A Transesterication Double Step Process TDSP for biodiesel preparation from fatty
acids triglycerides
D. Samios , F. Pedrotti, A. Nicolau, Q.B. Reiznautt, D.D. Martini, F.M. Dalcin
Laboratory of Instrumentation and Molecular Dynamic, Institute of Chemistry, Federal University of Rio Grande do Sul 9500, Bento Gonalves Av., Box 15003, Porto Alegre, RS, Brazil
a r t i c l e
i n f o
Article history:
Received 1 July 2008
Received in revised form 6 October 2008
Accepted 18 December 2008
Keywords:
Transesterication
Acid
Basic
Biodiesel production
Catalysis
a b s t r a c t
This study introduces a two consecutive steps basicacid transesterication process, (denominated
Transesterication Double Step Process TDSP) for biodiesel production from vegetable oils. The process
involves homogeneous consecutive basicacid catalysis steps and is characterized by formation of welldened phases, easy separation procedures, high reaction velocity and high conversion efciency. The
proposed TDSP is different in relation to other traditional two-step procedures which normally include acid
esterication followed by basic transesterication, or enzymatic or even supercritical transesterication
conditions. The biodiesel (fatty acid methyl esters) was analyzed by standard biodiesel techniques in
addition to 1H-NMR, indicating high quality and purity biodiesel products. The transesterication of
sunower and linseed oils resulted in oil conversions higher than 97% corresponding to yields of 85%. A
probable reaction mechanism responsible for the process is presented.
2009 Elsevier B.V. All rights reserved.
1. Introduction
1.1. Transesterication
600
601
2.1. Materials
3. Results and discussion
The present study uses different types of oils which mainly include
the unsaturated fatty acids: oleic acid (C181), linoleic acid (C182) and
linolenic acid (C183), The alcohol used in this process is methanol
(MeOH) and the catalysts are potassium hydroxide (KOH) and sulfuric
acid (H2SO4). The reactants used were sunower oil Molinos
(Rosario, ARG), linseed oil Farmaqumica, (Porto Alegre, Brazil),
methanol (99.9% P.A.) Synth (So Paulo, Brazil), potassium
hydroxide (98.1% Purity) Nuclear (Diadema, Brazil), H2SO4 (98% P.
A.) Merck (Darmstadt, Germany), CDCl3 (99.8% D with 0.03% (v/v)
TMS) Aldrich Chemical Co. (Milwaukee, WI).
2.1.1. The Procedure of the Transesterication Double Step Process
TDSP
The procedure is a sequence of operations, performed approximately in 4 h. Initially the alkali agent is dissolved in methanol (25 g
KOH in 1 L methanol) in a temperature near 45 C permitting the
formation of the basic catalysis active species. Forty mL of this solution
and 100 mL of vegetable oil, under vigorous and constant agitation, are
introduced in a simple reactor equipped with reux device. The molar
ratio of alcohol/oil is 10 and catalyst/alcohol is 1.78 .10 2. The
temperature is increased until 60 C, near the boiling point of the
alcohol. The system stays in this condition for approximately 1 h. After
this period the system is cooled down to approximately 25 C. The
second main step of the procedure consists of the addition of 60 mL
methanol and 1.5 mL sulfuric acid 18 mol/L in the reactions mixture
followed by soft heating. The reaction mixture is submitted to constant
agitation and the temperature is elevated until 60 C by using the reux
equipment. The heating stabilizes and the system remains in this
condition for 1 h. After this period the system is cooled slowly to
approximately 25 C. In the end of this step the formation of two
phases occurs. The two phases are separated and processed further.
The biodiesel phase is washed with cool water and the residual alcohol
is removed by evaporation under vacuum. The lower phase presents
pH approximately 6 and is used for recuperation of the methanol
excess, the glycerol, as well as, other secondary products.
2.1.2. Characterization
The oils used in this study, as well as, the biodiesel products of the
TDSP procedure were characterized using Nuclear Magnetic Resonance Analysis (Varian - INOVA 300, 300 MHz) in CDCl3 (99.8% D with
0.03% (v/v) TMS) solutions. The chemical characteristics of the
where Ii-TAG and If-TAG are the initial and nal normalized integrated
intensities of the signal in the range between 4.22 and 4.42 ppm.
Considering the integration values of the glyceridic (TAG), the methyl
ester (ME) hydrogens and the methylene groups adjacent (-CH2) to
the ester group NMR signals, the Eqs. (2) and (3) permit the
conversion calculation.
4xIME
2
CME = 100x
4xIME + 9xITAG
CME
!
6xIME
= 100x
:
9xIaQCH2
602
Fig. 5. 1H NMR spectrum of linseed oil and a general scheme, which includes the NMR shift values of protons for a vegetable oil.
IME is the integration value of the methyl ester peak and ITAG is the
integration value of the glyceridic peaks in the triacylglycerides (TAG)
of the vegetable oil. The factors 9 and 6 result from the fact that the
three methyl ester moieties resulting from one triglyceride molecule
have nine hydrogens (3.67 ppm) and the three methylene groups
adjacent to the ester group in both vegetable oil and biodiesel have six
hydrogens (2.31 ppm) [10]. With respect to Eq. (2), many authors
have erroneously used the factor 5, considering that the glycerol
moiety of a triglyceride has ve protons contributing at (4.22
4.42 ppm), however according to literature [35] the methine
hydrogens present signal at 5.37 ppm and the correct factor must be
Fig. 6. 1H NMR spectrum of biodiesel from linseed oil and a general scheme, which includes the NMR shift values of protons for a methyl ester.
603
Fig. 7. A suggested mechanism for the Transesterication Double Step Process TDSP.
There is no presence of triglyceride (4.224.42 ppm), di or monoglycerol (small peaks at 3.44.1 ppm) evidenced. In other words the
proposed procedure results to high purity fatty acid methyl ester and
this is coherent with the nal elevated value of methanol/triglyceride
ratio used for this purpose.
The yields (w/w %), by using the TDSP procedure, were
calculated by Eq. (4) taking into account the initial volume of the
Table 1
Results of the Analysis Protocol for the biodiesel from linseed and sunower oils
Physicochemical property
Technique
0.88
163 4
0.88
140 4
3.9
4.3
K, mg/kg
Na, mg/kg
b 0.015
b 0.013
b 0.015
b 0.013
EN 14109b
EN 14108b
a
b
604
used oil (Voil), the volume of the biodiesel (VBD), the corresponding
densities (Oil, BD) and the conversion degrees XME obtained by 1HNMR technique.
= 100x
VBD xBD xXME
:
Voil xoil
requires extremely shorter times than the acid catalysis transesterication and results to high conversion degrees. From the other side,
the TDSP compared to the single step basic catalysis, needs the
employment of two catalysts and approximately double quantity of
methanol, which makes the process more expensive. This preliminary
evaluation of the TDSP is evidencing a capability to obtain biodiesel
with higher conversions than the basic one in operational times
sufciently smaller than the acid catalysis. It seems to be a new way
for biodiesel production. This initial study must be continued in order
to create a new opportunity for technological and/or industrial
purposes.
Acknowledgments
The authors acknowledge the Conselho Nacional de Desenvolvimento Cientco e Tecnolgico (CNPq) and Coordenao de Aperfeioamento de Pessoal de Nvel Superior (CAPES) for nancial support.
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