)2, CaCO3 and a calciumglycerol complex. A
study of the calcium leaching to the reaction system showed that only
5% of the leached calcium went to the biodieselrich phase as well as
that the calcium contents in the both obtained phases decreased with
the number of recycles. Contrary to Yoosuk et al. [38], Zhao et al.[37]
concluded that the catalyst leaching was not the main cause for the loss
of catalyst activity. A nano CaO catalyst can be reused up to 3 times in
the methanolysis of jatropha oil with the reduced eciency by about
20% in the third consecutive run Sarma et al. [46].
Using KF/CaO as doped nanocatalyst for application in the
biodiesel production, Wen et al. [20] and Hu et al.[39] demonstrated
its long lifetime, good stability and catalytic activity. A relatively high
biodiesel yield of above 91% was achieved in 16 successive cycles. From
the economic point of view, this catalyst can contribute much to
decrease the total cost of biodiesel production since the catalyst cost
is only 2% of the total cost of the continuous biodiesel production [39].
The deactivated catalyst can be regenerated by simple calcination in the
air [39]. Another advantage of this catalyst is the fact that the obtained
biodiesel should not be washed with water.
After the completion of the reaction, many catalysts can be
recovered using an appropriate procedure, which usually includes
ltration, washing with methanol or nhexane and drying or calcina-
Table 5
Kinetics parameters of oil transestefication reaction over nano CaO catalysts.
Feedstock Type of alcohol Catalyst
(oil)
Waste cottonseed Methanol K/CaO
Waste cottonseed Methanol Zn/CaO
Canola Methanol CaOa
CaOb
Jatropha Methanol Zr/CaO
Ethanol
Waste cottonseed Methanol KF/CaO/NiO
Canola Methanol K2CO3/CaO
Rapeseed Methanol KF/CaO
a
Moderate surface area.
b
High surface area.
Renewable and Sustainable Energy Reviews 72 (2017) 746760
tion [1517,40,41,43]. The regenerated catalyst can be employed for
the next successive cycles (usually 36) under the same experimental
and regeneration conditions with a partial or complete loss of activity.
The gradual activity loss occurs due to the structural changes during
the catalytic and/or regeneration process and the leaching of active
species, i.e. the impregnated metal ions and/or CaO from the catalyst
[15]. Metal ions, found in the reaction mixture, could aect the
catalysis similarly to homogeneous catalysts, but to an insignicant
extent [15] because the most of the leached metal ions are settled in the
glycerol layer [17]. The nanomagnetic KF/(CaO/Fe3O4) catalyst, after
proper regeneration, lose its activity signicantly only after the 14th
consecutive reaction cycle [43]. The decrease in the catalyst recovery
was related to the dissolution of catalyst and the loss of catalyst in the
middle of the collection operation.
A few studies demonstrated that nano CaO doped catalysts can be
used several times in transesterication reactions of oil to biodiesel
[32,44,45]. The CaO/graphite oxide nanocatalyst maintains its overall
activity for at least 4 successive cycles of the soybean oil methanolysis
after regeneration by calcination [44]. Lifetime tests of the nano
magnetic CaO/Fe3O4 catalyst showed the possibility of its application
in 4 consecutive reactions with no decrease in the activity [45]. The
magnetic nanocomposite (Ca/Al)/Fe3O4 catalyst can be easily recycled
with a little loss of activity after repeated 5times of uses in the
transesterication reaction, while the ultimately obtained ester yield
was 93.5% [30].
6. The kinetics of transesterication reaction with nano
CaObased catalyst
A numerous of researchers have investigated the kinetics of
transesterication reactions of various feedstocks in the presence of
CaObased catalysts [10]. These transesterication reactions are
reported to be the zeroth or rstorder with respect to TAG. In fact,
the reaction order varies with the progress of the methanolysis from the
zeroth order to the rst [11,53] because the synthesized fatty acid
methyl esters promote miscibility of the reactants. Since transester-
ication reaction can be controlled by mass transfer or chemical
reaction, two independent kinetic expressions are usually used for
the two regions with dierent dominant mechanisms [12]. More
complex models include the mass transfer limitation to predict the
reaction rate [11,55,56] and are capable modeling the kinetics during
the whole course of transesterication reactions over calciumbased
catalysts [57,58].
However, there are only a few papers dealing with the kinetics of
transesterication reaction over nano CaObased catalysts. In general,
when neat [37] or doped [15,17,41] forms of nano CaO are used for
the catalysis of oil conversion with an excess of methanol or ethanol,
then the pseudorstorder kinetic model can be applied. Values of
Rate constant (min1) Activation energy (kJ/mol) Reference
0.062 54 [17]
0.1 43 [41]
0.0698 136.5 [37]
0.0921 102.5
0.062 29.8 [15]
0.0123 42.5
0.023 41.2 [16]
25.34 [40]
17.3 [39]
757
 I.B. BankoviIli et al.

Table 6
Biodiesel properties synthesized by heterogeneously catalyzed oil alcoholysis over nano CaO catalysts.

Feedstock Soybean oil Soybean oil Jatropha oil Karanja oil Waste cotton- Jatropha oil Karanja oil Rapeseed oil Waste cotton- Jatropha oila Jatropha oilb Waste cotton- Jatropha oil EN14214
seed oil seed oil seed oil Min/max

Type of CaO catalyst Neat Doped Low cost

+
Li /CaO K/CaO KF/CaO Zn/CaO Zr/CaO KF/CaO/NiO

Properties, units

Ester content, % > 99 > 99 > 99 > 99 > 99 93.7 99 > 99 > 99 > 99 98 96,5 min
Density at 31 C, kg/m3 873.9 897.2 800 870 890 860 870 880 880 875c 860/900d
Viscosity at 40 C, mm2/ 4.05 4.42 6.02 3.94 4.5 6 4.6 3.9 4.5 4.83 4.5 5.7 3.5/5.0
s
Flash point, C 100 115 110 100 115 > 100 110 110 120 110 110 101 min
Sulfur content, mg/kg 1.4 12 10 max
Carbon residue, % 0.28 0.3 max
Cetane number 52 48.6 51 min
Ash content, % 0.020.004 0.01 0.02 0.02 0.01 0.02 0.02 0.02 0.01 0.02 max
Water content, % 0.5 0.05 0.05 0.5 0.05 traces 0.05 0.07 0.5

758
Oxidative stability at 1.1 6.0 min
110 C, h
Acid value, mg KOH/g 0.33 0.5 0.1 0.3 0.5 0.36 0.1 0.7 0.8 0.5 max
Iodine value, g I2/100 g 91 103 84 90 86 98 75.9 87.8 119 120 max
Saponication value 180 182.32 ND
Monoglyceride content, 0.014 0.80 max
%
Diglyceride content,% 0 0.20 max
Triglyceride content,% 0.01 0.20 max
Free glycerol, % 0.155 0.02 max
Total glycerol, % 0.14 0.179 0.25 max
Group I metals (Na+K), 5.0 5.0 max
mg/kg
Pour point, C 1 5 6 1 5 1 4 1 2 1 +3 NDe
Caloric value, MJ/kg 38.6 24.4 40 39 25 40 39.25 ND
Reference [19] [35] [14] [17] [39] [41] [15] [16] [46]

a
Methanolysis.
b
Ethanolysis.
c
At 15 C,
d
At 25 C,
e
ND not dened
Renewable and Sustainable Energy Reviews 72 (2017) 746760
I.B. BankoviIli et al.
the reaction rate constant and the activation energy under the optimum
reaction conditions are presented in Table 5. The activation energy in
the case of doped CaO catalysts are within the range of 17.354 kJ/
mol, depending on the type of oily feedstock while much higher values
are observed in the case of neat nanopowder CaO catalysts [37]. In
addition, the kinetic study of Degirmenbasi et al. [40] showed that the
transestecation of canola oil in the presence of excess methanol and
the nano K2CO3/CaO catalyst occurred with the apparent reaction
order of 0.98 with respect to the oil concentration, followed the mass
transfer controlled regime.
The kinetic analysis of the abovementioned gasliquid counter-
current integrated process for continuous biodiesel production using
the microporous base KF/CaO nanocatalyst showed that the initial
concentration oil/methanol ratio and the initial catalyst concentration
aected the rate of transesterication reaction [39]. The apparent
reaction orders were calculated as 2.09 for the catalyst and 0.56 for the
concentration oil/methanol ratio.
It is wellknown that the catalytic data should be independent of all
transport inuences in order to study the pure kinetics of a
transesterication reaction. To estimate if the catalyst activity was
independent of the transport phenomena, a group of researchers
[15,17,41] employed the KorosNowak criterion test modied by
MadonBoudart. The logarithm of the reaction rate vs the logarithm
of the weight of the impregnated ion (K+, Zn2+ or Zr4+) on the catalyst
carrier was plotted at dierent temperatures. The KorosNowak
number, estimated from the slope a straight line dependence, had
the value close to unity. It denoted that the transesterication reaction
of oil over nano CaO catalysts obeyed to this criterion and the reaction
rate was not masked by the transport rate.
7. Statistical optimization of oil transesterication over nano
CaO
Only Hu et al. [39] optimized a biodiesel synthesis in the presence
of nano CaO using the statistical method. Based on the orthogonal
experiment design they determined that the reaction temperature and
the full height of the catalyst had the greatest eect on the biodiesel
yield. A secondorder polynomial regression model for the biodiesel
yield was estimated and validated experimentally. The established
model matched the experimental data so that a very low pvalue of
probability ( < 0.0001) and a very high determination coecient
(R2=0.9898) of the model indicated its signicance in the representa-
tion of the actual relationship between the biodiesel yield and the two
process variables. The actual average biodiesel yield (93.7%) was very
close to that predicted by the model (95.8%), indicating the adequacy of
the applied model for the continuous ow process.
8. The quality of biodiesel synthesized in the presence of
nano CaO catalysts
Physicochemical properties of biodiesel obtained by transester-
ication reactions over nano CaO catalysts are given in Table 6.
Generally, the values of the studied properties were found in accor-
dance with the acceptable limits of European standards (EN14214).
9. Conclusion
This overview considers the current status and promising potential
of using nano CaObased catalysts as heterogeneous catalysts in
biodiesel production. It demonstrates that dierent forms of nano
CaO catalysts (neat, doped, loaded) are used in biodiesel synthesis. As
their eectiveness is dependent on their basicity, specic surface area
and activity even at room temperature, as well as the possibility of
regeneration and reusability, the proper preparation, activation and
regeneration methods should be applied in order to obtain an
adequately active and stable form of nano CaO catalysts. These
759
Renewable and Sustainable Energy Reviews 72 (2017) 746760
catalysts are especially attractive for biodiesel synthesis due to their
large surface area, surface reactivity and catalytic activity that increase
the reaction rate and shorten the reaction time, contributing to the
enhanced process productivity. Also, some of them, like doped nano
CaO catalysts, are very ecient in the conversion of low-quality oily
feedstocks as being tolerant to FFA and moisture contents. Another
way to improve the biodiesel synthesis over nano-CaO is the addition of
an appropriate cosolvent to the reaction mixture, which will promote
the reactants miscibility and accelerate the reaction. Besides high yield
and fast reaction at mild reaction conditions, good quality of obtained
biodiesels is also important characteristic of the transesterication
reactions over nano CaO catalysts.
Since nano CaO catalysts are signicant for developing the modern
technologies for biodiesel synthesis based on nanomaterials, much
more research work is needed to discover new inexpensive precursors
and carriers for the preparation of nano CaO, to improve catalytic
activity and reusability and to reduce the leaching of active species.
Also, much further eort must be made to eliminate or reduce the
problems met in the overall process, such as dicult separation and
complex recycling, which prevent the commercialization of nanocata-
lyzed biodiesel production. The use of ferromagnetic nano CaO
catalysts seems to be a promising way to overcome some of these
obstacles. Also, it is necessary to improve the existing and to develop
new techniques for biodiesel production with the use of nano CaO
catalysts. A potential solution is to apply nano CaO catalysts in novel
reactor types, such as microwave-irradiated reactor and continuous
reactor with countercurrent ow of alcohol vapor and liquid oily
feedstock, which can reduce the overall production cost. In addition,
being fundamental to reactor design and process optimization, further
investigation of the kinetics of transesterication reactions over nano
CaO catalysts are needed in order to develop the reliable kinetic
models. Furthermore, statistical optimization methods are recom-
mended as eective tools for the improvement of biodiesel production
processes over nano CaO. These all investigations might result in novel
technologies aiming at a high biodiesel yield and process productivity,
which will have further positive implications, such as simplicity,
eciency, economy and safety of biodiesel production processes.
Acknowledgment
This work has been funded by the Ministry of Education, Science
and Technological Development of the Republic of Serbia, Serbia
(Project III 45001).
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