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Bioresource Technology 99 (2008) 6793–6798

Catalysts of Cu(II) and Co(II) ions adsorbed in chitosan used

in transesterification of soy bean and babassu oils – A new route
for biodiesel syntheses
Rondinelly Brandão da Silva a, Alcides Fernandes Lima Neto a,
Lucas Samuel Soares dos Santos a, José Renato de Oliveira Lima a, Mariana Helena Chaves a,
José Ribeiro dos Santos Jr. a, Geraldo Magela de Lima b, Edmilson Miranda de Moura a,
Carla Verônica Rodarte de Moura a,*
a
Departamento de Quı́mica – CCN, Universidade Federal do Piauı́, 64049-550 Teresina, PI, Brazil
b
Departamento de Quı́mica – ICEx, Universidade Federal de Minas Gerais, 31270-901 Belo Horizonte, MG, Brazil

Received 18 September 2007; received in revised form 23 January 2008; accepted 27 January 2008
Available online 28 April 2008

Abstract

Catalysts of Cu(II) and Co(II) adsorbed in chitosan was used in transesterification of soy bean and babassu oils. The catalysts were
characterized by infrared, atomic absorption and TG, and biodiesels was characterized by infrared, NMR, CG, TG, physic chemistry
analysis. The maximum adsorption values found for copper and cobalt cations were 1.584 and 1.260 mg g1, respectively, in 180 min.
However, conversion of oils in biodiesel was better when used Co(II) adsorbed in chitosan.
Ó 2008 Published by Elsevier Ltd.

Keywords: Biodiesel; Babassu; Catalysts; Metals; Chitosan

1. Introduction
The growing need of energy is a strategic matter of the
nations and its use is associated to level of development
of a country. The history shows that human well-being
and goods production are linked to the readiness and
accessibility of energy. The petroleum discovery combined
with the development of diesel engine produced a revolu-
tion in the industrial world. However the energy depen-
dence on renewable sources turned to be one of the
drawbacks. After more than one hundred years serious
problems have emerged. Some of them concerns to envi-
ronmental problems due to the pollutants generated dur-
ing the burning process. Furthermore, the dilemma
associated to the exhaustion of the petroleum sources
*
Corresponding author. Tel.: +55 86 3215 5840; fax: +55 86 32155692.
E-mail address: carla@ufpi.br (C.V.R. de Moura).
has not yet been overcome. On the other side the energy
demands continues to increase, so the need of alternatives
energy sources is urgent (Ma and Hanna, 1999). In this
context vegetable oils appear as an alternative to mineral
diesel oil. The possibility of using plants-derived fuels in
diesel engines is quite attractive (Li and Xie, 2006). Some
of the advantages are (i) they are produced from renew-
able sources, (ii) its use can reduce the petroleum needs
and not less important (iii) they are less aggressive to
the environment (Ferrari et al., 2005; Wu et al., 1998).
Brazil has an enormous potential to produce biodiesel,
in view of its vast oleaginous biodiversity spread over
its extensive territory. Moreover, it is very well geograph-
ically located and has a strong agricultural tradition (Par-
ente et al., 2003).
Biodiesel possess excellent properties as diesel engine
fuels; it can be used in compression–ignition engines with
little or no further modifications (Meher et al., 2006).

0960-8524/$ - see front matter Ó 2008 Published by Elsevier Ltd.

doi:10.1016/j.biortech.2008.01.047
6794 R.B. da Silva et al. / Bioresource Technology 99 (2008) 6793–6798
Among the attractive features of biodiesel fuel are (a) it is
not petroleum derived, (b) its combustion does not
increase the current atmospheric levels of CO2, (c) it is
biodegradable, (d) relative to conventional diesel fuel, its
combustion products have reduced levels of CO and
SOx emissions, and hydrocarbons, (e) it is not inflamma-
ble in normal conditions of transport, handling and stor-
age, (f) possesses a high cetan number that result in higher
ignition power and higher combustion, (g) posses an
appropriate viscosity, (h) possess an excellent lubricity
(Fukuda et al., 2001).
Some aspects are important in the biodiesel produc-
tion, through transesterification reaction: temperature,
type of alcohol (ethanol or methanol), type of catalyst
(alkaline or acid), alcohol/oil molar ratio, purity of the
reactants, mainly water content, and free fatty acids con-
tent in the oil (Schuchardt et al., 1998). Regarding cata-
lyst type, several have been tested. Basic catalysts as
magnesium or calcium oxides, sodium or potassium meth-
oxide, calcium, potassium and sodium hydroxides are the
most used in the transesterification reaction (Li and Xie,
2006; Reddy et al., 2006). Low cost and favorable kinetics
turned NaOH into the most used catalyst in industries
(Schwab et al., 1987). However, soaps and emulsions
can be formed during the reaction, which complicates
the purification process. Acid catalysts avoid soap forma-
tion, but it is associated to corrosion and lower catalytic
activity, compared to the basic system, and higher temper-
atures, above 100 °C, are required (Schuchardt et al.,
1998). Hence, one of the technological challenges of the
biodiesel industry is the search for alternative catalysts
that avoid emulsions and soap formation, presents high
activity and require low temperature and pressure. One
alternative is the use of the enzymatic catalysts, because
these systems do not generate any waste materials (Shi-
mada et al., 2002). Another possibility, described in the
literature, is the substitution of the acidic, basic or enzy-
matic systems by heterogeneous catalytic systems (Xie
and Huang, 2006), that utilizes metal complexes such as
Sn(3-hidroxi-2-metil-4-pirona)2(H2O)2 (Abreu et al.,
2005). Heterogeneous catalysts have significant advanta-
ges if compared to acids or bases as they are not corro-
sive, do not originates, emulsions or soap, the products
are easily separated, and they can be recovered. However,
some of these catalysts are not economically viable. In
this work it is described (i) the synthesis of a heteroge-
neous catalyst obtained by the adsorption of copper and
cobalt cations in pure chitosan, and (ii) its use in the bio-
diesel synthesis originated from babassu almonds and soy-
bean oils.
2. Experimental
Reagent grade CuCl22H20 (Vetec), CoCl26H2O
(Vetec), methyl alcohol (Synth), Sodium hydroxide (Vetec),
hydrochloric acid (Vetec), of analytical grade were used
without further purification. All vegetables oil were
obtained from commercial sources and used as received.
Chemical characterizations were accomplish according to
the Instituto Adolfo Lutz Norms (Instituto Adolfo Lutz,
1985, Normas analı́ticas do Instituto Adolfo Luts, vol.1),
United States Pharmacopeial (USP) (The United States
Pharmacopeial the National Formulary: USP 24, USA,
2000) and AOCS-Cd-1c-85 method (Official Methods and
Recommended Practices, 2000). Chitosan (Polymer), was
previously characterized according to the methods
described in the literature (Santos et al., 2003; Tonhi and
Plepis, 2002). Viscosity was measured using a viscosimetric
cinematic tube Cannon Fensk 350 in thermal bath Koehler
KV3000 in agreement with NBR-10441. Density was mea-
sured in an automatic densimeter Anton Par DMA 4500
following at ASTM D-4052. Sulfur was determined by
Ray-X, Horiba SLFA 1800H, in a accordance ASTM D-
4994. Flash Point was measured by Pensky Martens HFP
380, closed cup, in accordance to ASTM D-93. Atomic
absorption analysis were done using a spectrometer Spec-
tra-AA 220 FS models, Varian, with a GTA-100, with fire
and bottom broker deuterium lamp. Were used hollow
cathode lamps and fire of air–acetylene, in the following
wavelengths, 324.7 nm (Cu) and 240.7 nm (Co). Others
instrumental parameters were selected in agreement with
the recommendations of the analytical methods flame
atomic absorption spectrometry (Varian) (Analytical
Methods, Flame Atomic Adsorption, 1989). Thermogravi-
metric analysis (TGA) data were obtained with a TA
Instruments Model TGA-2050, thermobalance. At ambient
pressure, a 50 mL min1 nitrogen purge flow was used. The
heating rate was 10 °C min1 and was used a aluminum
pan of 20 lL with a ±0.5 mm diameter hole. The initial
temperature was 30 °C and the final one was 450 °C for
the biodiesels and 550 °C for the in natura oils. Infrared
analyses data were accomplished in CsI windows, in a
Spectrum GX-FT-GO System-Perkin Elmer. Analyses of
fatty acid esters was analysed by gas chromatography on
a Varian CP-3380 chromatograph with FID detector,
equipped with a polar polyethylenoglycol column BP 20,
12 m, 0.32 i.d. and film thickness of 0.25 lm. Oven temper-
ature ranged from 150 to 260 °C, using a heating rate of
10 °C min1. Spectra 1H-NMR were obtained under ambi-
ent conditions on a Bruker advances DRX-500 spectrome-
ter, using CDCl3 as solvent and TMS as reference.
2.1. pH and adsorption time of metals by chitosan
Nine Erlenmeyers flasks, containing 50 mL of
CuCl22 H2O or CoCl26H2O solutions (0.01 mol L1) were
stirred with 1 g of chitosan powder for 2 h. HCl and NaOH
solutions (0.1 mol L1) were used to adjust the pH between
2 and 10. Soon after the mixture were, filtered the Cu(II)
and Co(II) ions were analysed by atomic absorption. To
a becker of 250 mL was added 1 g of chitosan (PC) powder
and 100 mL of a CuCl22 H2O or CoCl26H2O solutions
(0.05 mol L1). This mixture was stirred for 3 h. Then,
every 30 min a sample was analysed by atomic absorption.
 R.B. da Silva et al. / Bioresource Technology 99 (2008) 6793–6798 6795

2.2. Catalyst preparation

0.7 Cu (II)
Co (II)
To a becker of 250 mL was added 1 g of chitosan pow-
0.6
der and 100 mL of CuCl22H2O or CoCl26H2O solution
(0.05 mol L1) and was stirred for 3 h in pH 6.5. The solu-

Concentração (mg/g)
0.5
tion was filtered and the solids (CCu and CCo) were dried
at 110 °C and stored.
0.4

2.3. Biodiesel preparation

0.3

A 250 mL two-necked flask fitted with a water-cooled

0.2
condenser was charged with 100 g of oil (soybean or
babassu), 20 g of methanol and 2 g of catalyst (CCu or
0.1
CCo) and three drops of NaOH solutions (0.01 mol L1). 2 4 6 8 10
The mixture was stirred vigorously and refluxed at 70 °C pH
for 3 h in pH 8.5. The organic phase was separated by
Fig. 1. pH adsorption study of Cu and Co ions in chitosan.
centrifugation and dried with anhydrous sodium sulfate.
The same experiment was performed in the absence of
catalyst. The adsorption capacity, Qe (mg metal g1 adsorbent)
was determined based on the difference of metal ions con-
3. Results and discussion centrations in the solution using the following equation
(Ruthven, 1984)
3.1. Infrared spectroscopy
ðC o  C e ÞV
Qe ¼ ð1Þ
The IR spectrum of pure chitosan (PC) revealed bands m
in the following wavelength: 3500 cm1 (O–H or N–H), where Co is the solution initial concentration (mg L1); Ce
1051 cm1 (C–O), 1654 cm1 (C@O), 1308 cm1 (C–N), is the equilibrium concentration of adsorbent (mg L1); V
2900 cm1 (C–H) e 1420–1380 cm1 (d–CH2 and CH3). is the solution volume (L) and m is the mass of the adsor-
Spectra IR of CCu and CCo showed the same bands of bent (g). The maximum adsorption values found for copper
PC, besides, it was observed bands at 518, 590, 446 and and cobalt were 1.584 mg g1 and 1.260 mg g1, respec-
420 cm1 which were attributed to the Co–N, Cu–N, Co– tively, in 180 min. Some studies in the literature revealed
O and Cu–O stretching frequencies, respectively (Nakam- that copper adsorption is larger than others transitions
oto, 1986). metals (Ruthven, 1984). The coordination of metals by
The main difference observed between spectra IR of polymeric ligands is governed by the microambient around
babassu and soybean oils (BO and SO) and their biodiesels the ligands and the solution polymer conformation (Klug
(BBCu, BBCo SBCu, SBCo) was a small displacement of et al., 1998). The amino groups of chitosan coordinated
the stretching C@O band of the biodiesels to lower energy in Cu(II) presents charge transfer bands, which can be
(1757–1741 cm1). This was attributed to the substitution attributed to strong interaction between Cu(II) and chito-
of the glycerol by the methoxylic group (Zagonel et al., san (Chiessi et al., 1992).
2004).
3.4. Thin layer chromatography (TLC)
3.2. pH effect in the metal chitosan adsorption
This analysis was performed in order to verify the oil to
The pH is of fundamental importance in the metal biodiesel conversion. The results of Rf of the oils in nature
adsorptions process in chitosan. Protonation of the amino (BO and SO) and the biodiesels (BBCu, BBCo, SBCu and
groups decreases the adsorption of metals (Guibal et al., SBCo) are listed in Table 1.
2000). Therefore, it was important to establish the best Rf of babassu and soy oils, were smaller than the biodie-
pH in which the ions Cu2+ and Co2+ are adsorbed. The sels, because the methyl esters present in biodiesels are
best range of pH for the adsorption of the cations situates lighter than the triacylglycerides present in crude oils.
between pH 6 and 8. Therefore, the catalyst was prepared Besides, residues of biodiesels were observed in the chro-
in pH 6.5.
Table 1
3.3. Atomic adsorption spectroscopy
Retention factor (Rf) of oils and biodiesels
Oil Biodiesel
Fig. 1 shows the adsorption isotherms of the Cu(II) and
Co(II) in chitosan. It was observed that saturation of chito- Babassu Soybean BBCu BBCo SBCu SBCo
0.32 0.30 0.46 0.45 0.42 0.42
san with the cations occurred after 3 h.
6796 R.B. da Silva et al. / Bioresource Technology 99 (2008) 6793–6798

matograms suggesting that the transesterification reaction Table 3

was not complete. Esters concentration in biodiesels of babassu and soybean
Esters BBCo BBCu Oliveira et al. SBCo SBCu Costa Neto
(1999) et al. (2000)
3.5. Yield of transesterification reaction
C8:0 5.04 4.60 5.50 – – –
C10:0 1.69 6.50 6.10 – – –
Conversion of oils in alkyl esters, were determined by C12:0 34.98 40.50 34.00 – – 0.10
NMR spectra9 according to Eq. (2) where relate integrated C14:0 13.23 15.01 19.20 – – 0.20
area of the signs due to methylene protons adjacent to the C16:0 3.01 2.16 10.60 11.65 5.85 9.90–12.20
ester group in tryglycerides and methyl ester (d 2.3) with C18:0 1.59 0.99 4.30 2.32 3.56 3.00–5.40
C18:1 7.20 4.38 17.10 19.85 22.23 17.70–26.00
methoxy protons of the methyl ester (d 3.7). The results
C18:2 5.62 2.65 3.10 45.73 47.60 49.70–59.60
found are, SBCo (94.01%), SBCu (88.82 %), BBCo (86.65 C18:3 0.87 – – 0.55 6.54 5.50–9.50
%) and BBCu (71.89 %).
ð2AME Þ nent. To be noted is the amount of methyl oleate, above
C ¼ 100  ð2Þ the expected. Nevertheless, it is not a conflicting value so
ð3ACH2 Þ
that it can be considered as contamination by other oil
types (Oliveira et al., 1999).
3.6. Physico-chemical analysis For the soybean biodiesels no discrepancy was found as
compared to results described in the literature (Costa Neto
The results for crude soybean and babassu oils were et al., 2000). The main esters were those derived from fatty
saponification index (SI) = 194 mg KOH g1 and 228 acids having 16–18 carbons chains and two or three
mmg KOH g1, acidic index (AI) = 0.4 mg KOH g1 and unsaturated.
0.6 mg KOH g1, iodine index (II) = 108.67 g/100 g1 and In soybean biodiesels methyl oleate and methyl linoleate
18.2 g/100 g, respectively. These results agree to literature were the most abundant esters.
data (Simões et al., 1997; Oliveira et al., 1999). The phys-
ico-chemical parameters for biodiesels (BBCu, BBCo, 3.8. Nuclear magnetic resonance results (1H and 13
C)
SBCu and SBCo) can be found in Table 2.
1
The acidic index, free glycerin and total glycerin were H NMR spectra of the biodiesels (SBCu, SBCo, BBCu
below the allowed limits by ANP (Agência Nacional de e BBCo), have not revealed signals assigned to the methy-
Petróleo, Gás Natural e Biocombustı́veis). Density, viscos- lene carbinol protons of triglycerides, d 4.15–4.33 (Gelbard
ity and flash point were in agreement with the resolution et al., 1995). Instead, an intense singlete, d 3.61, attributed
042-ANP. It was measure the amount of Cu and Co in bio- to the methoxylic protons of methyl esters, was observed. It
diesels prepared, using atomic adsorption spectroscopy. was confirmed by the results of 13C NMR as a strong signal
We found the following values, BBCu: 0.254 lg g1 and at d 51.2 was observed in the spectra of SBCo and SBCu.
13
BBCo: 0.198 lg g1, SBCu: 0.249 lg g1 and SBCo: C NMR have also showed other signals of low intensity
0.194 lg g1. The results of physico-chemical analysis sug- at d 62.0 (CH2O) and d 68.8 (CHO) attributed to the resid-
gest that the biodiesels can be used in diesel engines and the ual triglycerides. In addition resonances of low intensity at
amounts of Cu and Co found at biodiesels are not very d 61.0–72.5 were observed that could be attributed to digly-
problematic to fuel. cerides and monoglycerides. It is an indication that only a
small amount of babassu oil has not converted into
3.7. Gas chromatography (CG-FID) biodiesel.

In Table 3 are shown the results of gas chromatography 3.9. Reactions without catalyst
(CG-FID) for the biodiesels.
These results are in agreement with literature data (Oli- Tests were performed in order to verify if the NaOH
veira et al., 1999; Costa Neto et al., 2000). Babassu biodie- employed in this work was in fact the effective catalyst.
sel is predominantly composed by chain esters having 8–14 The products BBNa and SBNa were characterized by vis-
carbons, being methyl laurate the most abundant compo- cosimetric and thermogravimetric techniques. The viscosity
results are above the values normally found for biodiesels
Table 2
Physico-chemistry parameters of biodiesels
prepared with CCu and CCo catalysts. The high viscosity
indicates that the amount of NaOH was not enough to pro-
Parâmeters BBCu BBCo SBCo SBCu 042 ANP
1
mote the transesterification reactions.
Acidity (mg KOH 1g ) 0.310 0.540 0.200 0.360 0.800
Free glycerin (% mass) 0.010 0.020 0.017 0.018 0.020
Total glycerin (% mass) 0.200 0.198 0.210 0.230 0.380 3.10. Thermogravimetric analysis (TGA)
Density at 20 °C (g cm31) 0.880 0.870 0.880 0.880 0.880
Viscosity at 40 °C (cSt) 4.100 4.300 4.700 4.800 Max. 6.000 The thermal behavior of biodiesel was determined by
Flash point (°C) 120 125 170 186 Min. 100
thermogravimetric studies. As biodiesel is a substitute to
 R.B. da Silva et al. / Bioresource Technology 99 (2008) 6793–6798
mineral diesel, is necessary to assure that the quality and
properties of this fuel is reliable and consistent with the stan-
dards of Control Agency of fuels around the world (Lima
et al., 2007). Boiling point is an important property of the
biodiesels and it is a parameter that relates to the quality
of the biodiesel, as determined by ANP (Lima et al.,
2007). Thermogravimetric analysis is a fast, easy, cheap
and very useful technique to measure the biodiesel boiling
point (Goodrum and Siesel, 1996; Dunn, 1999). Besides,
thermogravimetric analysis can confirm the occurrence of
transesterification reaction, because the boiling points of
the triglycerides and esters (biodiesel) are different (Goo-
drum et al., 1998). This technique was also used to charac-
terize chitosan, the catalysts (CCu and CCo), one of the
biodiesels (BBCu, BBCo, SBCu, SBCo) and the crude oils
(BO and SO). Fig. 2 shows the thermogravimetric curves,
obtained in nitrogen, of chitosan (PC), CCu and CCo.
TG curve of chitosan (PC) presented two events, one at
89 °C, associated with water loss, and another one at
285 °C that is associated to the degradation and de-acetyla-
tion of chitosan (PC). TG curves of CCu and CCo adsorb-
ants also presented two events, at 73–76 °C and at 231 °C
(CCu) and 273 °C (CCo), corresponding to the degradation
and de-acetylation of chitosan modified. This fact can be
attributed to changes in the polymer natural order, due
to chelation process, leading to thermal instability (Sreeni-
vasan, 1996).
The boiling points of biodiesels were taken as the onset
of the isothermal boiling temperature. Since this method is
based on weight-mass loss of the sample as it began to boil,
the onset of the isothermal boiling temperature was taken
as the intersection of the tangent of the isothermal
weight-mass slope with the initial base line (Goodrum
and Geller, 2002). The boiling point of BO could be deter-
mined as 396 °C, and can be observed that it has just one
mass loss that was attributed to triglycerides of the babassu
oil. In the TG curves of BBCu and BBCo can be observed
two events, one of them at 190/193 °C, that was attributed
to the boiling point of the esters (biodiesels) and another
5.5
CCo PC
5.0
CCu CCu
4.5 PC CCo
Weight (%)
4.0
3.5
3.0
2.5
2.0
1.5
0 100 200 300 400 500
O
Temperature ( C)
Fig. 2. TG curve of PC, CCu and CCo.
6797
one at 370/376 °C, related to the presence of the crude
oil, indicating that the conversion was not complete.
SO boiling point of was determined to be 395 °C, SBCu
255 °C and SBCo 250 °C. The TGA curves of SBCu and
SBCo showed the same behavior as BBCu and BBCo
biodisels.
TG results of babassu and soybean biodiesels reveal the
occurrence of the transesterifications reaction of these oils,
however, the conversion was not complete as explained
above. It is in accordance to the results of thin layer chro-
matography and NMR.
In order to confirm that the amount of NaOH used in
the transesterification reactions has not catalyzed the for-
mation of the biodiesel, a thermogravimetric study was
accomplished under the same conditions without the cata-
lyst. It can be concluded that the amount of alkali used is
not enough to promote the transesterification reaction.
4. Conclusion
In this work it is described biodiesel syntheses from
babassu almonds and soybean oils using a heterogenous
catalyst, Cu(II) and Co(II) adsorbed in chitosan. Atomic
absorption spectroscopy studies attested the adsorption
process and it was more efficient with Cu(II). The chelating
process occurs through the N and O electron donor centre
of the polymer according to infrared spectroscopy. The
physicochemical results obtained agree with the established
ANP specifications. Thermogravimetry showed to be a
helpful technique in determining boiling points of the prod-
ucts, as well to in showing the effectiveness of the transeste-
rification reaction.
Acknowledgements
The authors would like to thanks the Brazilian agencies
CAPES (Coordenacßão de Aperfeicßoamento de Pessoal de
Nı́vel Superior) and CNPq (Conselho Nacional de Desen-
volvimento Cientı́fico e Tecnológico) for financial support.
Moura, C.V.R. would like to express her gratitude to the
FAPEPI (Fundacßão de Amparo à Pesquisa do Estado do
Piauı́) for financial support.
References
Abreu, F.R., Alves, M.B., Macedo, C.C.S., Zara, L.F., Suarez, P.A.Z.,
2005. New multi-phase catalytic systems based on tin compounds
active for vegetable oil transesterificaton reaction. J. Mol. Catal. A:
Chem. 227 (1–2), 263–267.
Analytical Methods, 1989. Flame Atomic Absorption Spectrometry.
Manual of Varian.
A.O.C.S., 1990. Official Methods and Recommended Practices, fourth ed.
American Oil Chemists Society, Champaign.
Chiessi, E., Paradossi, G., Venanzi, M., Pepisa, B.J., 1992. Copper
complexes immobilized to chitosan. Inorg. Biochem. 46 (2), 109.
600 700 Costa Neto, P., Rossi, L.F.S., Zagonel, G.F., Ramos, L.P., 2000.
Producßão de biocombustı́vel alternativo ao óleo diesel através da
transesterificacßão de óleo de soja usado em frituras. Quim. Nova 23
(4), 531–537.
6798 R.B. da Silva et al. / Bioresource Technology 99 (2008) 6793–6798
Dunn, R.O., 1999. Thermal analysis of alternative diesel fuels form
vegetable oils. J. Am. Oil Chem. Soc. 76 (1), 109–115.
Ferrari, R.A., Oliveira, V.S., Scabio, A., 2005. Biodiesel de soja, taxa de
conversão em ésteres etı́licos, caracterizacßão fı́sico-quı́mica e consumo
em gerador de energia. Quim. Nova 28 (1), 19–23.
Fukuda, H., Dondo, A., Noda, H., 2001. Biodiesel fuel production by
transesterification of oils. J. Biosci. Bioenerg. 92 (5), 405–416.
Gelbard, G., Bres, O., Vargas, R.M., Vilfaure, F., Schuchardt, U., 1995.
1
H nuclear magnetic resonance determination of the yield of the
transesterification of rapeseed oil with methanol. J. Am. Oil Chem.
Soc. 72 (10), 1239–1241.
Goodrum, J.W., Siesel, E.M., 1996. Thermogravimetric analysis for
boiling points and vapour pressure. J. Therm. Anal. Calorim. 46 (5),
1251–1258.
Goodrum, J.W., Geller, D.P., Lee, S.A., 1998. Rapid measurement of
boiling points and vapour pressure of binary mixtures of short-chain
triglycerides by TGA method. Thermochem. Acta 311,
71–79.
Goodrum, J.W., Geller, D.P., 2002. Rapid thermogravimetric measure-
ments of boiling points and vapour pressure of saturated medium-and
long-chain triglycerides. Bioresour. Technol. 84, 75–80.
Guibal, E., Milot, C., Roussy, J., 2000. Influence of hydrolysis mecha-
nisms on molybdate sorption isotherms using chitosan. Separ. Sci.
Technol. 35 (7), 1021–1038.
Instituto Adolfo Lutz, 1985. Normas analı́ticas do Instituto Adolfo Lutz,
vol. 1. In: Métodos Quı́micos e Fı́sicos Para análise de Alimentos, third
ed. São Paulo, pp. 245–250.
Klug, M., Sanches, M.N.M., Laranjeira, M.C.M., Favere, V.T., Rodri-
gues, C.A., 1998. Analysis of adsorption isotherms of Cu(II), Ni(II),
Pb(II) and Zn(II) by N-(3,4-dihydroxybenzyl) chitosan using nonlinear
regression method. Quim. Nova 21 (4), 410–413.
Li, H., Xie, W., 2006. Transesterification of soybean oil to biodiesel with
Zn/I2. Catal. Lett. 107 (1–2), 25–30.
Lima, J.R.O., Silva, R.B., Santos, L.S., Moura, C.V.R., 2007. Biodiesel de
Babacßu (Orbignya sp.) obtido por via etanólica. Quim. Nova 30 (3),
600–603.
Ma, F., Hanna, M.A., 1999. Biodiesel production: a review. Bioresour.
Technol. 70, 1–15.
Meher, L.C., Sagar, D.V., Naik, S.N., 2006. Technical aspects of biodiesel
production by transesterification – a review. Renew. Sust. Energy Rev.
10 (3), 248–268.
Nakamoto, K., 1986. Infrared and Raman Spectra of Inorganic and
Coordination Compounds. Wiley, NY.
Oliveira, A.L.A., Gioielli, L.A., Oliveira, M.N., 1999. Hidrólise parcial
enzimática da gordura de babacßu. Ciênc. Tecnol. Aliment. 19 (2).
Parente, E.S., Santos Junior, J.N., Pereira, J.A.B., Parente Junior, E.S.,
2003. Biodiesel: Uma Aventura Tecnológica Num paı́s Engracßado.
Tecbio, Fortaleza, p. 68.
Reddy, C., Reddy, V., Reed, O., Verkade, J.G., 2006. Room-temperature
conversion of soybean oil and poultry fat to biodiesel catalyzed by
nanocrystalline calcium oxides. Energy Fuels 20, 1310–1314.
Ruthven, M.D., 1984. Principles of Adsorption and Adsorption Processes.
John Wiley & Sons.
Santos, J.E., Soares, J.P., Dockal, E.R., Campana, S.P.F., Cavalheiro,
E.T.G., 2003. Caracterizacßão de quitosanas comerciais de diferentes
origens. Polı́m. Ciênc. Tecnol. 13 (4), 242–249.
Schwab, A.W., Baghy, M.O., Freedman, B., 1987. Preparation and
properties of diesel fuels from vegetable oils. Fuel 66 (10), 1372.
Schuchardt, U., Sercheli, R.R., Vargas, M., 1998. Transesterification of
vegetable oils: a review. J. Brazil Chem. Soc. 9 (3), 199–210.
Shimada, Y., Watanabe, Y., Sygihara, A., Tominaga, Y., 2002. Enzymatic
alcoholysis for biodiesel fuel production and application of the
reaction to oil processing. J. Mol. Catal. B: Enzym. 17 (3–5), 133–142.
Simões, I.S., Gioielli, L.A., Oliveira, M.N., 1997. Misturas binárias e
ternárias de gorduras hidrogenadas e óleo de soja. Ciênc. Tecnol.
Aliment. 17 (3).
Sreenivasan, K., 1996. Thermal stability studies of some chitosanmetal ion
complexes using differential scanning calorimetry. Polym. Degrad.
Stab. 52 (2), 85–87.
Tonhi, E., Plepis, A.M.G., 2002. Obtencßão e caracterizacßão de blendas de
colágeneo-quitosana. Quim. Nova 25 (6), 943–948.
United States Pharmacopeial (USP), 2000. Convention. The United States
Pharmacopeial the National Formulary: USP 24, NF 19. United States
Pharmacopeial Convention, Rockville, p. 780.
Wu, W.H., Foglia, T.A., Marmer, W.N., Dunn, R.O., Goering, C.E.,
Briggs, T.E., 1998. Low-temperature property and engine performance
evaluation of ethyl and isopropyl esters of tallow and grease. J. Am.
Oil Chem. Soc. 75 (9), 1173–1178.
Xie, W., Huang, X., 2006. Synthesis of biodiesel from soybean oil using
heterogeneous KF/ZnO, catalyst. Catal. Lett. 107 (1–2), 53–59.
Zagonel, G.F., Zamora, P.P., Ramos, L.P., 2004. Multivariate monitoring
of soybean oil ethanolysis by FTIR. Talanta 63 (4), 1021–1025.