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Chemical Engineering Journal 168 (2011) 1522
Contents lists available at ScienceDirect
Chemical Engineering Journal
j our nal homepage: www. el sevi er . com/ l ocat e/ cej
Review
Performance of calcium oxide as a heterogeneous catalyst in biodiesel
production: A review
Peng-Lim Boey
a
, Gaanty Pragas Maniam
a,
, Shada Abd Hamid
b
a
School of Chemical Sciences, Universiti Sains Malaysia, 11800 Minden, Penang, Malaysia
b
Kulliyyah of Science, International Islamic University Malaysia, Jalan Sultan Ahmad Shah, Bandar Indera Mahkota, 25200 Kuantan, Pahang, Malaysia
a r t i c l e i n f o
Article history:
Received 21 September 2010
Received in revised form
28 December 2010
Accepted 4 January 2011
Keywords:
Calcium oxide
Biodiesel
Methyl ester
Transesterication
Heterogeneous catalyst
a b s t r a c t
The accelerating and frequently uctuating price of conventional diesel, together with growing environ-
mental concerns has sparked renewed attention on the search for an alternative fuel. The awareness
of the toxic effects related to the tailpipe emissions of vehicles has driven many countries to look for a
less-polluted transportation fuel. In this regard, biodiesel (alkyl esters) fromvegetable oils or animal fats
via transesterication is regarded as the most viable alternative as a green fuel for diesel engines. Trans-
esterication is a catalyzed process and, traditionally, homogeneous catalysts are employed. However,
this type of catalyst is not able to be reused and requires tedious washing and separating steps, hence,
stimulating the conceptionof heterogeneous-catalyzedtransesterication. Despite the success of various
heterogeneous catalysts, many are not viable for wide industrial usage as most of the catalysts are expen-
sive and need additional preparation effort. Among them, CaO seems to have a promising place and the
increasing research on CaO is self-evidence of its capability in catalyzing the reaction. Therefore, in this
paper, various issues regarding CaO-catalyzed transesterication are reviewed. The diverse performance
of CaO in neat, loaded and mixed forms, as well as a support for other catalyst systems, CaO reaction
mechanism, CaO tolerance to low to moderate oil qualities and reaction conditions, the conformance of
CaO-catalyzed biodiesel to key specications and the future outlook and the challenges of the catalyst
are suitably addressed.
2011 Elsevier B.V. All rights reserved.
1. Introduction
Biodiesel, also known as fatty acid alkyl ester, is regarded as the
best substitute for conventional petro-based diesel fuel. The cur-
rent oil consumption of about 86 million barrels per day (Fig. 1)
[1] and the limited oil reserves has positioned biodiesel as a future
fuel for diesel engines. Biodiesel is prepared via a catalytic reaction
between triglycerides and alcohol. Glycerol is the by-product of the
reaction. The reaction involves the breakage of the glycerol struc-
ture and exchanges of alkyl groups between the alcohol and ester
part of the triglyceride molecule; as such, the reaction is known as
transesterication. Among the three major routes, transesterica-
tion seems to be the best compared to heating and microemulsions
for reducing the viscosity as well as minimizing engine complica-
tions [2]. The main purpose of transesterifying the vegetable oil is
to lower its viscosity while at the same time raising the volatil-
ity. The direct use of vegetable oils as a fuel poses several engine
complications [3,4].

Corresponding author. Tel.: +60 16 4110236; fax: +60 4 6574854.

E-mail address: gaanty@hotmail.com (G.P. Maniam).
Producing biodiesel is not a new idea as the concept dates back
to the 1800s when the French government, at the Paris Exhibition,
demonstrated the use of peanut oil as a fuel. As an improvement,
transesterication of vegetable oil was carried out with success by
Duffy and Patrick in 1853. Forty years later, in 1893, Rudolph Diesel
successfully inked an important research article on biodiesel enti-
tled The theory and construction of a rational heat engine. He had
intensively researched the potential of vegetable oils as a replace-
ment for conventional diesel, which marked the invention of the
diesel engine (from whence the engine obtained the name). It is
worth noting here that Nicklaus Otto had already invented a sim-
ilar internal combustion engine much earlier (1876), however, it
was less efcient than that of Diesel [5].
Biodiesel is a renewable fuel since it is produced from innite
sources of plant oils and animal fats. This makes biodiesel readily
obtainable as long as the supplies of vegetable oils or animal fats
are available. Unlike petro-based fuels, searching for oil wells is not
required for this green fuel. From the environmental viewpoint,
biodiesel is a clean burning fuel (for its oxygen content) with low
exhaust emissions, freefromsulphur andcarcinogencontent, andis
a non-toxic andbiodegradable fuel. Inaddition, the use of waste oils
and fats in biodiesel production also reduces many environment-
related complications. As a fuel, biodiesel has a comparable caloric
1385-8947/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.cej.2011.01.009
Author's personal copy
16 P.-L. Boey et al. / Chemical Engineering Journal 168 (2011) 1522
Fig. 1. World petroleum consumption between year 1960 and 2007 [1].
value to petro-diesel, has shown higher combustion efciency, a
higher cetane number and possesses excellent lubricity. As far as
the safety is concerned, the higher ash point makes biodiesel
safer to handle, transport and store. The option of direct blending
with petro-diesel as a fuel in compressionignition engines at any
blending ratio adds merit to biodiesel. At present, biodiesel is not
economically favourable as its cost is more than that of conven-
tional diesel fuel. However, if the various benets of the fuel are
accounted for, including environmental gains, enhancing the rural
socio-economic status and reducing foreign exchange, the eco-
nomic competitiveness can be truly realized. Politically, producing
biodiesel makes a nation totally, or at least partially independent
of other oil producing countries [58].
One of the main reasons for the conceptualization of biodiesel is
the environmental pollution, specically CO
2
emission. Concern-
ing the CO
2
emission, in 2005 the EU introduced an innovative
cost-effective scheme termed the Emission Trading Scheme (ETS),
a scheme that Australia, New Zealand and the United States are
keen to adopt in their long-term plan for dealing with green house
gases. Fig. 2 provides evidence of the EUs CO
2
-reduction pledge, in
which it targeted to achieve a moderate emission of 130g CO
2
/km
in 2012 and an ultimate low emission of 95g CO
2
/km in 2020. In
addition, the French government has suggested that an incentive
to be given for lower CO
2
emission vehicles as well as penalties
for those that cross the set CO
2
threshold (Table 1) [9]. Although
the cost of biodiesel is still high, the pollution-control pledges and
anticipation by the developed continents are conrmation of the
demand for biodiesel and its impending usage in both short and
long term. Nowit is the developing nations responsibility, to a cer-
tain extent, to assist the developed nations in realizing the green
targets. By looking at these scenarios, research related to biodiesel
is going to be ever more intense as the momentumquickens across
the world.
In general, transesterication is a catalyzed chemical reaction.
Hydroxide or methoxide of sodium or potassium is used, con-
ventionally, as a homogeneous catalyst in this reaction. However,
due to various drawbacks, such as its intolerance of moisture and
free fatty acids (FFA) in feedstock, the generation of a substantial
amount of process wastewater, and incapable of catalyst reuse,
the conception of heterogeneous catalysts evolves. Among the
researched heterogeneous catalysts, CaO shows potential in the
transesterication reaction. The catalyst is able to be reused (cost-
effective), has atoleranceof moistureandFFA(whichallows theuse
of lower-quality used/waste oils), is inexpensive (obtainable from
waste shells), has low methanol solubility, is non-corrosive and
is environmental friendly. On the other hand, enzymatic catalysts
are gaining attention as catalysts in transesterication. Although
this type of biocatalyst has recorded success, their utilization needs
more stringent reactionconditions, comparedtohomogeneous and
heterogeneous catalysts, in terms of the amount of methanol in the
reaction media (since methanol inhibits activity of lipase at cer-
tain concentrations), temperature suitability to a specic enzyme
type, pH and the type of co-solvent used in the reaction, otherwise
deactivation of enzyme takes place easily. However, for extremely
lowgrade feedstock, such as oil with 160mg KOH/g [10] and 55mg
KOH/g [11], solid acid catalysts are the preferred choice. Very often,
such reactions require much accelerated reaction conditions, in
terms of the amount of methanol and catalyst as well as higher
reaction temperature, pressure and longer reaction time. However,
if the feedstock has a lower FFA content, then CaO or other basic
catalysts are the option, in which conventional reaction conditions
Fig. 2. Declining trend of CO
2
-emission-per-km of vehicles in US and EU-15 [9].
Table 1
Bonus and penalty for new vehicles in France for their corresponding level of CO
2
emissions [9].
Emission levels (g CO
2
/km) <60 <100 101120 121130
Bonus in Euro (effective from 5-December-2007) 5000 1000 700 200
Emission levels (g CO
2
/km) 161165 166200 201250 >250
Penalty in Euro (effective from 1-January-2008) 200 750 1600 2600
Author's personal copy
P.-L. Boey et al. / Chemical Engineering Journal 168 (2011) 1522 17
can be employed. In short, heterogeneous catalysts have consider-
able potential in the transesterication reaction. In viewof this, the
utilization of CaOas a heterogeneous catalyst in transesterication
is presented in this review.
2. Catalysts in transesterication
2.1. Homogeneous catalyst
As far as the catalyst is concerned, a homogeneous catalyst is the
preferred choice for producing biodiesel. Hydroxides and methox-
ides of sodiumand potassiumare the most common homogeneous
catalysts. Freedman et al. [12] found that 0.5% NaOCH
3
performs
much better than 1% NaOH. This is understood since methoxide
ions are readily available in the case of the former catalyst and the
latter has to react with methanol rst. However, both catalysts are
able to transesterify to near completion within one hour of reac-
tion time at 60

C. Amuch longer reaction duration (4h) is required

for similar performance at 32

C. It appears that the reaction tem-

perature very much implicates the kinetics of transesterication.
The authors also noted that acid-catalyzed transesterication is
much slower compared to alkali-catalyzed reaction, although an
acid catalyst is preferred for transesterifying feedstock with higher
FFA content. In such a situation, a higher temperature and pressure
is oftenemployedtospeedupthereactionratebut withimplication
on the production cost.
Meher et al. [13] demonstrated that in the transesterication
of Karanja oil, KOH performed excellently with a methyl esters
yield of above 90% at 1% and 1.25% catalyst dosage, in 1h reac-
tion at 65

C with a stirring speed of 600rpm. Similarly, sodium

based homogeneous catalysts (NaOH and NaOCH
3
) have shown
remarkable performances inthe transestericationof rapeseedand
soybean oils. Rapeseed methyl esters yield between 93 and 96%.
This was achieved in a 1h reaction time with 12% NaOH in the
following conditions: 7:1 molar ratio, 60

C, 600rpm mechanical
stirring. Whereas inthe transestericationof the soybeanoil a yield
of more than80%was obtainedwith0.1%NaOCH
3
ina 2.5hreaction
time at 65

C with 10:1 MeOH/oil molar ratio, and 450rpmshaking

speed [14,15]. Despite the merits, as discussed earlier, homoge-
neous catalysts have several drawbacks. As a result, interest has
shifted towards heterogeneous catalysts.
2.2. Heterogeneous catalyst
In recent years, researchers have shifted their focus to
heterogeneous-catalyzed transesterication as the homogeneous-
catalyzed transesterication consumes more energy and requires
a costly product separation process [16]. Sercheli et al. [17] exhib-
ited the use of alkylguanidines attached to modied polystyrene or
siliceous MCM-41 in the methanolysis of soybean oil and inter-
estingly, its activity was comparable to that of homogeneous
catalysts. Kim and co-workers [18] experimentally described the
use of Na/NaOH/-Al
2
O
3
in producing near-completion soybean
oil methyl esters in 2h. A tin complex [Sn(3-hydroxy-2-methyl-
4-pyrone)
2
(H
2
O
2
)] has been successfully utilized in soybean oil
methanolysis, giving a 93% yield in 3h and with the added advan-
tage of the possibilityof recyclingthe catalyst [19]. Jitputti et al. [20]
demonstrated a series of acidic as well as basic heterogeneous cat-
alysts in the transesterication of palm kernel and crude coconut
oils. The catalysts used were ZrO
2
, ZnO, SO
4
2
/SnO
2
, SO
4
2
/ZrO
2
,
KNO
3
/KL zeolite and KNO
3
/ZrO
2
. The authors found that among the
researchedcatalysts ZnOandSO
4
2
/ZrO
2
showedthehighest activ-
ity, 95.8wt.% methyl esters content is achievable in a 1h reaction
time. However, a much accelerated temperature of 200

C had to be
employed (as the usual case for acid catalysts) and the need to pro-
long the reaction further (than 1h) to meet the minimum required
methyl esters content of 96.5% by EN14214:2003. In another study,
Xie et al. [21] proved that potassium loaded on alumina could be
a potential solid catalyst in the methanolysis of soybean oil. The
calcined (at 500

C, 5h) catalyst system at 35wt.% loading, with a

molar ratio of 15:1 (MeOH/oil) and catalyst concentration of 6.5%,
87% triglyceride was converted in 7h. When loaded on a meso-
porous MSU-type alumina, KF, LiF and CsF demonstrated to be
potential solid catalysts in the transesterication of vegetable oils
[22]. Hameed et al. [23] successfully used a KF/ZnO systemin palm
oil transesterication with yields exceeding 89% in less than 10h
with a MeOH/oil molar ratio of 11.43:1 and 5.52% catalyst amount.
As shown by Zhang et al. [24], heteropolyacid (Cs
2.5
H
0.5
PW
12
O
40
)
is another solid system in the microwave-assisted methanolysis of
yellow horn oil at 60

C. The highest yield of more than 96% was

attained in 10min with 12:1 MeOH/oil molar ratio. The catalyst
was able to be reused for nine cycles. This overwhelming result
was made possible with the assistance of a 500W microwave, the
use of alkaline cations which are insoluble in reaction media, and of
course, with a higher catalyst cost. If the process is adopted by the
industry, technical matters regarding the microwave setup facility
need to be addressed.
2.3. Enzymatic catalyst
The potential of biocatalysts in biodiesel production is attract-
ing continuous attention and the catalysts perform equally well
with their chemical-based counterparts. Shieh et al. [25] immobi-
lized lipase from Rhizomucor miehei (Lipozyme IM-77) to catalyze
the methanolysis of soybean oil to achieve more than 92% methyl
esters conversion. Dizge and Keskinler [26] demonstrated the
use of 80% immobilized Thermomyces lanuginosus lipase in the
transesterication of canola oil with a remarkable yield of 90%.
A series of lipase (Pseudomonas uorescens, Burkholderia cepacia
and Penicillum camembertii) were utilized in the transesterica-
tion of babassu oil by Freitas et al. [27] to obtain a yield of
more than 98% in a reaction time of 48h. Xie and Ma [28] used
lipase (Thermomyces lanuginose) that was covalently immobilized
onto magnetic Fe
3
O
4
nano-particles by using an activating agent
[1-ethyl-3-(3-dimethylaminopropyl)carbodiimide] in the transes-
tericationof soybeanoil. The conversionof over 90%was achieved
in the three-step transesterication when 40% immobilized lipase
was used. Interestingly, the enzyme catalyst could be used more
thanthree times without a signicant loss inthe catalytical activity.
However, as mentioned earlier, biocatalysts need more stringent
reaction conditions and in terms of cost, enzyme catalysts are
expensive and generally require a longer reaction time.
3. Calcium oxide
Calcium oxide (CaO) has many industrial applications. Its phys-
ical and chemical properties and the related uses are listed in
Table 2 [2932]. The use of CaO as a heterogeneous catalyst has
been around for many years. In 1984, Peterson and Scarrah [33]
reportedonthe transestericationof rapeseedoil using CaO. Atotal
of 28 heterogeneous catalyst systems were examined comprising
MgO, CaO, ZnO, Al
2
O
3
, SiO
2
, K
2
CO
3
, Na
2
CO
3
, transition metals and
an anion exchange resin. Among the examined catalyst systems,
CaOMgO gave the most promising results followed by, in turn,
K
2
CO
3
, K
2
CO
3
MgO, K
2
CO
3
Al
2
O
3
, CaO, NaOCH
3
SiO
2
, Na
2
CO
3
,
CaOMgOAl
2
O
3
and ZnOMgO. The last two catalyst systems
shared equal activities, whereas for the case of the anion exchange
resin, under moderate conditions (91

C and 9.2atm pressure)

only traces of methyl esters were detected and a slightly better
performance (equal to NaOCH
3
SiO
2
) was spotted under much
Author's personal copy
18 P.-L. Boey et al. / Chemical Engineering Journal 168 (2011) 1522
Table 2
Properties of calcium oxide [2932].
Item Description
Chemical name Calcium oxide
Chemical formula CaO
Common name Lime, calx, quicklime, burnt lime,
unslaked lime, uxing lime, caustic
lime
Density (g/cm
3
) 3.40
Melting point (

C) 2572
Boiling point (

C) 2850
Heat of formation (kcal/mol) 151.9
Heat of hydration (kcal/mol) 15.1
Solubility of Ca(OH)
2
(g/100g H
2
O) 0.219
Decomposition temperature (

C) 547
Applications In furnace lining, metal smelting, glass
making, fertilizer, drying agent,
mortar, paper and pulp production,
drilling uid, pollution control, water
purication, sugar and cellulose
industries, medical (destroys warts,
moles)
accelerated reaction conditions of 200

C and 68atm pressure. The

ndings proved CaO as a potential solid catalyst in transesterifying
triglycerides to methyl esters. Since then, many researchers have
reportedonthe use of CaOas a heterogeneous catalyst inproducing
biodiesel. Unlike many other solid catalysts, CaOcould be prepared
without much preparation effort.
3.1. Neat CaO
Typically, CaO requires a thermal activation to remove the
adsorbedCO
2
andmoisture. Theusual reportedcalcinationtemper-
ature is 700

C and the temperature is dependent on the pressure,

as depicted in Fig. 3 [34]. In the transesterication of sunower
oil, thermally activated CaO at 700

C demonstrated a good yield

(94wt.%) at reactionsettings of 60

Cand1:13MeOH:oil molar ratio

[35]. Interestingly, the catalyst could be reused up to eight times
with a minimum yield of 73wt.%. Kouzu et al. [36] found 900

C
(1.5h) calcined-CaO to be a very active catalyst in the transesteri-
cation of soybean oil to biodiesel. In similar work, the researchers
also experimented CaO, Ca(OH)
2
and CaCO
3
in producing soybean
oil methyl esters [37]. With a 1h reaction at the reuxing temper-
ature of methanol the reported methyl esters yield were 93% using
CaO and 12% with Ca(OH)
2
. No product was obtained using CaCO
3
.
The authors extended their experiments using waste oil with an
acid value of 5.1mg KOH/g, and obtained above 99% methyl esters
Fig. 3. Dissociation pressure and temperature of CaCO
3
[34] (replotted).
in a 2h reaction time. This shows that CaO is tolerant of low FFA
content oil. However, they noted the formation of calcium soap,
the deactivating reaction of the catalyst with FFA, at the end of the
reaction. A similar observation was reported by Arzamendi et al.
[38], where CaO had a much higher reactivity than its hydroxide.
Unexpectedly, the study revealed that uncalcined CaOhad a higher
catalytic activity than 12h 500

C-calcined CaO, however, with a

longer reactiontimeof 10h. Althoughthis ndingis incontrast with
others, the authors reasoned that the presence of surface hydrox-
ide sites in uncalcined CaO which enhances the reaction rate. It is
worth noting here that the calcination period used in this work is
longer than the usual duration (23h).
In the transesterication of rapeseed oil, using Ca(OCH
3
)
2
,
formed by the pre-treatment of CaO with methanol for 1.5h, the
Ca(OCH
3
)
2
was found to act as an initiating agent in the reac-
tion [39]. The yield of methyl esters of about 90% was obtained
in a 3h reaction time at 60

C. Further transesterication work on

Ca(OCH
3
)
2
was carried out by Liu et al. [40] using soybean oil.
They achieved a 98% biodiesel yield in a 2h reaction time. Inter-
estingly, in a reusability study, it was found that the catalyst was
still active after the twentieth use. The same authors reported on
the success of CaOin soybean oil transesterication [41]. By adding
about 2% water in methanol, the biodiesel yield exceeded 95% in
a 3h reaction with a 12:1 MeOH:oil molar ratio with 8% catalyst.
By adding a little water, the authors concluded that CaO generates
more methoxide anions, which form the actual catalyst that drives
the reaction. As such, CaO not only tolerates moisture in the feed-
stock but also elevates the activity of the catalyst. In contrast, it was
found that atmospheric H
2
O and CO
2
could easily poison the cata-
lyst, CaO [37,40]. They noted that the effect of moisture-poisoning
is less pronounced than the carbonates.
We have also reported on the success of CaO in transesteri-
fying the adsorbed waste palm oil on spent bleaching clay [42].
Compared to the conventional catalysts (NaOHand KOH), the CaO-
catalyzed reactionyielded muchhigher biodiesel (about 90%) using
the waste oil (6.66.8% FFA content) compared to only 46 and 61%
yield using NaOH and KOH, respectively. This again proves the tol-
erance of CaO against low FFA content feedstock. Gryglewicz [43]
reported that CaO is a potential catalyst in the preparation of rape-
seed oil methyl esters. However, the author noted that the reaction
time is longer, 24-fold, compared to homogeneous NaOH. Nev-
ertheless, CaO has advantages in terms of catalyst cost and the
simpler production process. Furthermore, the use of ultrasonic and
co-solvent (tetrahydrofuran) considerably increased the reaction
rate. Among the ways to enhance the performance of neat CaO,
the hydrationdehydrationmethod is anoption[44]. The produced
CaO via this modied method has a much higher surface area and
basic sites, as such, 94wt.% methyl esters content was achieved in
less than an hour with 7wt.% catalyst and 15:1 MeOH/oil molar
ratio.
Nanocrystalline CaO has performed excellently at room tem-
perature in the methanolysis of soybean oil and poultry fat [45].
As stated earlier, temperature implicates the reaction kinetics and,
as a result, a longer reaction time is required for room temper-
ature reaction. In addition, for reactions at lower temperature
(than methanol reuxing temperature), a higher MeOH/oil ratio
is essential. Accordingly, in this work 27:1 MeOH/oil molar ratio
was needed. The higher surface area of the catalyst, coupled with
the smaller crystallite size and defects, assist in the kinetics of
the reaction. At much accelerated reaction conditions (5ml oil,
15ml MeOH) with 0.056g catalyst, tetrahydrofuran (as a phase-
merging agent to increase miscibility of oil and MeOH) was found
to reduce the reaction duration from 12 to 6h. In the study of the
etherication of glycerol to di- and triglycerol, CaOperformed well
as a heterogeneous catalyst [46]. The authors found that in the
course of the reaction the catalyst formed colloidal CaOparticles of
Author's personal copy
P.-L. Boey et al. / Chemical Engineering Journal 168 (2011) 1522 19
about 50100nm, which enhanced the reaction activity. The stud-
ies linked CaOcrystalline size and the types of CaO-based materials
to the success of their reactions.
3.2. Loaded CaO
To enhance the performance of CaO, a few researchers have
tried to load an active ingredient onto CaO. Watkins et al. [47]
evaluated Li-loaded CaO in the transesterication of glyceryl trib-
utyrate to methyl butanoate. Experiments with lithium loading
ranges from 0.26 to 4.0wt.%. The authors found that the optimum
loading amount of 1.23wt.% exhibited maximumactivity. The dop-
ing of lithiumonCaOincreases the basicity of the catalyst. Li-doped
CaO was also examined by Alonso et al. [48] in transesterifying
sunower oil into methyl esters. This report concluded that an
activated catalyst at 500

C and a lithium loading of 4.5wt.% onto

CaOgave the highest catalytical activity. The authors noted that the
catalyst activation temperature should be higher than the melting
point of LiNO
3
(219

C). However, catalyst activation above 500

C
caused the active species to leach into the reaction media, thus,
affecting the heterogeneous catalytical route.
Ngamcharussrivichai et al. [49] found that Ca(NO
3
)
2
loaded on
dolomites canbe aneffective heterogeneous catalyst inthe transes-
tericationof palmkernel oil at 60

C. Under a MeOH/oil molar ratio

of 15 and 10wt.% catalyst, the Ca(NO
3
)
2
loaded on 600

C-calcined
parent dolomite whichwas thencalcinedagainat 800

C, generates
a higher catalyst activity that produces 99.9%methyl esters content
in a 3h reaction time. The Calcination temperature of the parent
dolomite prior to the metal loading is crucial in determining the
nal activity of the catalyst. Before the metal loading, calcination of
the parent dolomite at 800

Cseems to be inferior to that of 600 and

700

C. The latter calcination temperatures provide two active CaO

sites, one generated from Ca(OH)
2
and the other one from CaCO
3
.
The observation stresses the importance of the right calcination
temperature, which has a great inuence on the catalyst basicity,
prior to the loading process. Aseries of alkali-doped CaOwas tested
by MacLeod et al. [50]. CaO and MgO were loaded with nitrate
of Li, Na and K in the production of methyl esters using rapeseed
oil. Dried (110

C, 5h) and calcined (600

C, 5h) catalysts, Na/CaO,

K/CaO and Li/MgO at 5wt.% loading, exhibited 100% methyl esters
conversion in a 3h reaction with 5% catalyst. Calcined Li/CaO gave
99% conversion; uncalcined Na, K and Li/CaO resulted in 98%, 90%
and 85% conversions, respectively. The performance of these cata-
lysts relates well with their basic strengths. As for species leaching,
it was found that calcined Li/CaO gave the lowest metal leaching
of 18ppmfollowed by uncalcined Li/CaO (22ppm), calcined K/CaO
(32ppm) anduncalcinedK/CaO(36ppm). CalcinedLi/MgOresulted
in the highest metal leaching of 98ppm, followed by uncalcined
Na/CaO and calcined Na/CaO at 78 and 52ppm, respectively. Thus,
as far as lixiviation is concerned, lithium is the most stable loading
species and calcination seems to further improve the stability of
Li/CaO and K/CaO catalyst systems.
3.3. Mixed CaO
CaO also has a potential to be mixed with other oxides in the
transesterication activity. In the transesterication of palm ker-
nel oil, CaO again showed a good performance. Calcined (at 800

C)
10wt.% dolomite gave 96.1% methyl esters conversion in 3h at
60

C with a MeOH:oil molar ratio of 50:1 [49]. Higher conversion

with unloaded neat dolomite was possible with the aid of a larger
amount of catalyst as well as greater methanol ratio. In addition,
there is also an indication from the work that CaO performs very
much better than MgO. In a similar work, CaO mixed with ZnO
at Ca/Zn ratio of 0.25, palm kernel methyl esters above 94% was
obtainedin3h. Themixedcatalyst couldbereuseduptothreetimes
withamethyl esters content of morethan90%[51]. Inanother study
[52], Mg/Ca with a molar ratio of 3 performed well in the transes-
terication of ethyl butyrate with methanol due to the presence of
stronger basic sites related to Ca
2+
O
2
and much higher surface
area (10-fold) than pure CaO. Furthermore, the active species were
not leached during the course of the reaction proving the stabil-
ity of the heterogeneous state of the mixed catalyst. However, the
nding that MgO is insoluble in methanol is different from a pre-
vious study [43] which reports that MgO solubility in methanol is
more intense than CaO. The disagreement may be attributed to the
different reaction systems being used.
3.4. Waste CaO
In order to make the biodiesel production more sustainable, the
utilization of waste heterogeneous catalysts was of recent inter-
est. The shells of oysters and chicken eggs have been evaluated
as effective catalysts in converting soybean oil to methyl esters.
Nakatani et al. [53] showed that by using 25wt.% of thermally
activated (at 700

C) oyster shell at 6:1 MeOH:oil molar ratio, a

biodiesel product with a yield of over 70% and purity of 98.4wt.%
was achieved in a 5h reaction time. The conversion at a moder-
ate 6:1 (MeOH:oil) ratio was achievable at the expense of a higher
catalyst and longer reaction time. With 3wt.% of calcined egg shell
(at 1000

C), Wei et al. [54] transesteried soybean oil to obtain

over 95% yield in a 3h reaction time with the following conditions;
9:1 MeOH:oil molar ratio and a 65

C reaction temperature. The

authors found that the waste catalyst is capable of being reused
up to 13 times without much loss in the activity. In addition, we
have reported the similar catalyst potential of mud crab shells in
palmoleintransesterication[55,56]. The activated(at 900

C) crab
shell was able to transesterify palm olein to 98.8wt.% purity at
5wt.% concentration with the following reaction settings: 65

C,
0.5:1 MeOH:oil mass ratio and 2.5h reaction time. As shown in
Table 3 [55], the prepared methyl ester was found to comply with
several key properties of biodiesel. Most recently, waste mollusc
shells (apple snail and meretrix venus) together with eggshell were
successfully employed as a heterogeneous catalyst in palm olein
transesterication [57]. The authors concluded that the catalyst
surface area and Ca content were responsible for the catalytical
activity, which yielded 90% biodiesel in a 2h reaction period, with
the following conditions: 18:1 MeOH:oil molar ratio, 10wt.% cata-
lyst (calcined at 800

C, 4h) and at a reaction temperature of 60

C.
It was found that eggshells exhibited the best catalytic activity fol-
lowed by apple snail shells and, lastly, meretrix venus shell; the
order in agreement with their surface area and Ca content. More
recently, we have demonstrated the co-use of CaO from two dif-
ferent waste sources (crab and cockle shells) as a heterogeneous
catalyst in the transesterication of chicken oil [58]. In this work,
we found that the performance of different combinations of CaO
from different sources at various ratios was similar to each other.
This opens up an avenue to co-use CaO from different sources as
a solid catalyst in transesterication and implies a positive impact
on overall catalyst costing.
3.5. Supported CaO
In the methanolysis of soybean oil, 15wt.% CaO loaded onto
mesoporous silica gave a 95.2% biodiesel yield at 5wt.% catalyst
amount for a 8h reaction at 60

C. In an attempt to transester-
ify the lipid of yellow green micro algae (Nannochloropsis oculata),
Umdu et al. [59] used Al
2
O
3
supported CaO and MgO as hetero-
geneous catalysts. The researchers found that supported CaO and
MgO showed far more activity than unsupported CaO and MgO.
Again, CaOprovedto be superior to MgOat bothloading levels of 50
and 80%. Among the tested catalyst systems, CaO/Al
2
O
3
at 80wt.%
Author's personal copy
20 P.-L. Boey et al. / Chemical Engineering Journal 168 (2011) 1522
Table 3
Properties of the prepared biodiesel using waste crab shell as a source of CaO [55].
Property Unit Specication Results Test method
Ester content % (m/m) 96.5 Min. 98.8 EN 14103
Density (at 15

C) kg/m
3
860900 884 EN ISO 3675
Viscosity (at 40

C) mm
2
/s 3.55.0 4.2 EN ISO 3104
Cetane number 47 Min. 61 ASTM D6890
Cloud point

C Report 15 ASTM D2500
Pour point

C Report 12 ASTM D97
Cold lter plugging point

C Report 9 EN 116
Monoglyceride content % (m/m) 0.80 Max. 0.20 EN 14105
Diglyceride content % (m/m) 0.20 Max. 0.01 EN 14105
Triglyceride content % (m/m) 0.20 Max. Not detected EN 14105
loading system gave the best yield (97.5%) at a higher MeOH:oil
molar ratio (30:1) in 4h. Interestingly, the catalyst system could
be reused twice in the reaction and further reuse has yet to be
tested. The author concluded that the basic site density and basic
strength are the factors driving the catalytic activity. In the trans-
esterication of ethyl butyrate with methanol, CaO supported on
SBA-15, MCM-41 and fumed silica was utilized [60]. Among them,
the CaO/SBA-15 support system gave the best activity at 14wt.%
loading, and distinct from commercial CaO, the supported sys-
tem does not shown any lixiviation into the reaction medium. In
a similar research, Albuquerque and co-workers [61] found that
Mg/Ca was more active than Mg/Al in the transesterication of
ethyl butyrate with methanol. In addition, the methanolysis of sun-
ower oil also follows the same trend giving a methyl esters yield
of 92% at a MeOH:oil molar ratio of 12 and at 2.5wt.% of Mg/Ca
(at 3.8 ratio) catalyst system. As discussed earlier, Peterson and
Scarrah [33] also concluded that CaO loaded onto MgO exhibits
the most active catalysts among 28 studied catalysts and catalyst
systems.
3.6. Mechanism of CaO in transesterication
The reaction mechanism for CaO-catalyzed transesterication
has been studied by many researchers [35,37,43]. As described in
Fig. 4, the methoxide ion that is attached to the catalyst surface
attacks the carbonyl carbon of the triglyceride molecule (step 1).
This results in the formation of a tetrahedral intermediate (step 2).
Then the intermediate is rearranged to form a diglyceride anion
and a mole of methyl ester (step 3). The charged-anion is then sta-
bilized by a proton from the catalyst surface to form diglyceride
and at the same time regenerates the catalyst. The cycle contin-
ues until all three carbonyl centres of the triglyceride have been
attacked by the methoxide ions to give one mole of glycerol and
three moles of methyl esters. Calcium diglyceroxide, a compound
formed from the reaction between calcium oxide and glycerol, has
also been recognized as a catalyst [43,62,63].
3.7. Catalyst leaching
As far as solid catalysts are concerned, catalyst active species
leaching into the reaction media is always the prime concern. The
extent of the catalyst leachability is the yardstick, inversely, for the
solid catalysts practical usage as well as their ability to be reused.
For the case of CaO, past results indicate that it has a considerably
low leaching property and lower (0.035%) solubility in methanol
[43]. A work by Granados and et al. [35] revealed that the contri-
bution of CaO heterogeneity is more crucial and relevant to obtain
a higher yield. For reutilization of the catalyst, the leaching of CaO
was not so intense (able to be reused eight times with a yield rang-
ing from 81 to 73%), as long as a sufcient amount of catalyst is
employed in each reuse. Arzamendi et al. [38] found that for a 7.3h
reaction period, 25% CaO was dissolved at 50% conversion versus
30% for 100% conversion after a 10h reaction duration. In another
related study [36], a 10.5% soluble substance was found in 2h for
the rst reaction and for subsequent reuses, the amount reduced
drastically to around 4%. It is worth noting here that at a 0.5h reac-
tion time, only 2.6% catalyst was soluble. However, the authors
reported that the soluble substance could be removed completely
using cation-exchange resin. Comparing the leaching data in these
works, it can be deduced that the intense of active species leaching
is proportionate with the reaction time, hence, reaction conditions
with a shorter catalyst residing time could be the possible solu-
tion, of course, without compensating the purity and yield of the
nal product. In sum, although there is CaOlixiviation into reaction
media, the heterogeneity of CaOstill plays a dominant role over the
homogeneity route and by controlling the reaction duration, the
degree of catalyst leaching can be further minimized.
4. The way forward
Numerous research articles on CaO-catalyzed transesterica-
tion are evidence of its potential as a heterogeneous catalyst in
biodiesel production in the near future. Calcined CaO in neat form
Fig. 4. Mechanism of CaO-catalyzed transesterication [35,37,43].
Author's personal copy
P.-L. Boey et al. / Chemical Engineering Journal 168 (2011) 1522 21
has already had substantial catalytic activity and as to further
enhance its performance, current researches are in effort by num-
ber of possible ways and means. This scenario gives even a brighter
outlook for CaO in transesterication. The catalyst has also been
recognizedas one of the heterogeneous catalysts that canbe reused
for several consecutive runs and has tolerance towards lower grade
feedstock. In addition to these merits, CaOis easily obtainable from
various waste sources, at low-cost. Reports indicate that CaO does
not actively leach into the reaction medium; interprets the solid-
state stability of the catalyst in the reaction solution.
However, manyareas needtobeexploredtofurther enhancethe
performance of CaO. For instance, there are not many reports con-
cerning the possibility of co-use CaO from different sources. Such
a possibility is valid since several calcined waste shells have a high
CaO content. Pelleting CaO, with sufcient pores, is another area
that researchers can explore to simplify the catalyst recovery as
well as to stretch the number of reuse cycles. Since CaO lixiviation
is not a serious issue, the chances of extending its reusability are
substantial. Another potential niche area to be looked into is sim-
pler and cost-effective ways to transformCaCO
3
to CaO. At present,
almost all are using the calcination method at high temperatures,
which translates into higher catalyst preparation costs in terms of
furnace energy. Ways to minimize Ca content in the nal products
(methyl esters and glycerol) are essential as well. The major chal-
lenge of CaO is its unsuitability towards the very high FFA content
feedstock. In this regard, the oil needs to be treated rst to lower
the acid content to a more affordable level. Reports conrmed that
CaOcould tolerate moisture and FFA, however, to drawa solid con-
clusion on their inuences, more comprehensive investigation is
needed. Notwithstanding the many areas to be explored further,
the outlook of progressing intense and diverse research on CaO is
evidence of its potential as a heterogeneous catalyst in producing
biodiesel at the industrial level.
Acknowledgements
Financial support by Universiti Sains Malaysia (USM) under
USM-RU-PRGS Grant (1001/PKIMIA/841005), and the award of
USM Fellowship (G.P. Maniam) are gratefully acknowledged.
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