Rapid Communication

Received: 24 July 2012 Revised: 9 November 2012 Accepted: 20 November 2012 Published online in Wiley Online Library: 7 December 2012

([Link]) DOI 10.1002/mrc.3913

Soybean biodiesel methyl esters, free glycerin

and acid number quantification by 1H nuclear
magnetic resonance spectroscopy
Natasha Coral,a* Elizabeth Rodrigues,b Victor Rumjanek,c
José Roberto Zamian,a Geraldo Narciso da Rocha Filhoa and
Carlos Emmerson Ferreira da Costaa
Production of alternative fuels, such as biodiesel, from transesterification of vegetable oil driven by heterogeneous catalysts is
a promising alternative to fossil diesel. However, achieving a successful substitution for a new renewable fuel depends on
several quality parameters. 1H NMR spectroscopy was used to determine the amount of methyl esters, free glycerin and
acid number in the transesterification of soybean oil with methanol in the presence of hydrotalcite-type catalyst to produce
biodiesel. Reaction parameters, such as temperature and time, were used to evaluate soybean oil methyl esters rate
conversion. Temperatures of 100 to 180  C and times of 20 to 240 min were tested on a 1 : 12 molar ratio soybean oil/methanol
reaction. At 180  C/240 min conditions, a rate of 94.5 wt% of methyl esters was obtained, where free glycerin and free fatty
acids were not detected. Copyright © 2012 John Wiley & Sons, Ltd.

Keywords: NMR; 1H; soybean oil; transesterification; biodiesel; methyl esters; free glycerin; acid number

Introduction Experimental Procedure

Biodiesel is defined as alkyl esters of fatty acids produced from Methyl esters were obtained by soybean oil (SINHÁ) transesterifi-
vegetable oils and animal fats. Nowadays, there has been an cation reaction with methanol in a 250-ml volume reactor
increasing interest in biodiesel as a green and alternative fuel [PAAR 4560 (Caramuru Alimentos S.A., Itumbiara, Goiás, Brazil)]
because of of recent legislations requiring a major reduction of connected to a temperature controller (PAAR 4853). Tests were
vehicle gas emissions, as well as the soaring price of petroleum.[1] carried out at soybean oil/methanol 1 : 12 molar ratio under
Heterogeneous catalysts for fatty and oil transesterification 700 rpm stirring conditions and 5 wt% of hydrotalcite-type
processes were the subject of some reviews.[2,3] Hydrotalcite-type (Mg0.75Al0.25(OH)2CO3(0.125)0.5H2O) as catalyst, synthesized at
catalysts were very helpful in the transesterification reaction 110  C/300 min according to the coprecipitation method,[14]
of vegetable oil because of their variable composition and under microwave irradiation (Panasonic NN-ST357W 22L equipped
structural/morphological/textural properties that allow a with a temperature controller INCON CNT120), at 2.45 GHz/800 W
significant reduction on biodiesel cost of production.[4,5] conditions. Several transesterification reaction temperatures
Production of a high quality biodiesel is extremely important, (100, 120, 140 and 180  C) and times (20, 40, 60, 120, 180 and
and so minimum quality standards require methyl esters, free 240 min) were tested.
glycerin and acid number quantification to determine maximum Organic and inorganic phases were separated by decantation
contaminant levels to assure engine integrity and performance. process. The organic phase was washed with a saturated NaCl
In the literature, several analytical methods have been used for solution to remove glycerin and dried with anhydrous Na2SO4.
this purpose, such as gas chromatography[6] or size-exclusion Biodiesel samples in this work at 180  C will be designated as
chromatography,[7] and recently 1H NMR spectroscopy was
employed to evaluate biodiesel quality parameters.[8]
Biodiesel esters quantification by 1H NMR is a simple and faster
technique in comparison with gas chromatography and HPLC.[9] * Correspondence to: Natasha Coral, LCO, Laboratório de Catálise e Oleoquímica,
Free glycerin and acid number can also be determined by 1H Faculdade de Química, UFPA, Rua Augusto Corrêa s/n, Guamá, CEP: 66075-110,
NMR and present a nice correlation with official methods data Belém, Pará, Brazil. E-mail: [Link]@[Link]
(ASTM D6584 and ASTM D664)[10] validating 1H NMR as biodiesel a LCO, Laboratório de Catálise e Oleoquímica, Faculdade de Química, UFPA, Rua
quality parameters methodology. Augusto Corrêa s/n, Guamá, CEP: 66075-110, Belém, Pará, Brazil
In this work, a quantitative study of temperature and time
reaction was carried out to investigate the transesterification b ICEN, Instituto de Ciências Exatas e Naturais, Rua Augusto Corrêa, Guamá,
CEP:66075-110, Belém, Pará, Brazil
reaction of soybean oil in the presence of hydrotalcite-type
catalyst based on 1H NMR spectroscopy to determine methyl c Departamento de Química, UFRRJ, BR 465, Km 7, CEP 23890-000, Seropédica,
69

esters, free glycerin and acid number of biodiesel.[11–13] Rio de Janeiro, Brazil

Magn. Reson. Chem. 2013, 51, 69–71 Copyright © 2012 John Wiley & Sons, Ltd.
 N. Coral et al.

Bio20, Bio40, Bio60, Bio120, Bio180 and Bio240, obtained with V = number vinyl hydrogen = (L rg)/rg, L = d 5.2 ppm, rg = d
reaction times of 20, 40, 60, 120, 180 and 240 min, respectively. 4.2 ppm and a and b = aliphatic hydrogens (d 0.8–1.0 ppm).[12]
Biodiesel samples were dissolved in CDCl3 for 1H NMR analysis The parameters a and b are related to C15–C16 insaturation by
on a Bruker AVANCE-500 spectrometer, using TMS as an internal anisotropic effects, which shifted downfield of 0.88 to 0.95 ppm.
standard. The following experimental conditions were used: These signals can be integrated separately from terminal CH3 signal
11.7 T magnetic field (500 MHz), 45º radiofrequency pulses, 13 s of fatty acid chains.[15]
interpulse delay (acquisition time + relaxation time), 4.120 Hz
scan width, 0.3 Hz resolution and 16 scans.
Conversion degree of the transesterification reaction based Results and Discussion
on quantitative analysis was carried out using the relationship
1
between the areas of the methyl ester hydrogen signal H NMR spectra of soybean oil and its respective methyl esters
(I3.7 = CH3 OCO– d 3.7 ppm) and of the a-carbonyl methylene were very similar (Fig. 1), except for the 3–5 ppm region,
hydrogen signal (I2.2–2.4 = –OCOCH2– d 2.2–2.4 ppm),[13] established where this behavior changes drastically. Soybean oil spectrum
by the equation CME = 100  (2 I3.7/3 I2.2–2.4). The 2/3 factor is related presented intense doublet and double doublets signals
to the different numbers of hydrogen atoms in methyl and at 4.05–4.35 ppm, attributed to four hydrogen atoms at sn-1 and
methylene groups. sn-3 positions in the glycerol moiety of the triglyceride molecule.
Free glycerin was determined using the equation FG = (I5.3–5.2 r)/ Glycerol hydrogen atoms at sn-2 and olefinic hydrogen atoms
(r.W), where I5.3–5.2 = glycerol hydrogen atoms at sn-2 position were overlapped at 5.3–5.2 ppm. The methyl esters spectra
(d 5.3–5.2 ppm), r = I4.05–4.35/2 and I4.05–4.35 = hydrogen atoms at exhibited a singlet at 3.7 ppm due to monoesters in agreement
sn-1 and sn-3 positions (4.05–4.35 ppm), and W = glycerin with previous works.[12,13,16]
molecular weight.[11] The acid number was calculated using the Brazilian fuel regulations [Brazilian agency of petroleum, gas and
equation AN = 0.0298 (R)2 + 0.1265 (R) + 0.683, where R = V/(a + b), biofuels/resolution 14 (ANP)] establish minimum values of 96.5 wt%
methyl esters, 0.02 wt% free glycerin and 0.50 mg KOH/g acid
number.[10] Data obtained in this work were very close to these
values.
Conversion rate data of transesterification of soybean oil to
methyl esters indicated that this reaction is strongly temperature
and time dependent, as predicted by the literature.[2] Table 1
presents all data, but only the best results, at 180  C, will be
detailed. At temperatures lower than 180  C, conversion rate of
soybean oil to methyl esters is lower than ANP standards because
of incomplete conversion reagent/product (37.5–88.5%). In the
presence of hydrotalcite-type catalyst at 180  C, the reaction rate
raises from 65.5 to 94.5 wt% when the time is raised from 20 to
240 min (Table 1). The reaction carried out over 20 min afforded
0.048 wt% of free glycerin and 0.71 for acid number.
Free glycerin and free acids were not detected when longer
reaction times were employed, proving the efficiency of biodiesel
purification process and catalyst used to convert free fatty acids
into methyl esters. At higher temperatures (140/180  C), 40 min
of time reaction is sufficient to obtain an appropriate conversion
rate. At 100 and 120  C, all time reaction tested presented a high
Figure 1. 1H NMR spectra of the soybean oil and its methyl esters amount of free glycerin than expected, despite several NaCl
(180 C/240 min). leaching performed, probably because of the presence of a

Table 1. Methyl esters, free glycerin and acid number data of biodiesel samples
Samples/time (min) Temperature ( C)
100 120 140 180
CH3-E Glic. Acid. CH3-E Glic. Acid. CH3-E Glic. Acid. CH3-E Glic. Acid.
(wt%) (wt%) (mg/g) (wt%) (wt%) (mg/g) (wt%) (wt%) (mg/g) (wt%) (wt%) (mg/g)

Bio20 (20) 37.5 0.144 0.79 41.0 0.096 0.76 52.0 0.053 0.72 65.5 0.048 0.71
Bio40 (40) 41.0 0.080 0.76 51.0 0.078 0.73 76.8 — — 81.8 — —
Bio60 (60) 52.0 0.073 0.75 57.0 0.067 0.72 82.0 — — 87.1 — —
Bio120 (120) 67.1 0.043 0.73 76.6 0.037 0.72 88.5 — — 93.2 — —
Bio180 (180) — — — — — — — — — 93.9 — —
Bio240 (240) — — — — — — — — — 94.5 — —

CH3-E, methyl esters (wt%); Glic., free glycerin (wt%); Acid., acid number (mg KOH/g).
70

[Link]/journal/mrc Copyright © 2012 John Wiley & Sons, Ltd. Magn. Reson. Chem. 2013, 51, 69–71
Soybean biodiesel methyl esters, free glycerin and acid number quantification by 1H NMR spectroscopy

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Magn. Reson. Chem. 2013, 51, 69–71 Copyright © 2012 John Wiley & Sons, Ltd. [Link]/journal/mrc