Energy Conversion and Management 65 (2013) 647–653

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Energy Conversion and Management

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

Biodiesel production using calcium manganese oxide as catalyst

and different raw materials
Joana Maia Dias a,b,⇑, Maria Conceição Machado Alvim-Ferraz a, Manuel Fonseca Almeida b,
José Diego Méndez Díaz c, Manuel Sánchez Polo c, José Rivera Utrilla c
a
Departamento de Engenharia Química, LEPAE, Faculdade de Engenharia, Universidade do Porto, R. Dr. Roberto Frias, 4200-465 Porto, Portugal
b
Departamento de Engenharia Metalúrgica e de Materiais, LEPAE, Faculdade de Engenharia, Universidade do Porto, R. Dr. Roberto Frias, 4200-465 Porto, Portugal
c
Departamento de Química Inorgánica, Faculdad de Ciencias, Universidad de Granada, 18071 Granada, Spain

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

Article history: The use of heterogeneous catalysts for biodiesel production aims to simplify the production process as
Received 8 August 2012 well as to reduce purification costs and related environmental impacts. Calcium manganese oxide was
Received in revised form 6 September 2012 recently identified by the authors as an interesting heterogeneous catalyst for biodiesel production from
Accepted 6 September 2012
animal fat; however, the difference between this and other catalysts, the catalyst activation/deactivation
Available online 13 November 2012
mechanisms, its behaviour in the synthesis using different raw materials as well as the impacts of its use
on product quality remained unclear. Therefore, the present work: (i) compared biodiesel production
Keywords:
using calcium manganese oxide and other catalysts (CaO and NaOH); (ii) studied the reasons leading
Biodiesel
Heterogeneous catalyst
to activation/deactivation of the heterogeneous catalyst; (iii) analysed biodiesel heterogeneous synthesis
Transesterification using calcium manganese oxide and different raw materials (lard, waste frying oil and a mixture); and
Waste (iv) evaluated raw material and catalyst impact on the product quality. Considering the use of different
Mixture catalysts, the results showed that, after 8 h of reaction, product purity was similar using the different cat-
alysts, being 92.5 wt.% using both NaOH and calcium manganese oxide and 93.8 wt.% using CaO. The
active species of the heterogeneous catalysts were CaO, in the case of calcinated calcium carbonate,
and Ca0.9Mn0.1O, in the case of calcinated calcium manganese oxide. Because the deactivating species
were different for both catalysts, the calcium manganese oxide required lower activation temperature,
which should be an advantage. When using different raw materials, the reaction was slower when lard
was used for biodiesel synthesis. Leaching results showed that catalytic behaviour was heterogeneous
but further purification of biodiesel might be needed. Using heterogeneous catalysis, after 8 h of reaction,
independently of the raw materials used, similar results were obtained regarding the reaction progres-
sion; the quality was generally maintained but the water content of the product was improved compared
to the homogeneous process.
Ó 2012 Elsevier Ltd. All rights reserved.

1. Introduction
The emergent need to find viable alternatives for the reduction
of fossil fuel dependency, more specifically regarding diesel
consumption, led to the increase of research work on biodiesel pro-
duction processes. Currently, the major industrial application com-
prises the use of first generation plants whereby vegetable oils,
generally used as food resource, are converted chemically into a
diesel substitute, by a simple transesterification reaction using a
basic homogeneous catalyst [1].
⇑ Corresponding author at: Departamento de Engenharia Química, LEPAE,
Faculdade de Engenharia, Universidade do Porto, R. Dr. Roberto Frias, 4200-465
Porto, Portugal. Tel.: +351 22 5081422; fax: +351 22 5081447.
E-mail address: jmdias@fe.up.pt (Joana M. Dias).
The need to find alternative raw materials, that do not compete
as food resource, and develop more efficient production processes,
less costly and more environmental friendly, has shifted the re-
search interests towards the production of second generation
(non-edible oils and advanced technologies) [2–5] and third gener-
ation (advanced raw materials) biodiesel [6,7]. There are several
different approaches regarding the definition of such generations.
From the author’s perspective, second generation biodiesel results
from the application of alternative feedstocks such as non-edible
oils and wastes as well as advanced technologies such as oil hydro-
genation and gasification/Fischer–Tropsch synthesis of lignocellu-
losic biomass. Third generation biodiesel results from the
application of advanced raw materials, with much greater produc-
tivities, such as microalgae and cyanobacteria.
In order to justify the large investments made on the currently
existing plants and avoid the high costs of implementing new

0196-8904/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.enconman.2012.09.016
648 J.M. Dias et al. / Energy Conversion and Management 65 (2013) 647–653
advanced technologies, the most attractive alternative solutions in
the short term are the ones that can easily substitute raw materials
and improve conventional processes in place. Accordingly, most
promising raw materials are alternative triglyceride sources, which
can be processed similarly, such as algae and cyanobacteria, non-
edible vegetable oils and waste raw materials.
The productivities achievable using third generation raw mate-
rials might enable a greater impact on overall biodiesel production
in the future; however, their application in a short term is limited
due to high associated costs, namely during harvesting [8]. Regard-
ing second generation raw materials, non-edible oils are very rele-
vant [4], but also dependent upon high land availability [9].
The use of waste materials has a very important role both in the
reduction of biodiesel production costs and the environmental im-
pacts caused by their incorrect management [10]. The use of raw
material mixtures is also important as they allow raw material
management according to availability, being even possible to cre-
ate benefits regarding product quality specifications [10,11].
Among the research work which considers the improvement of
current production processes, heterogeneous catalysis presents
great relevance.
In fact, one of the great limitations of the conventional homoge-
neous catalytic process is its high dependence upon the purity of
reactants (they need to be water free) and the sensitivity to the
presence of free fatty acids in raw materials. In both cases, catalyst
is consumed, soaps are produced and product yield is reduced
[12,13]. In addition, the need to perform extensive purification pro-
cedures to remove the dissolved catalyst brings high economic and
environmental impacts. The application of heterogeneous catalysts
in industrial processes might bring great advantages in overcoming
such technological challenges as they avoid the use of further puri-
fication steps (catalyst might be removed by simple filtration),
generally do not lead to soap production, can be used in the pres-
ence of free fatty acids and allow product quality improvement and
reduction of corrosion and toxicity problems compared to the
homogeneous process [13–15]. The search for the best heteroge-
neous catalyst and the use of reaction conditions that are compet-
itive with the homogeneous process is, however, still a challenge.
The reversibility of the transesterification reaction is another
technological challenge, because great limitations are imposed to
achieve high product conversions (namely the use of high alco-
hol/oil molar ratios). In agreement, research is emerging on the
development of innovative technological approaches, by the inte-
gration of reaction and separation processes into one operating
unit (reactive separation), which can be combined with the use
of heterogeneous catalysts to overcome equilibrium limitations
and offer high conversions and selectivity. These technologies, also
called process intensification technologies, might not only offer
high conversions but also increase deeply the economic effective-
ness of the biodiesel production process, by reducing capital costs
and energy requirements. Several interesting related studies are
reported in the literature [16–22].
The search for an efficient heterogeneous catalyst and the opti-
mization of such integrated processes is therefore of great rele-
vance within the context of improving biodiesel production
technologies.
In relatively recent years, several studies have been developed
on heterogeneous catalysis for biodiesel production [23–25], an
overview of such studies might be found in several reviews [25–
32]. Different heterogeneous catalysts might be used, including ba-
sic, acid, mixtures of materials, materials generated from bio-
waste, and enzymes [26].
According to the different studies, calcium oxide, both alone or
supported, is the mostly used heterogeneous catalyst, because it
presents high basicity, low solubility, acceptable reaction condi-
tions and relatively low price [26,33]. Alternative catalysts, such
as mixed oxides containing calcium, have shown good results
regarding biodiesel synthesis through heterogeneous catalysis
[34]; however, the use of such mixed oxides is still understudied.
To deeply study these catalysts, calcium manganese oxide was re-
cently investigated by the authors as heterogeneous catalyst for
biodiesel production through transesterification of lard [35]; de-
spite the good results obtained, the difference between this and
other catalysts, the catalyst activation/deactivation mechanisms,
its behaviour in the synthesis using different raw materials as well
as the impacts of its use on product quality remain unclear. There-
fore, the present work aims to complete previous work regarding
the use of calcium manganese oxide as catalyst and also to provide
additional information, not reported in the literature, regarding the
catalyst activation and deactivation, the use of different raw mate-
rials and the quality of the obtained fuel, compared with the homo-
geneous process. The specific objectives were to: (i) compare
biodiesel production using calcium manganese oxide, calcium
oxide and sodium hydroxide; (ii) study the reasons leading to acti-
vation/deactivation of the heterogeneous catalysts; (iii) evaluate
biodiesel heterogeneous synthesis using calcium manganese oxide
and different raw materials, namely, lard, waste frying oil and a
mixture; and, (iv) evaluate process impacts on the product quality,
according to EN 14214.
2. Experimental
2.1. Material
The raw materials used were: pork lard, waste frying oil and a
mixture of waste frying oil (78 wt.%) and pork lard. The pork lard
was supplied by Irmãos Monteiro S.A, a Portuguese meat process-
ing industry, being kept in the freezer at 4 °C during the experi-
mental period. The waste frying oil was from different domestic
sources, obtained at a voluntary collection system implemented
at Faculdade de Engenharia da Universidade do Porto.
Methanol 99.5% (analytical grade, Fischer Scientific) was used
for biodiesel synthesis and n-Heptane (analytical grade, Merck)
was used for catalyst cleaning. Heterogeneous catalysts were pre-
pared using CaCO3, CaO (analytical grade, both supplied by Sigma–
Aldrich) and MnO2 (analytical grade, supplied by Riedel-de-Haën).
For homogeneous synthesis, sodium hydroxide powder 97% (re-
agent grade, Aldrich) was used.
2.2. Catalyst preparation
CaO was prepared by calcination of CaCO3. Calcium manganese
oxide was prepared conducting a solid-state reaction by mixing
both oxides (CaO and MnO2) in an agate mortar using an equimolar
proportion. After, the material was calcined.
The calcination temperatures were selected after thermogravi-
metric (TG) analysis of the materials using a heating rate of
20 °C min 1.
When catalyst was not immediately used, calcination procedure
was repeated to avoid catalyst deactivation. After calcination, cat-
alyst was kept for a few minutes in a desiccator under vacuum be-
fore use.
2.3. Characterization procedures
Raw material characterization, evaluation of biodiesel conver-
sion, biodiesel quality determinations and catalyst analysis were
performed.
The following properties of the raw materials were determined:
(i) acid value, by volumetric titration according to the standard NP
EN ISO 660 (2002); (ii) iodine value, determined from ester content
 J.M. Dias et al. / Energy Conversion and Management 65 (2013) 647–653
according to annex B of EN 14214 (2009); and (iii) composition,
from the methyl ester content using gas chromatography (GC)
according to EN 14103 (2003) and NP EN ISO 5508 (1996).
The evaluation of biodiesel conversion was performed by mea-
suring the product methyl ester content using GC according to EN
14103 (2003). GC analysis was performed in a Dani GC 1000 DPC
gas chromatograph (DANI Instruments S.p.A.), with an AT-WAX
(Heliflex capillary, Alltech) column (30 m, 0.32 mm internal diam-
eter and 0.25 lm film thickness). The injector temperature was set
at 250 °C, while the detector (FID) temperature was set at 255 °C.
The carrier gas used was N2 with a flow of 2 mL/min. Injection
was made in a split mode, using a split flow rate of 50 mL/min,
the volume injected was 1 lL. The following temperature program
was used: 120 °C, heating at a rate of 4 °C/min until 220 °C and
holding at that temperature for 10 min.
Biodiesel quality was evaluated according to the European bio-
diesel standard EN 14214 (2009). The following parameters were
determined: (i) acid value, by volumetric titration according to
the standard EN 14104 (2003); (ii) kinematic viscosity at 40 °C,
using glass capillary viscometers according to the standard ISO
3104 (1994); (iii) water content, by Karl Fischer coulometric titra-
tion according to the standard NP EN ISO 12937 (2003); (iv) ester
and linolenic acid methyl ester contents, by GC according to the
standard EN 14103 (2003); and, (v) iodine value, determined from
ester content according to annex B of EN 14214 (2009).
The calcium content of biodiesel was determined through
atomic absorption spectrophotometry at an external laboratory.
The sample used for analysis was obtained by evaporation, calcina-
tion at 550 °C and nitric acid attack of the residue obtained from
the biodiesel sample.
Catalysts were analysed by X-ray diffraction analysis (BRUKER
D8 Advance) in order to identify the compounds in their structure.
The thermogravimetric analysis was made in a Setaram (model 92-
16.18) thermobalance.
2.4. Biodiesel production procedures
2.4.1. Biodiesel heterogeneous synthesis
The production process included pre-treatment, transesterifica-
tion and purification procedures, described as follows.
2.4.1.1. Pre-treatment. The raw materials were dehydrated at
100 °C and after cooled to near the reaction temperature (50 °C).
2.4.1.2. Transesterification. Synthesis was performed in a glass reac-
tor consisting of a 250 mL round-bottom flask with three necks im-
mersed in a temperature controlling bath; the reactor was
equipped with a water-cooled condenser, a magnetic stirrer, a sep-
tum for syringe sample collection, an entrance for nitrogen and a
dropping funnel. To start the reaction, catalyst (3 wt.% relative to
fat weight) was placed into the reactor which was under controlled
nitrogen atmosphere; following, the necessary amount of metha-
nol (methanol to fat molar ratio of 18:1) was added to the catalyst
using the dropping funnel and both were kept under mixing until
the reaction temperature was reached; finally, the raw material
(70 g of the raw material at the reaction temperature (50 °C))
was slowly added to that mixture, also using the dropping funnel.
The starting of the reaction was considered to be after the addition
of all the raw material into the reactor; at that time, mixing of the
reactants was changed from medium to vigorous stirring.
2.4.1.3. Purification. The reaction mixture was filtered under vac-
uum and left to complete phase separation overnight. The catalyst
collected in the filter was washed with 40 mL of heptane using vac-
uum filtration and after dried in the oven at 100 °C. The organic
649
phases were finally separated and the methanol in excess was
recovered from each, separately.
In order to evaluate the progress of the reaction, samples were
taken at 0.25, 0.5, 1, 2, 4 and 8 h. The sampling was made through
the septum using a syringe. Each time, around 1 mL was taken and
filtered through a syringe filter of 25 mm diameter and 0.2 lm
pore size (VWR brand) to remove residual catalyst and immedi-
ately inserted in an ice bath to ensure the reaction end. After, the
reaction mixture was distilled under vacuum, in a rotary evapora-
tor and the lighter phase was analysed in terms of its methyl ester
content, according to EN 14103 (2003) as described in Section 2.3.
2.4.2. Biodiesel homogeneous synthesis
To compare the progression of the reaction using heterogeneous
and homogeneous processes, homogeneous synthesis was per-
formed in the same reactor used in the heterogeneous process,
but not with nitrogen atmosphere; reaction conditions were se-
lected according to previous work [11]. To start the reaction, 70 g
of the raw material were used and a solution of 0.8 wt.% of NaOH
(percentage relative to lard amount) with methanol (6:1 methanol
to lard molar ratio) was added using the dropping funnel to the
reactor which contained the lard at 60 °C.
In order to evaluate the progress of the homogeneous reaction,
samples were taken at 0.25, 0.5, 1, 2 and 4 h. After each period, 1 g
of the reaction mixture was added to 1 mL of an HCl solution (pre-
pared considering the calculated amount of HCl needed to stop the
reaction by neutralising NaOH in the mixture). The organic phase
was separated, washed with 2 mL of distilled water and dried in
a rotary evaporator at 90 °C. After, the sample was analysed in
terms of its methyl ester content according to EN 14103 (2003),
as described in Section 2.3.
3. Results and discussion
3.1. Raw material properties
The waste frying oil presented an acid value of 0.91 mg KOH/g.
Lower acid values of such raw material, around 0.8 mg KOH/g,
were reported [11]; however, it is not common, since the exposure
to humidity during storage and other environmental factors tend
to cause the degradation of the triglycerides in the oil, conse-
quently increasing its acid value. For instances, in a study by Ber-
rios et al. [36], the acid value of the waste frying oil was 3.7 mg
KOH/g.
The iodine value of the raw material is directly related with the
one determined in the resulting biodiesel. The iodine value of the
waste frying oil was 129 g I2/100 g, being higher than the limit,
according to biodiesel quality standard (120 g I2/100 g); therefore,
a raw material mixture was prepared aiming to reduce such iodine
value [11]. The determined iodine value of the mixture was 117 g
I2/100 g, close to the estimated one, which was 115 g I2/100 g.
The pork lard presented an acid value of 0.71 mg KOH/g and an
iodine value of 68 g I2/100 g, values similar to the ones of commer-
cial lard [11], showing very low degree of oxidation.
The composition of the pork lard, the waste frying oil and the
mixture might be analysed from their respective methyl ester com-
position, presented in Table 1.
The pork lard presented a very similar composition to the com-
mercial lard [11]. The waste frying oil showed a composition rela-
tively different from other obtained at the same voluntary
collection system [11]; however, that should be expected because
it varies according to each frying oil source, that can be very di-
verse depending upon each person’s habits. The composition of
the mixture was, as expected [11], a reflection of the composition
of each component.
650 J.M. Dias et al. / Energy Conversion and Management 65 (2013) 647–653

Table 1 3.2. Catalysts activation/deactivation mechanisms

Methyl ester profile obtained using pork lard (L), waste frying oil (WFO) and a 78/22
mixture (weight fraction) of waste frying oil and lard (78WFO/22L) as raw materials
for biodiesel production and mean molecular weight of raw materials.
Without calcination, the studied heterogeneous catalysts were
inactive in the transesterification reaction; therefore, in order to
Raw material composition L WFO 78WFO/22L define the best suited catalyst calcination temperature, thermo-
Methyl ester profile, wt.% gravimetric (TG) analysis of CaCO3, the mixed oxide and also of
Myristate (C14:0) 1.5 0.1 0.4 Ca(OH)2 were performed. The respective profiles are presented in
Palmitate (C16:0) 23.9 7.3 10.7
Palmitoleate (C16:1) 2.1 0.1 0.6
Fig. 1.
Stearate (C18:0) 12.2 4.0 5.4 Fig. 1 indicates that calcination leads to the decomposition of
Oleate (C18:1) 42.5 26.9 31.5 the hydroxide and carbonate species, which are responsible for
Linoleate (C18:2) 15.1 60.0 50.2 the inactivation of the catalysts. By comparing the TG analysis of
Linolenate (C18:3) 0.9 0.5 0.7
Ca(OH)2 with that of the calcium manganese oxide, one concludes
Others 1.8 1.1 0.5
that calcination of the mixed oxide eliminates the calcium hydrox-
Mean molecular weight (g moL 1) 863.4 877.7 873.6
ide specie present in the mixed oxide (representing around 10 wt.%
of initial mass). Similarly, taking in account the starting decompo-
sition temperature of calcium carbonate, of about 600 °C, it can be
assumed that a meaningless fraction of the mixed oxide was car-
bonated. Also, it can be concluded that the activation of the mixed
oxide requires a lower temperature than the one of calcium
carbonate.
According to the results, the selected temperatures were 900 °C
and 750 °C for CaCO3 and calcium manganese oxide calcinations,
respectively.
As the deactivating species in both catalysts are not equal, the
calcium manganese oxide requires lower activation temperature,
which should be an advantage in the production process (less costs
regarding the catalyst preparation and regeneration).

3.3. Catalysts characterisation

In order to identify the active species, X-ray diffraction analysis

was performed in the materials prior and after calcinations. The
mixed oxide was also characterised after being used in the transe-
Fig. 1. Thermogravimetric profiles of calcium carbonate, calcium manganese oxide
sterification reaction.
and calcium hydroxide (heating rate: 20 °C min 1). Prior to calcination, calcium carbonate material was mainly
constituted by CaCO3 and by a small amount of Ca(OH)2 (Fig. 2A).

Fig. 2. X-ray diffraction pattern for: (A) CaCO3 prior to calcination; (B) calcium manganese oxide prior to calcination; (C) calcium manganese oxide after calcination; and (D)
calcium manganese oxide after being used in the transesterification reaction.
 J.M. Dias et al. / Energy Conversion and Management 65 (2013) 647–653
Fig. 3. Product methyl ester content (wt.%) over time using homogeneous and
heterogeneous catalysts for lard transesterification (heterogeneous transesterifica-
tion: 50 °C; 18:1 methanol to lard molar ratio and 3 wt.% of lard as catalyst;
homogeneous transesterification: 60 °C, 6:1 methanol to lard molar ratio and
0.8 wt.% of lard as catalyst).
Regarding calcium manganese oxide, prior to calcination was
fundamentally constituted by Ca(OH)2, presenting in smaller rep-
resentation Ca2MnO4 and Mn3O4 and a very small amount of CaCO3
(Fig. 2B).
As CaCO3 and Ca(OH)2 were the main species present in both
materials used, the results showed that they are inactive in the
transesterification reaction.
The thermal decomposition of calcium carbonate occurs during
calcination leading to the production of calcium oxide. After calci-
nation of the mixed oxide, the major specie resultant was a calcium
manganese oxide with an empirical formula close to Ca0.9Mn0.1O;
additionally, small amounts of Ca2MnO4 and Mn3O4 were also
present, but not CaO alone (Fig. 2C).
After being used in the reaction, the X-ray diffraction analysis of
the mixed oxide catalyst showed that the catalyst was mainly con-
stituted by Ca(OH)2 (Fig. 2D). Regarding Ca2MnO4 and Mn3O4, they
remained closely in the same proportion as before calcination.
The results showed that, when used in the reaction, the calcium
manganese oxide probably releases CaO that becomes hydrated
with the consequent formation of Ca(OH)2; regarding Ca2MnO4
and Mn3O4, as they remain practically in the same proportion as
before calcination, the results suggest that they are inactive in
the reaction. Accordingly, the hydration, which might result from
the contact of the mixed oxide with air and possibly with residual
water existing in the reaction media, seems to be the main reason
for catalyst inactivation.
According to several authors [33,37,38], the CO2 is known to be
the main deactivating agent of the CaO catalyst, whereas the
hydration and formation of Ca(OH)2 is less important.
Catalyst characterization showed, therefore, that the active spe-
cies were CaO, in the case of calcinated calcium carbonate, and
Ca0.9Mn0.1O, in the case of calcinated calcium manganese oxide.
3.4. Biodiesel production using calcium manganese oxide and other
catalysts
The results regarding the progression of the reaction using the
studied heterogeneous catalysts and the most commonly used
homogeneous catalyst are presented in Fig. 3.
It is clear that the reaction rate of the heterogeneous catalysis
does not compete with the homogeneous one. In fact, after
15 min of reaction, the maximum methyl ester content was ob-
tained using the homogeneous catalyst.
Regarding the use of the heterogeneous catalysts, CaO showed
faster reaction rate until 4 h of reaction, showing after very similar
651
behaviour compared to the calcium manganese oxide. Considering
that the same amount of the active specie existed, this fact shows
that the calcium manganese oxide was less active than the CaO in
the transesterification reaction; as hydration plays the main role in
calcium manganese oxide deactivation, as previously reported, the
use of anhydrous conditions might improve calcium manganese
oxide activity in the transesterification reaction.
After 8 h, the conversion was very similar independently of the
catalyst used and a final methyl ester content of 92.5 wt.% was ob-
tained using NaOH and calcium manganese oxide as catalysts and
93.8 wt.% using CaO as catalyst.
It should be referred that the comparison between heteroge-
neous and homogeneous catalysis was made using different reac-
tion conditions; however, they were selected as being within the
optimum range for both processes according to previous work [35].
A higher catalyst amount (3 wt.% compared to 0.8 wt.%) and
molar ratio of methanol to fat (18:1 compared to 6:1) were used
in heterogeneous catalysis; however, methanol and catalyst can
be reused in the transesterification process [35,39], which can min-
imize these disadvantages. On the other hand, much higher reac-
tion times were needed to ensure reaction completion in
heterogeneous catalysis (4–8 h compared to 15 min). Nevertheless,
it should be considered that the introduction of an heterogeneous
process reduces the need of purification steps, which are also time
consuming; this means that a global evaluation of production time
should be conducted in each case to conclude if in fact the higher
reaction times can be compensated by the reduction of the number
of purification steps.
3.5. Leaching of the heterogeneous catalysts
Catalyst leaching was evaluated by measuring the amount of
calcium in the produced biodiesel using both heterogeneous cata-
lysts and lard as raw material.
A content of 35.4 mg of calcium per kg of biodiesel was found in
biodiesel produced using the calcium manganese oxide catalyst
and a content of 15.8 mg of calcium per kg of biodiesel was found
in biodiesel produced using calcium oxide catalyst.
Regarding the calcium manganese oxide, considering that the
mass of catalyst used was essentially constituted by Ca0.9Mn0.1O,
such amount represents around 0.16 wt.% of the initial amount of
catalyst used, corresponding to a catalyst concentration in the
raw material of around 0.005 wt.% (considering a product yield of
86 wt.% and using a product loss estimate of 5 wt.% by sampling).
Regarding the calcium oxide, considering that the mass of cata-
lyst corresponds to CaO, such amount represents around 0.06 wt.%
of the initial amount of catalyst used corresponding to a catalyst
concentration in the raw material of around 0.002 wt.% (also con-
sidering a yield of 86 wt.% and using a product loss estimate of
5 wt.% by sampling).
The amount of catalyst found (0.005 and 0.002 wt.%), that could
be responsible for homogeneous synthesis, is between 200 and 500
times smaller than the concentrations usually used in homoge-
neous catalysis (around 1 wt.%).
In the previous study [35], the reusability of the calcium man-
ganese oxide catalyst was evaluated under different reaction con-
ditions. To be reused, the catalyst was first oxidised at 550 °C to
ensure removal of organics and after activated by calcination at
750 °C. After being used in the reaction, no significant loss of activ-
ity was found. Therefore, the present study confirms that the cata-
lytic behaviour was in fact essentially heterogeneous. However,
despite the small percentages relatively to the initial amount, cal-
cium concentration exceeded the standard limit imposed by the
European quality standard EN 14214 (5 mg/kg biodiesel). There-
fore, the results showed that when using these heterogeneous cat-
alysts, some degree of purification (that might be considerably less
652 J.M. Dias et al. / Energy Conversion and Management 65 (2013) 647–653

Table 2 were determined in biodiesel obtained using different raw materi-

Product methyl ester content of biodiesel produced from pork lard (L), waste frying oil
(WFO) and a 78/22 mixture (weight fraction) of waste frying oil and lard (78WFO/
22L), using calcium manganese oxide as catalyst.
Raw material Methyl ester content (wt.%)
4h 8h
L 81.9 92.5
WFO 94.9 94.3
78WFO/22L 94.8 92.1
than with homogeneous catalysis) needs to be done to ensure the
removal of such residual catalyst that might leach into the biodie-
sel phase.
3.6. Comparison of the catalyst performance using different raw
materials
Biodiesel production from lard, waste frying oil and a mixture of
waste frying oil and lard was evaluated using calcium manganese
oxide as catalyst during an 8 h period, considered the time which
ensured the same purity regardless the catalyst used, according
to Section 3.4.
In addition, results regarding product methyl ester content
using the different raw materials, after 4 h of reaction (determined
to evaluate reaction progression) and after 8 h of reaction, are pre-
sented in Table 2.
Results showed that after 4 h of reaction, when the waste frying
oil and the mixture were used as raw materials, the reaction was
almost completed; however, when lard was used alone, a greater
reaction time was needed. The differences between the results
probably relate with the higher viscosity of the lard which conse-
quently retards the reaction due to more difficult contact between
the three phases (alcohol/catalyst/trygliceride phase).
The slight decrease in the methyl ester content when reaction
time increased from 4 to 8 h using the waste frying oil and the mix-
ture as raw materials was not considered significant.
After 8 h of reaction, purity was similar independently of the
raw material used. The purity obtained was very close to the min-
imum required according to EN 14214, however slightly lower.
Similar values have been reported for biodiesel production from
fats [10,11,40].
3.6.1. Biodiesel quality
Most studies considering the use of heterogeneous catalysts for
biodiesel production do not evaluate overall biodiesel quality; they
focus essentially in evaluating the reaction progression, similarly
to what was done in the previous sections.
In the present study, some quality parameters, considered the
most relevant according to previously developed work [11,39],
als and calcium manganese oxide as catalyst (after 8 h of reaction).
Table 3 presents the results and compares them with those ob-
tained using homogeneous catalysis.
It can be seen that the water content of biodiesel obtained using
homogeneous catalysis, the iodine value when using waste frying
oil and heterogeneous catalysis and the methyl ester content in
all cases were the parameters that were not in agreement with
the specifications according to EN 14214.
As expected, the fulfilment of the water content specification
was more difficult when homogeneous catalysis was used due to
the washing step of the product (to remove the catalyst) and the
extreme dependency of this parameter upon the purification meth-
ods applied.
The differences in the iodine value of the waste frying oils relate
to the different sources and probably different storing conditions (at
the source). Heterogeneous synthesis using the mixture ensured, as
predicted, the agreement with the iodine value specification.
Regarding the methyl ester content, slightly higher values were
obtained using homogeneous catalysis. However, using different
raw materials, the obtained biodiesel showed a methyl ester con-
tent varying from 92.1–96.3 wt.%, being very close to the minimum
required (96.5 wt.%) according to EN 14214.
The acid value of the product was higher using heterogeneous
catalysis compared to homogeneous catalysis (0.17–0.25 mg
KOH/g compared to 0.04–0.08 mg KOH/g) but still significantly be-
low the maximum standard limit (0.50 mg KOH/g). Such differ-
ences might be related with the fact that the homogeneous
catalysts tend to react with free fatty acids to generate soaps, caus-
ing the reduction of the acid value of the final product.
It should be noted that the viscosities of the products were sim-
ilar (from 4.59 to 4.75 mm2s 1) independently of the process and
raw material used. The other evaluated parameters were in agree-
ment with the product quality specifications.
4. Conclusion
The present work intended to complete a previous study by
evaluating the difference between calcium manganese oxide and
other catalysts, the catalyst activation/deactivation mechanisms
and the biodiesel synthesis and quality using different raw
materials.
It was possible to obtain similar biodiesel purity (higher than
92 wt.%) using calcium manganese oxide, calcium oxide and so-
dium hydroxide as catalysts for biodiesel production from pork
lard.
Regarding the studied heterogeneous catalysts, CaO showed
higher reaction rates than calcium manganese oxide but the mixed
oxide required lower activation temperature, which should be an
advantage in the production process. The active species were iden-
tified and the hydration of the mixed oxide seemed to be the main

Table 3
Quality parameters of biodiesel obtained through heterogeneous catalysis (HtC, calcium manganese oxide) and homogeneous catalysis (HmC, NaOH) a of pork lard (L), waste
frying oil (WFO) and a 78/22 mixture (weight fraction) of waste frying oil and lard (78WFO/22L) and comparison with European biodiesel quality standard.

Property L WFO 78WFO/22L EN 14214

HtC HmC HtC HmC HtC HmCb
Water content (wt.%) 0.04 0.11 0.04 0.10 0.04 0.06 <0.05
Acid value (mg KOH/g) 0.25 0.04 0.28 0.08 0.17 0.07 <0.50
Iodine value (g I2/100 g) 68 67 129 117 117 108 <120
Kinematic viscosity at 40 °C (mm2s 1) 4.59 4.71 4.70 4.69 4.74 4.75 3.50–5.00
Methyl ester content (wt.%) 92.5 94.4 94.3 96.3 92.1 96.3 >96.5
Linolenic acid methyl ester content (wt.%) 0.9 1.0 0.5 0.6 0.7 0.7 <12.0
a
Dias et al. [14] (60 °C, 6:1 molar ratio of methanol: raw material, 0.8 wt.% NaOH).
b
A mixture of waste frying oil (80 wt.%) and lard was used.
 J.M. Dias et al. / Energy Conversion and Management 65 (2013) 647–653
reason for catalyst inactivation, whereas the CO2 was probably the
main deactivating agent of the CaO catalyst.
Compared to the homogeneous process, using different raw
materials and calcium manganese oxide as catalyst, product qual-
ity was generally maintained and better results were achieved
regarding the water content of the product. Leaching results
showed, however, that some degree of purification is required to
ensure product compliance with European quality standards
regarding calcium content.
Acknowledgments
The authors thank the Project QREN 3491: Fat-Value. J. M. Dias
thanks the FCT for the fellowship SFRD/BD/22293/2005 and SFRH/
BPD/73809/2010.
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