Navas et al. Bioresour. Bioprocess.

(2020) 7:4
https://doi.org/10.1186/s40643-019-0291-3

RESEARCH Open Access

A sustainable process for biodiesel

production using Zn/Mg oxidic species
as active, selective and reusable heterogeneous
catalysts
Marisa B. Navas, José F. Ruggera, Ileana D. Lick and Mónica L. Casella*

Abstract 
This paper describes the preparation and characterization of MgO and ZnO-based catalysts, pure and mixed in differ-
ent proportions, supported on γ-Al2O3. Their catalytic performance was studied in the transesterification of soybean
oil and castor oil with methanol and butanol, attempting to produce biodiesel. XRD (X-ray diffraction), SEM–EDS
(scanning electron microscopy–energy dispersive X-ray spectroscopy), ­CO2-adsorption and ­N2-adsorption allowed
characterizing the prepared catalysts. The characterization results were in all cases consistent with mesoporous solids
with high specific surface area. All the catalysts exhibited good results, especially in the transesterification of castor oil
using butanol. For this reaction, the reuse was tested, maintaining high FABE (fatty acid butyl esters) yields after four
cycles. This good performance can be attributed to the basic properties of the Mg species, and simultaneously, to the
amphoteric properties of ZnO, which allow both triglycerides and free fatty acids to be converted into esters. Using
these catalysts, it is possible to obtain second-generation biodiesel, employing castor oil, a raw material that does not
compete with the food industry. In addition, butanol can be produced from renewable biomass.
Keywords:  Biodiesel, Heterogeneous catalysts, Soybean oil, Castor oil, Transesterification, Mg/Zn species

Introduction including biofuels produced from genetically modified

The growing demands of energy in sectors such as trans- algae (Hoekman et al. 2012; Abdullah et al. 2019).
port or various industries, require the need for replace- Biodiesel attracted much attention as alternative
ment of non-renewable fossil fuels. Renewable fuels energy source, since it is renewable, sustainable and bio-
appear as an attractive option to satisfy this demand. degradable. In addition, biodiesel presents a lower emis-
Nowadays, there is a classification for these biofuels, sion of particulate matter and NOx. These environmental
which include: first generation, those produced from benefits are due to the absence of sulfur compounds and
highly available food sources; second generation, those aromatic residues in the oils (Alaei et al. 2018; Shan et al.
generated using non-edible raw materials or involving 2018). Biodiesel not only has environmental advantages,
advanced technologies; third generation, including bio- but also has properties that make it a good fuel, such as
fuels from algae; and finally, fourth generation, those its high ignition point, excellent lubricity and miscibility
with petroleum fuels, what allows it to produce different
blends (Knothe and Razón 2017). Nowadays, biodiesel
can be produced in a cleaner and less expensive way,
*Correspondence: [email protected]
Centro de Investigación y Desarrollo en Ciencias Aplicadas “Dr. Jorge J.
using advanced technologies and waste sources, like bio-
Ronco” (CINDECA) (CCT‑La Plata CONICET, UNLP, CICPBA), Departamento waste oil (Chuah et al. 2017).
de Química, Facultad de Ciencias Exactas, Universidad Nacional de La
Plata, Calle 47 No 257, 1900 La Plata, Argentina

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Navas et al. Bioresour. Bioprocess. (2020) 7:4 Page 2 of 13

Biodiesel is defined as a mixture of alkyl esters of long- acceptors (Sun et al. 2019). On the contrary, butanol has
chain fatty acids. For the production at an industrial level, not been so extensively investigated. This alcohol pre-
generally short-chain alcohols (methanol, ethanol or sents a higher boiling point in comparison with other
butanol) are used in the transesterification of vegetable short-chain alcohols; it is also less corrosive and less solu-
oils or animal fats (Lin et al. 2006). The transesterification ble in water, and consequently has a greater miscibility
reaction involves three consecutive and reversible steps. with the oil phase (Steen et al. 2008). The use of butanol
At each step, an alkyl ester of a fatty acid molecule is gen- over other short-chain alcohols, such as methanol or
erated for each molecule of alcohol consumed. Triglycer- ethanol, would be preferred, since its longer chain favors
ides are converted into diglycerides and monoglycerides, the properties of the final biodiesel, as well as its blend-
and finally into glycerol, the main byproduct (Issariyakul ing with conventional diesel. Besides, the butyl ester
and Dalai 2014). Biodiesel can be also produced through has a higher energy value than the analogues methyl or
the esterification of the free fatty acids (FFA) present in ethyl esters, since it contains more carbon atoms. More-
the raw material (da Silva Filho et al. 2018). over, butyl ester has a higher cloud point than methyl
Vegetable oils are the most chosen source of triglyc- esters (Hájek et  al. 2017). In addition, butanol also has
erides in biodiesel production. The climatic, socio-eco- the advantage of being produced from different types of
nomic and cultural conditions are fundamental in the renewable sources. Then, bio-butanol can be produced
choice of the oil. The characteristic crops of each region by fermentation of lignocellulosic materials (agricultural
are the essential source for obtaining these oils. For or paper waste, for example), or non-cellulosic materials
example, in Argentina and Brazil soybean, canola or sun- (corn or molasses, for example) (Kumar and Gayen 2011;
flower oil are used, in India, on the other hand, jatropha Kolesinska et  al. 2019). Given the properties of butanol
oil is mostly used (Ullah et  al. 2016). Vegetable oils are for biodiesel production, more research is needed in this
chosen over animal fats due to their renewability, bio- regard.
degradability and lower content of aromatic compounds The biodiesel production can be carried out using
and sulfides, producing biodiesel in a less harmful way to homogeneous and heterogeneous catalysis. Nevertheless,
the environment (Koh and Mohd Ghazi 2011). Further- the use of homogeneous catalysts favors the formation
more, considering the world demand for food, biodiesel of unwanted soaps, which is a disadvantage in the sepa-
can be produced using vegetable oils that do not compete ration and purification steps of the process (Margellou
with food industry. This is called, as mentioned previ- et al. 2018). In this sense, heterogeneous catalysis is more
ously, second-generation biodiesel. The biodiesel produc- convenient, mainly thanks to an easier separation of the
tion from non-edible raw materials is a field that is being catalyst from the reaction products. This allows the cata-
extensively explored, so it is necessary to develop studies lysts to be washed and reused. In addition, heterogeneous
on different sources of triglycerides that do not compete catalysis does not produce soaps (Boonyuen et al. 2018).
with the food industry. Selecting these types of vegetable Nevertheless, the presence of FFA can generate soaps,
sources allows, in turn, to reduce biodiesel production which is why more efficient catalysts have to be studied,
costs (Zhang et  al. 2018a). Among the options already and these systems must be optimized. An example of this
known and studied are Jatropha curcas crude oil, Silybum is the work developed by Sun et al. (Sun and Li 2016). The
marianum oil, Firmiana platanifolia L.f. oil and Euphor- basic catalysts are preferred, since they allow using mild
bia lathyris crude oil (Adeniyi et  al. 2019; Zhang et  al. reaction conditions. Catalysts with a good performance
2018b, Pan et  al. 2018). Castor oil is an excellent alter- have been reported, including supported metal oxides
native (Elango et  al. 2019). This oil is mainly composed and hydrotalcites (Lee and Wilson 2015).
of the ester derived from the ricinoleic acid (9Z, 12R)- MgO has been used as a transesterification catalyst,
12-hydroxy-9-octadecenoic acid). Also, castor seeds although it presents limitations regarding its weak basic
have greater potential over other crops, since it contains strength and solubility (Sharma et al. 2011). To improve
40–55 wt% of oil. The soybean oil contains 15–20% of oil, its catalytic performance, a possible alternative is to gen-
for example (Keera et al. 2018). It has been demonstrated erate a binary system with another species like other
that the presence of hydroxyl group in the ricinoleic acid metal oxides. It is known from the literature that the
favors both the synthesis and the use of the derived bio- addition of ZnO can enhance the activity of MgO, given
diesel (Wang and Sun 2016). Due to this particular chem- its amphoteric properties (Veiga et al. 2016).
ical composition, castor oil presents higher viscosity and In this work, in order to develop a more sustainable
polarity than other oils, what allows its employment in process, the transesterification of soybean oil and castor
various industries (Conceição et al. 2007). oil, using methanol and butanol has been investigated.
Transesterification is generally carried out using meth- Different mixtures of Mg and Zn oxidic species were
anol or ethanol as reagents, both good fatty acid acyl developed as catalysts. Castor oil was chosen because it
Navas et al. Bioresour. Bioprocess. (2020) 7:4 Page 3 of 13

is a non-edible raw material, aiming to solve the issue of equipment. The analysis conditions are detailed in Navas
competition with the food industry. Therefore, it allows et al. 2018.
obtaining second-generation biodiesel. Given the supe- Scanning electron microscopy images were obtained
rior properties of biodiesel prepared from butanol, with a Philips Scanning Electron Microscope 505. The
instead of methanol or ethanol, butanol was selected energy dispersive X-ray analysis (EDS) was performed
for the transesterification reaction. It is important to using an EDAX DX PRIME 10 analyzer at a working
highlight that butanol can also be obtained from renew- potential of 15  kV. To establish the dispersion of the
able sources, since bio-butanol can be obtained by fer- active species on the catalysts, a qualitative mapping of
mentation, generating a sustainable process to produce the surface was performed.
biodiesel. The combination of two renewable, environ- FTIR spectra of both the fresh and post-reaction  0.5
mentally friendly raw materials that improve the bio- Zn/Mg catalyst were recorded in the diffuse reflectance
diesel properties, is an important step oriented to the mode on a Thermo Avatar 360 instrument, using a DTGS
production of second-generation biodiesel. detector. The spectra were averaged from 120 scans in
the range of 400–4000 cm−1 at a resolution of 4 cm−1. To
detect the probable presence of carbonaceous deposits
Materials and methods on the post-reaction catalyst, oxidation thermogravimet-
Catalyst preparation ric analysis was performed using a thermobalance (Shi-
Mg and Zn catalysts, pure and mixed in different pro- madzu TGA-50) with a heating rate of 10 °C/min and an
portions, were prepared by the conventional method air/He feed (2:1). For both the fresh and post-reaction
of coprecipitation of carbonates, followed by calcina- catalyst, the mass used was 10  mg. The weight loss and
tion [Lee et al. 2013]. The precursors were supported on the temperature were recorded as a function of time. The
γ-Al2O3, meshed and sieved to 60–100 mesh. The total derivative curve (DTGA) was obtained from the weight
amount of supported oxides was 0.17 mol (MgO + ZnO) loss information as a function of time.
per 100  g of alumina. Mg/Zn mixtures were prepared
with Zn/Mg atomic ratios of 0.5, 1.0, 1.5 and 2.0. Transesterification procedure
In a typical preparation, the necessary amount of Mg The catalysts performance was studied in the transes-
and Zn nitrates (supplied by Biopack and Anedra) were terification reaction, employing two vegetable oils, soy-
dissolved in an aqueous suspension of γ-Al2O3. Then, bean oil and castor oil (one at a time, without mixtures
­(NH4)2CO3 1 M was added under vigorous stirring. The between them) and two alcohols, methanol (Cicarelli,
pH was controlled at a value of 9, using ­NH4OH. The 99.8%) and butanol (Merck, 99.4%) (again, one at a time).
solution was stirred for 2 h, aged, and then the solid was In order to differentiate the studied oils, in terms of
filtered and dried at 60  °C overnight. The active phases their characteristics, their compositions are presented in
were obtained after calcination at 500 °C. Table 1.
The reaction was conducted in a 250-cm3 three-necked
Catalyst characterization batch glass reactor, provided with a reflux condenser
The elemental composition of the catalysts was deter- reflux and a mechanical stirrer. Alcohol/oil molar ratio,
mined by atomic absorption spectroscopy using a Varian
240 equipment. For each sample, the digestion was car-
ried out using concentrated HCl on hot plate. The lines Table 1  Typical fatty acid composition (%) of  soybean oil
employed were 202.6 nm for Mg lamp, and 213.9 nm for and castor oil (Meneghetti et al. 2006, 2007)
Zn lamp.
Fatty acid Fatty acid content (%)
The textural properties of the different catalysts were
determined by N ­ 2 physisorption at − 196  °C, employing Soybean oil Castor oil
a Micromeritics ASAP 2020 analyzer, and the total sur-
Myristic (14:0) 0.2 –
face area ­(SBET) was calculated by the BET (Brunauer–
Palmitic (16:0) 16.0 1.8
Emmett–Teller) method.
Stearic (18:0) 2.4 –
The crystalline phases present were determined using
Oleic (18:1) 23.5 –
an X-ray diffractometer Philips PW 1740 (Cu Kα radia-
Linoleic (18:2) 51.2 11.2
tion, λ = 0.154 nm). The samples were scanned from 5° to
Linolenic (18:3) 8.5 –
75° at the scanning speed of 1 min−1.
Ricinoleic (18:0(OH)) – 87.0
In order to study the basicity of the prepared cata-
Total C18 85.6 98.2
lysts, the amount of adsorbed ­CO2 was quantified by
Free fatty acids (FFA) 0.1 1.2
thermogravimetric analysis, using a Shimadzu TGA-50
Navas et al. Bioresour. Bioprocess. (2020) 7:4 Page 4 of 13

catalyst amount and reaction temperature were estab- Table  2 also presents the textural properties of differ-
lished at 6:1; 5 wt%, and 60  °C for methanol and 80  °C ent catalysts, determined by ­N2 physisorption. For all the
for butanol (Navas et al. 2018). These values were deter- catalysts, the pore distribution showed the presence of
mined from a previous optimization study on the soy- macro and mesoporous. The mesopore diameters for the
bean–methanol oil system carried out by our research Zn/Mg catalysts were slightly higher than for the pure
group (Sánchez et al. 2014). oxide catalysts. Observing the macropore values, ZnO/γ-
The product analysis was carried out by a GC (gas Al2O3 catalyst presented a value of 67 Å, a considerably
chromatography) method according to EN (Euro- higher value than that observed for MgO/γ-Al2O3 cata-
pean Standard) 14105 and ASTM (American Society of lyst and the Zn/Mg mixtures, that range between 52 and
Testing Materials) D6584 [EN 14105; ASTM D6584], 57 Å. The pore distribution graphs can be found as Addi-
using a GC-2010 Plus Tracera Gas Chromatograph, tional file 1.
equipped with a BID detector. A MEGA-Biodiesel 105 For 0.5 Zn/Mg and 2 Zn/Mg catalysts, the specific sur-
(15  m × 0.32  mm ×  0.10  μm) capillary column was face area decreases with respect to the pure γ-Al2O3. This
used. Samples were taken after 2, 4 and 6  h of reaction, result is a sign of the existence of an interaction between
except other specified. The pre-injection treatment of both metals with the support. It is worth noting that the
the samples, as well as the chromatographic conditions, catalyst with the Zn/Mg atomic ratio of 1.5 has the high-
is detailed in Navas et  al. 2018. This previous work also est specific surface and also shows a slight decrease in the
specified the equations used for the calculation of triglyc- pore volume, which could indicate the presence of some
eride conversion, selectivity to monoglycerides or diglyc- segregated phase on the surface. On the other hand, the
erides, and FAME (fatty acid methyl ester) or FABE yield 2 Zn/Mg catalyst presented a S ­ BET value quite similar
and selectivity (Navas et al. 2018). to that of the ZnO/γ-Al2O3 catalyst, maybe due to its
high Zn proportion. The synthesis method used in this
Results and discussion work allows obtaining catalysts whit high specific sur-
Catalyst characterization face areas. Olutoye and Hameed have studied mixed Mg
The elemental composition of the catalysts was deter- and Zn supported oxides, using Al(NO3)3 as a precursor
mined by AAS (atomic absorption spectroscopy). Table 2 instead of commercial ­Al2O3 and found that this method
gathers these results, and the nominal contents of the led to the formation of mixed phases with surfaces
oxides have also been included. As can be observed, the around 50  m2  g−1, while in this work values of between
experimental atomic ratio was quite similar to the theo- 150 and 250  m2  g−1 have been obtained (Olutoye and
retical one, for all the studied catalysts, except for the 2 Hameed 2013). Considering that these solids will be used
Zn/Mg catalyst in which the zinc content is substan- in a heterogeneous process, a high surface area is a desir-
tially lower than expected. The difference found may be able property.
accounted for the pH control in the preparation, since Figure 1 depicts the obtained isotherms, which are type
MgO and ZnO require different pH values for an optimal IV for all catalysts, attributed to macro and mesoporous
precipitation (Ngamcharussrivichai et al. 2008; Lee et al. materials (Thommes et  al. 2015). The isotherms of the
2011). mixed oxides are more similar to MgO/γ-Al2O3 (Fig.  1,

Table 2  Textural properties and chemical composition of the prepared catalysts

Catalyst SBET ­(m2/g) Vpore ­(cm3/g) dpore (Å) MgO (wt%)a MgO (wt%)b ZnO (wt%)a ZnO (wt%)b Zn/Mgc Zn/Mgd
Mesopores Macropores

MgO/γ-Al2O3 223 0.43 32 57 6.85 nd – – – –

0.5 Zn/Mg 168 0.32 36 57 4.67 4.14 4.61 5.72 0.5 0.68
1 Zn/Mg 232 0.35 37 51 3.42 3.81 6.26 5.47 1.0 0.71
1.5 Zn/Mg 266 0.41 37 52 2.74 3.15 8.30 9.21 1.5 1.45
2 Zn/Mg 182 0.39 37 51 2.28 1.82 9.22 6.22 2.0 1.69
ZnO/γ-Al2O3 173 0.42 32 67 – – 13.83 nd – –
γ-Al2O3 216 0.45 nd 75 – – – – – –
a
  Nominal value
b
  Measured by AAS
c
  Theoretical atomic ratio
d
  Experimental atomic ratio (through AAS measurements)
Navas et al. Bioresour. Bioprocess. (2020) 7:4 Page 5 of 13

Fig. 2  Results of C
­ O2 adsorption for the prepared catalysts

Fig. 1  BET isotherms for the prepared catalysts: (a) MgO/γ-Al2O3;

(b) 0.5 Zn/Mg; (c) 1 Zn/Mg; (d) 1.5 Zn/Mg; (e) 2 Zn/Mg and (f )
ZnO/γ-Al2O3 similarity could be associated to the presence of basic
sites of the MgO, as well as to a certain adsorption capac-
ity of the alumina, which, being the support, is found in
curve a) than to ZnO/γ-Al2O3 (Fig.  1, curve f ). All the the highest proportion in all the catalysts.
desorption branches indicate percolation of pores, espe- The XRD patterns obtained are shown in Fig.  3. In
cially in 2 Zn/Mg catalyst, where the percolation evi- every pattern, the broad peaks corresponding to the
dently occurs in two different types of pores, due to the presence of a transition alumina phase, located at 37.6°,
observed irregularity. Hysteresis loops for the isotherms 45.8° and 66.8° (JCPDS (Joint Committee on Powder Dif-
of all studied catalysts correspond to H2 type, according fraction Standards) card no 29-1480) can be observed.
to IUPAC classification (Thommes et  al. 2015). H2 type It was not possible to identify peaks of MgO phase in
loop is broad with a long and almost flat plateau and a the MgO/γ-Al2O3 catalyst, even though Mg has been
steep desorption branch. Many inorganic oxides give measured by atomic absorption (Table  2). This could
the more common type H2 loops. The pore structures be due to the fact that the crystals are too small to be
in these materials are generally complex and tend to be detected by XRD technique. The MgO phase was neither
made up of interconnected networks of pores of different
size and shape (Neimark et al. 2008).
To estimate the basicity of the catalysts, ­CO2 adsorp-
tion tests were carried out. The obtained results, pre-
sented in Fig. 2, are expressed as mg of ­CO2 adsorbed per
100 mg of catalyst. The 1.5 Zn/Mg catalyst exhibited the
highest value of ­CO2 adsorption (0.282 mg%), this result
being even higher than those of MgO/γ-Al2O3 and ZnO/
γ-Al2O3 (0.258  mg% and 0.259  mg%, respectively). It is
possible to infer that the 1.5 Zn/Mg catalyst has higher
density of basic sites than the monometallic catalysts and
probably this fact can be associated with a higher expo-
sure of the active sites because of the higher surface area
presented by this catalyst. The 0.5 Zn/Mg catalyst pre-
sented a slightly lower value than the monometallic cata-
lysts. On the other hand, 1 Zn/Mg and 2 Zn/Mg catalysts
presented values considerably smaller than those sam-
ples. It can be considered that, despite the small differ-
ences observed, the amount of ­CO2 adsorbed is similar
Fig. 3  XRD patterns for the prepared catalysts. (a) MgO/γ-Al2O3;
for all the catalysts, indicating the presence of basic sites (b) 0.5 Zn/Mg; (c) 1 Zn/Mg; (d) 1.5 Zn/Mg; (e) 2 Zn/Mg and (f )
in all of them, even in the ZnO/γ-Al2O3 catalyst. This ZnO/γ-Al2O3
Navas et al. Bioresour. Bioprocess. (2020) 7:4 Page 6 of 13

observed in the Mg nor Zn-containing catalysts. In the “flakes”. The images of the Zn/Mg catalysts showed that
zinc-containing catalysts, no diffraction lines associated those with a higher proportion of MgO have a morphol-
with the presence of crystalline phases of ZnO, either ogy similar to MgO, with small and thin filaments on
of hydroxides or of Zn aluminium oxide were observed. the surface; and those with a higher proportion of ZnO
The ZnO/γ-Al2O3 catalyst, despite having the highest exhibit the small “flakes”. In the surface of 1.5 Zn/Mg
concentration of Zn, did not exhibit peaks correspond- catalyst, the small particles appear to be melted together.
ing to the zincite phase (JCPDS no 22-1034). However, To investigate about the distribution of the different spe-
in the diffractograms of the Zn-containing catalysts cies on the surface of the catalysts, EDS analysis and a
very intense signals located at 2θ = 11.77°; 23.3°; 34.8°; qualitative mapping of Mg and Zn was carried out. Fig-
46.8°, 60.56° and 62.09° appear, which can be associated ure 5 shows the result of the mapping for the 0.5 Zn/Mg
with the presence of mixed aluminium and magnesium catalyst and, as can be seen, both elements have a homo-
oxidic phases, such as magnesium aluminium hydroxide geneous dispersion on the alumina surface. Regarding
(PDF 00-0351275) or magnesium aluminium hydroxide the Zn/Mg ratio measured by this technique, the results
hydrate (PDF 00-0350965). It should be noted that both were quite similar to those obtained by AAS for all the
1.5 Zn/Mg and 2 Zn/Mg catalysts, which contain the catalysts.
highest zinc content, the diffraction lines corresponding
to the magnesium aluminium hydroxide crystalline phase Catalytic activity
are more intense and narrower, indicating an increase Transesterification of soybean oil using methanol
in the crystallinity of the segregated phase. It is evident Initially, catalysts were used in the classical transesterifi-
that the addition of zinc modifies the characteristics of cation reaction of soybean oil with methanol. The selec-
the magnesium phases, segregating hydrated phases that tivities and FAME yield obtained are presented in Fig. 6.
modify the surface properties of the catalysts, its capacity The results show that the addition of Zn does not favor
to absorb ­CO2 among others. the transesterification of soybean oil with methanol,
The images obtained by SEM are presented in Fig.  4. as the FAME yield decreases progressively by increas-
Monometallic catalysts showed porous surfaces with ing the Zn proportion. The addition of Zn modifies the
small particles, exhibiting different morphologies: the basic properties of the catalyst, due to its amphoteric
MgO particles have small filaments on their surface, behavior. This makes the catalysts less active in the
while ZnO particles are small sheets with appearance of transesterification. The widely accepted mechanism for

Fig. 4  SEM images for catalysts

Navas et al. Bioresour. Bioprocess. (2020) 7:4 Page 7 of 13

Fig. 5  Qualitative mapping of 0.5 Zn/Mg surface. a Mg mapping; b SEM image (×200); c Zn mapping

Fig. 6  Selectivity to monoglycerides (black square), diglycerides Fig. 7  Selectivity to monoglycerides (black square), diglycerides
(green square) and FAME (blue square), and FAME yield (red square) (green square) and FAME (blue square), and FAME yield (red square)
obtained for each catalyst, in the transesterification of soybean oil obtained for each catalyst, in the transesterification of castor oil with
with methanol methanol

transesterification reaction by basic heterogeneous catal- catalysts tested, also improving the FAME selectivity
ysis, initially comprises the formation of the methoxide exhibited using MgO/γ-Al2O3 (94%). Therefore, using a
anion and an alkoxycarbonyl intermediary, on basic sites mixture of Mg and Zn oxides, even in a minimal propor-
on the surface (Pasupulety et al. 2015; Navas et al. 2018). tion of Zn, allows the transesterification reaction to pro-
The presence of Zn modifies the nature of the active sites, ceed more selectively to FAME.
disfavouring the yield of FAME.
These results are in accordance to those found by Lee
et  al., who reported the study of mixtures of Mg and Transesterification of castor oil using methanol
Zn oxides, in which the catalytic activity grows as the As a contribution to the development of a more sustain-
basicity increases (Lee et  al. 2013). Lee et  al. prepared able process, a non-edible oil was selected as reactive. To
mass catalysts; exhibiting BET surface values around 10 do so, castor oil was employed instead of castor oil. The
­m2  g−1. In this work, the applied catalysts present the results of the transesterification employing methanol are
advantage of exhibiting much larger surfaces, due to the presented in Fig. 7.
use of γ-Al2O3 as support, what would contribute to the All the catalysts showed good FAME selectivity, except
catalytic performance. for 0.5 Zn/Mg, which only reached 60%. The FAME
Using the mixed oxides, the FAME selectivity improved selectivity is increased by adding Zn, until it reaches
notably in relation to ZnO/γ-Al2O3 (61%). The FAME the 1.5 Zn/Mg ratio, and then it remains approximately
selectivity to FAME exceeded 95% for the rest of the constant. The 0.5 Zn/Mg catalyst presented the lowest
Navas et al. Bioresour. Bioprocess. (2020) 7:4 Page 8 of 13

performance in the series (15%); this can be attributed to FABE yield decreases to a large extent. This may be due
the low specific surface between all Zn/Mg catalysts. to the ZnO ratio is too high to allow transesterification
In general, Zn/Mg catalysts produced better yields of the soybean oil, a reagent without a significant propor-
using an oil with a higher amount of free fatty acids tion of FFA. Also, the specific surface increases as the
(FFA). MgO provides the necessary basicity to carry out amount of ZnO increases, except for 2 Zn/Mg catalyst.
transesterification, while ZnO favors the esterification of The same is observed for the FABE yields obtained. Then,
FFA, due to its amphoteric properties (Yan et al. 2009). for this mixture of reagents, the specific surface is a fac-
1.5 Zn/Mg catalyst presented the highest FAME yield tor to be taken into account.
(76%), and a high FAME selectivity (99%), so it can be It is notorious that the reaction using 2 Zn/Mg catalyst
considered as the best of the series in the transesterifi- reached lower FABE yield than the reaction using ZnO/
cation of castor oil and methanol. This same catalyst did γ-Al2O3, even when the catalysts exhibits similar specific
not show a good performance in the analogous reaction surfaces. This could be due to the low proportion of MgO
with soybean oil (31%). Then, 1.5 Zn/Mg appears to be a in the catalyst, which would notably decrease the density
more efficient catalyst in the transesterification of oils of of basic sites, and therefore, the catalytic activity (Lee
lower quality, due to the amphoteric properties of ZnO. et al. 2013). Also, the SEM micrographs obtained for this
Castor oil contains a greater amount of free fatty acids catalyst presented only large flake-like particles belong-
(FFA) than soybean oil (Table 1), which can be esterified. ing to ZnO.

Transesterification of soybean oil using butanol Transesterification of castor oil using butanol
The Zn/Mg catalysts were further evaluated in the trans- Finally, the prepared catalysts were evaluated in the
esterification of soybean oil using butanol, an alcohol that transesterification of castor oil, using butanol. The
can be obtained from biomass. Figure 8 presents the dif- obtained percentages of FABE yield are presented in
ferent selectivities and the performance to FABE for each Fig. 9. All catalysts reached FABE selectivity of approxi-
catalyst. It is remarkable that all catalysts showed FABE mately 100%. This means that the conversion of triglycer-
selectivities very close to 100%. The catalyst 1.5 Zn/ ides is complete, and also directed towards the esters, the
Mg presented the highest FABE yield (66%), which was desired reaction product. The prepared catalysts resulted
also the only one that exceeded the percentages exhib- exceptionally active in the transesterification between
ited by MgO/γ-Al2O3 and ZnO/γ-Al2O3 (50% and 42%, these reagents. The catalytic activity is favored for the
respectively). considerably values of specific surface exhibited by the
In general, the addition of ZnO increases the catalytic catalysts, which exposes a great number of pores. In
activity for transesterification between soybean oil and these pores, the active sites for the reaction are located.
butanol, except for 2 Zn/Mg catalyst. Using this catalyst, Besides, the mixture of MgO and ZnO allows produc-
ing simultaneously the transesterification of triglycerides
and the esterification of free fatty acids (FFA). Castor

Fig. 8  Selectivity to monoglycerides (black square), diglycerides

(green square) and FAME (blue square), and FAME yield (red square)
obtained for each catalyst, in the transesterification of soybean oil Fig. 9  FABE yield (%) obtained for the prepared catalyst, in the
with butanol transesterification of castor oil with butanol
Navas et al. Bioresour. Bioprocess. (2020) 7:4 Page 9 of 13

oil is considered a “low-quality oil”, due to its content of oils with a high FFA content require an initial stage that
approximately 1.2% of FFA (Table 1), susceptible of being allows them to be removed or converted into esters, to
esterified. ZnO, thanks to its amphoteric properties, pro- then perform transesterification, avoiding the saponifi-
motes both transesterification and esterification (Yan cation reaction (Borges and Díaz 2012).
et al. 2011). Castor oil presented a higher solubility in butanol,
FABE yield (%) was evaluated more in detail for 0.5 than in methanol or ethanol. This high miscibility is
Zn/Mg, due to the good result obtained with this cata- extremely favorable for the reaction and contributes
lyst. FABE yield obtained after each hour of reaction is to the interaction between the reagents (Baskar and
presented in Fig. 10. The reaction present good yields of Soumiya 2016; Keera et al. 2018).
FABE even after 1 h of reaction (95%), and the maximum These results are encouraging; facing the produc-
yield is reached at 3 h of reaction. tion of second-generation biodiesel, because castor oil
The advantage of using a catalyst of this type lies in is a non-edible raw material. Moreover, butanol is an
the fact that both transesterification and esterification attractive option, feasible to be produced from bio-
reactions can be carried out in a single step. Generally, mass, a renewable source.
Table  3 presents a comparison of our results and
different recently optimized catalytic systems, using
different alcohols and vegetable oils in the transesterifi-
cation reaction. The FABE yields obtained in our work,
specifically for the mixture castor oil–butanol are very
good. These results were achieved using an amount
of catalyst lower than that presented in the consid-
ered systems. Besides, the alcohol:oil ratio employed
is also lower than other transesterification reactions.
This indicates that, for the transesterification of castor
oil using butanol, and employing the prepared Mg/Zn
catalysts, excellent FABE yields can be obtained using
a minimum excess of alcohol over the stoichiometric
ratio.
It is worth mention that the same reaction conditions
optimized in a previous work for the soybean–metha-
nol oil system were used the present paper (Sánchez
et al. 2014), obtaining even better results.
Fig. 10  FABE yield (%) obtained in the transesterification between
castor oil and butanol, using 0.5 Zn/Mg

Table 3  Comparison of results between different catalytic systems

Catalyst Oil Alcohol Conditions Selectivity Yield Conversion
to esters of esters (%)
Alcohol:oil %wt Temperature (%) (%)
ratio catalyst (°C)

This work 1.5 Zn/Mg-γAl2O3 Castor oil Butanol 6:1 5 80 > 99 > 99 > 99
Mahdavi and CaO-MgO/Al2O3 Cottonseed Ethanol 8.5:1 14.4 95 – – 97.6
Monajemi oil
(2014)
Chuayplod Mg(Al)La hydro- Rice bran oil Methanol 30:1 7.5 75 97 78 –
and talcites
Trakarnpruk
(2009)
Rahman et al. Zn–CaO Eucalyptus oil Methanol 6:1 5 65 – 93.2 –
(2019)
Rubio-Cabal- CaZn2(OH)6·2H2O Sunflower oil Methanol 12:1 4 60 – > 90 –
lero et al.
(2009)
Navas et al. Bioresour. Bioprocess. (2020) 7:4 Page 10 of 13

Catalyst recycling any adsorbed species remaining on the surface. In both

An important aspect of a heterogeneous catalyst is its spectra, a broad band between 2700 and 3800  cm−1
stability and the possibility of being reused. After the can be identified, due to the stretching of the surface
transesterification of castor oil with butanol, 0.5 Zn/Mg hydroxyl groups. This band is usually found in materi-
catalyst was removed; then washed with methanol on a als such as MgO, ZnO and ­Al2O3 (Xi and Davis 2011).
hot plate to eliminate any oil residue adhered to the sur- The bands observed in the region between 1250 and
face. The catalyst was finally dried overnight and calcined 1800  cm−1 can be assigned to the symmetric and
2  h at 500  °C, in order to burn any organic deposit and antisymmetric water bending (Bagabas et  al. 2013).
regenerate the active sites in the surface. In the region below 1000  cm−1, a broad band can be
The 0.5 Zn/Mg catalyst was reused in the transesteri- observed, corresponding to the overlapping of the
fication of castor oil using butanol. The results obtained absorption bands assigned to the stretching of Al-O
are presented in Fig. 11. It is observed that after an initial (ca. 560, 788 and 940  cm−1), Mg–O (645  cm−1) and
decrease in the catalytic performance between the first Zn–O (430 cm−1) (Kuśtrowski et al. 2005).
and second catalytic runs, from then on, the obtained Thermogravimetric analysis performed on the 0.5
yield remains approximately constant. The catalyst con- Zn/Mg catalyst, fresh and post-reaction, showed simi-
tinued to generate acceptable results, preserving a 100% lar profiles and similar total mass losses (approximately
FABE selectivity. 15%) (Fig. 12c). The observed peaks most probably cor-
In order to obtain chemical information about the respond to adsorbed water. It is well known that this
post-reaction catalyst, XRD, FTIR and thermogravi- type of materials has the property of adsorbing water
metric analysis were carried out. The results obtained and a certain “memory effect” produced during their
are presented in Fig.  12a–c, respectively. Slight changes rehydration (Angelescu et  al. 2008; Kwon et  al. 2020).
in the physicochemical properties of the catalyst were No significant mass loss is observed in the post-reac-
observed. Figure  12a shows the diffractograms obtained tion catalyst that would have been associated with the
for the catalyst before and after its use in the reaction. total oxidation of carbonaceous species. These results
The crystalline phases initially detected remain after 4 agree with those obtained by FTIR.
recycling cycles. However, a higher degree of crystallinity
is observed in the regenerated sample, since the already
mentioned peaks at 2θ = 11.77°; 23.3°; 34.8°; 46.8°, 60.56° Conclusions
and 62.09° are sharper and more intense in this sample. All the catalysts prepared and evaluated in this work
Figure  12b exhibits the DRIFT spectra for the fresh demonstrated being active in the studied reactions.
0.5 Zn/Mg catalyst and the same catalyst after 4 reac- Among the prepared catalysts, the 1.5 Zn/Mg was the
tion cycles. No substantial differences between both one with the highest surface area, with the consequent
spectra can be observed, evidencing that there are not higher density of basic sites, attributed to the segre-
gation of a magnesium aluminium hydroxide hydrate
phase. These characteristics gave rise to a catalyst
having a high performance in the transesterification
of soybean oil and castor oil, with both methanol and
butanol.
An especially remarkable result was obtained in the
transesterification of castor oil with butanol. All the cata-
lysts exhibited excellent results, with FABE yields higher
than 94% and FABE selectivities of approximately 100%.
The catalysts presented good performance in the transes-
terification of low-quality oil with a high degree of FFA,
such as castor oil.
The prepared catalysts are an efficient alternative,
considering that castor oil is a nonedible and renewable
source, representing a cleaner approach to the produc-
tion of biodiesel. In addition, butanol is an alcohol that
can be obtained from renewable sources.
For this reaction, the reuse was tested, maintaining
Fig. 11  Recycling test of catalyst 0.5 Zn/Mg in the transesterification high FABE (fatty acid butyl esters) yields after four cycles.
of castor oil with butanol
Navas et al. Bioresour. Bioprocess. (2020) 7:4 Page 11 of 13

Fig. 12  a XRD spectra; b FTIR spectra and c thermogravimetric analysis for 0.5 Zn/Mg catalyst, a) fresh and b) after 4 reaction cycles

Additional file and contributed to the analysis of different characterization results. IDL also
contributed with the revision of the draft. MLC is the project director who
provided the funds for the realization of this work. MLC also contributed to the
Additional file 1. Additional figures. data interpretation and the revision of the draft. All authors read and approved
the final manuscript.

Abbreviations Funding
XRD: X-ray diffraction; SEM: scanning electron microscopy; EDS: energy This work was supported by the Agencia Nacional de Promoción Científica y
dispersive X-ray spectroscopy; FABE: fatty acid butyl esters; FFA: free fatty acids; Tecnológica (Argentina) (PICT 2015 No 0737), the Universidad Nacional de La
BET: Brunauer–Emmett–Teller; FTIR: Fourier transform infrared spectroscopy; Plata (Argentina) (Projects X700 and X7802) and the Comisión de Investiga-
GC: gas chromatography; EN: European Standard; ASTM: American Society of ciones Científicas de la Provincia de Buenos Aires (CICPBA) (Argentina).
Testing Materials; FAME: fatty acid methyl ester; AAS: atomic absorption spec-
troscopy; JCPDS: Joint Committee on Powder Diffraction Standards. Availability of data and materials
All data generated or analyzed during this study are included in this published
Acknowledgements article and its additional files.
The authors gratefully acknowledge Universidad Nacional de La Plata, Agencia
Nacional de Promoción Científica y Tecnológica, and Comisión de Investiga- Ethics approval and consent to participate
ciones Científicas de la Provincia de Buenos Aires for the financial support. The Not applicable.
authors also acknowledge the technicians working in the Centro de Investi-
gación y Desarrollo en Ciencias Aplicadas “Dr. Jorge J. Ronco” who performed Consent for publication
the analyses. Not applicable.

Authors’ contributions Competing interests

MBN carried out the synthesis of the different catalysts, performed the The authors declare that they have no competing interests.
transesterification reaction, with the previous set-up of the catalytic system,
and collaborated in the analysis of the obtained results. MBN also drafted the Received: 28 October 2019 Accepted: 30 December 2019
work. JFR collaborated in the data interpretation, and also with the writing
and revision of the draft. IDL performed the ­CO2-adsorption experiments,
Navas et al. Bioresour. Bioprocess. (2020) 7:4 Page 12 of 13

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