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Energy and Fuels 2006 20 1350 (RMN)
Energy and Fuels 2006 20 1350 (RMN)
Energy and Fuels 2006 20 1350 (RMN)
ReceiVed NoVember 14, 2005. ReVised Manuscript ReceiVed May 26, 2006
Methyl esters were produced at several temperatures (10, 35, and 45 °C) by transesterification batch reactions
of soybean oil with methanol utilizing KOH and NaOH catalysts. The reactions were monitored by aliquot
removal and subsequent proton nuclear magnetic resonance spectroscopy (1H NMR) analysis. 1H NMR analysis
allowed for the calculation of the average degree of fatty acid unsaturation (DU ) 1.52) in oil and methyl
ester. 1H NMR analysis also provided initial rates of methyl ester formation and an activation energy of 27.2
kJ/mol. The time-dependent concentration data revealed substantial reaction progress toward equilibrium after
only 120 s at a reduced temperature of 10 °C. Understanding the resonance shifts in the 1H NMR spectra of
starting materials and products allows for quantitation of reaction progress that is in good agreement with
results obtained using other analytical methods.
Introduction
Rudolf Diesel first envisioned his diesel engine invention as
a powerful engine that could operate on agricultural products
such as vegetable oils to counter the dependency on petroleum
fuels that was prevalent as early as 1905.1 His engine was a
great success, but his desire to use agricultural-derived fuels Figure 1. General reaction for the transesterifaction of a triglyceride
was not realized because of the inexpensive petroleum produc- using an alcohol.
tion of diesel fuels and the need to chemically modify plant
oils prior to use in the diesel engine. However, global events quantitative information pertaining to the chemical species
and rising petroleum costs have recently revitalized interest in present in the reaction. In this process, concentrations of reactant
Rudolf Diesel’s dream. The diesel engine can indeed be run on oil and product methyl ester can be determined at early times
straight vegetable oil, but many problems result ranging from during a batch reaction and the initial rates of the reaction can
starting failure and engine wear to polymerization of the be obtained. The rate of oil conversion to methyl ester has been
lubricating oils.2 Most of the problems associated with the use reported using aliquot sampling and 1H NMR analysis.5 The
of straight vegetable oil can be avoided by chemical modification work presented in this paper expands the previous study in three
through transesterification of the vegetable oil triglyceride significant ways: (i) a detailed interpretation of the 1H NMR
molecules to smaller alkyl esters of the fatty acids commonly spectrum of unsaturated vegetable oil is presented; (ii) initial
referred to as biodiesel.2 This transesterification is normally rates and activation energy for the reaction are obtained; and
accomplished using methanol as the alcohol and either NaOH (iii) the transesterification (alcoholysis) reaction is studied using
or KOH as a base catalyst (see Figure 1). Reviews of biodiesel a stoichiometric 3:1 molar ratio of alcohol/soybean oil as
production have been published, and the transesterification opposed to a 6:1 or larger ratio used in most previous
reaction has primarily been monitored using gas chromatography studies.3-5,7,8 Recent work has found that the optimum molar
(GC).3,15 ratio is approximately 3.5:1 and increased quantities of methanol
The use of proton nuclear magnetic resonance spectroscopy over this ratio result in separation problems during subsequent
(1H NMR) has recently been employed to monitor the kinetics steps in the process.9
and product distributions in transesterification reactions (alco- In previous 1H NMR studies of vegetable oil alcoholysis
holysis) between vegetable oils and alcohols.4-6 The use of 1H reactions, quantitation is achieved by comparing the integration
NMR is convenient and fast when monitoring a reaction, of the resonance signal from the glyceridic protons in the oil to
because a small aliquot can be extracted from the batch reaction the methyl ester protons in the product to determine the extent
at any given time and the 1H NMR spectrum analysis provides of the reaction at each sampling time.5 Additionally, the olefinic
proton signals in the product are compared to the methyl ester
* To whom correspondence should be addressed. E-mail: mmorgenstern@ signal in the product to determine the average degree of
coloradocollege.edu.
(1) Krawzcyk, T. Inform 1996, 7, 801-815. unsaturation in the fatty acid chains.4 However, previous work
(2) Harwood, H. J. J. Am. Oil Chem. Soc. 1984, 61, 315-324.
(3) Ma, F.; Hanna, M. A. Bioresour. Technol. 1999, 70, 1-15. (7) Darnoko, D.; Cheryan, M. J. Am. Oil Chem. Soc. 2000, 77, 1263-
(4) Suppes, G. J.; Bockwinkel, K.; Lucas, S.; Botts, J. B.; Mason, M. 1267.
H.; Heppert, J. A. J. Am. Oil Chem. Soc. 2001, 78, 139-145. (8) Freedman, B.; Butterfield, R. O.; Pryde, E. H. J. Am. Oil Chem. Soc.
(5) Knothe, G. J. Am. Oil Chem. Soc. 2000, 77, 489-493. 1986, 63, 1375-1380.
(6) Gelbard, G.; Bres, O.; Vargas, R. M.; Vielfavre, F.; Schuchardt, U. (9) Dorado, M. P.; Ballesteros, E.; Mittlebach, M.; Lopez, F. J. Energy
F. J. Am. Oil Chem. Soc. 1995, 72, 1239-1241. Fuels 2004, 18, 1457-1462.
incorrectly assigned the glyceridic proton signal at 4.2 ppm as Table 1. Reported Percent Fatty Acid Composition of Soybean Oil
a five-proton signal, while it is actually only a four-proton and Corresponding Degree of Unsaturation per Fatty Acid
(FA)10,11,12
dimethylene signal, with the remaining methine proton showing
up further downfield as part of the olefinic proton signal at 5.25 fatty acid identity average ( SD
ppm.5 The shift of the glyceridic methine proton can easily be myristic (14:0) 0.2 ( 0.1
established by obtaining the 1H NMR spectrum of a saturated palmitic (16:0) 10.7 ( 1.0
triglyceride, such as tributyrin or trimyristin, where there are stearic (18:0) 3.0 ( 0.9
oleic (18:1) 25.0 ( 3.5
no olefin protons and the methine glyceridic proton clearly linoleic (18:2) 53.4 ( 2.3
shows up as a multiplet downfield from the four methylene linolenic (18:3) 7.3 ( 1.2
glyceridic protons. Therefore, when using the 1H NMR integra- average degree of unsaturation per FA 1.54 ( 0.02
tion values in unsaturated oils, the olefinic proton integrations
must be corrected for the underlying glyceridic methine proton a test tube containing 2.5 µL of 12 M HCl (0.030 mmol) and placed
on ice to quench any further alcoholysis reaction in the test tube.
and the glyceridic methylene resonance should be treated as a
Acetone (0.100 mL, 1.35 mmol) was added to each aliquot to serve
four-proton signal. as an internal standard for the 1H NMR analysis of concentrations
The time interval used in aliquot removal from a vegetable present in a sample. Several 1H NMR analyzes were performed
oil alcoholysis reaction using methanol must be rapid when the with known concentrations of oil and methyl ester, and back
reaction is performed at room temperature or higher. Over 50% calculations using the acetone standard showed a consistent 10%
conversion to the product within the initial 5 min has been error. Individual spectra of each aliquot were obtained using a
reported for the reaction of soybean oil with methanol at 45 °C Varian 200 MHz NMR and CDCl3 (99.8%) as the solvent.
using the KOH catalyst.5 This fast reaction would require several Reagents. Soybean oil, King Soopers brand, was purchased in
aliquots to be removed and analyzed within the first minute to 1 gallon jugs from the local King Soopers grocery store (Colorado
obtain the initial rates for the disappearance of soybean oil and Springs, CO). Methanol (99.9% purity), KOH (88.1% purity),
NaOH (98.0% purity), and concentrated (12 M) HCl were all
the appearance of the methyl ester product.
certified ACS-grade and purchased from Fischer Scientific (Fair-
In the present work, the kinetics of a 3:1 stoichiometric ratio lawn, NJ). Acetone (99.8% purity) was certified ACS-grade and
of methanol/oil is studied in contrast to previous papers that purchased from the J. T. Baker Chemical Company (Phillipsburg,
utilize a 6:1 ratio of methanol/oil. It has been reported that NJ). The CDCl3 [99.8% D with 0.03% (v/v) tetramethylsilane
performing the transesterification as a two-stage reaction results (TMS)] used as the NMR solvent was purchased from Aldrich
in a more complete reaction.16 In the two-stage transesterification Chemical Co. (Milwaukee, WI). All reagents were used without
process, the first stage is allowed to approach equilibrium using further purification.
a 3:1 stoichiometric ratio of methanol/oil before the glycerol is
Results and Discussion
removed. The second stage consists of the addition of an
additional equivalent of methanol and stirring to drive the The general reaction for the transesterification of a triglyceride
equilibrium further to products and therefore a second separation with an alcohol (alcoholysis) is shown in Figure 1. Note that
of the glycerol byproduct. Therefore, this work is partially this reaction is reversible and every triglyceride molecule reacts
initiated to determine the time required for the first stage to with 3 equiv of the alcohol to produce glycerol and three fatty
approach equilibrium when a 3:1 stoichiometric ratio of reactants acid ester molecules. In base-catalyzed reactions, the catalyst
is used. 1H NMR can be used to monitor the extent of the is typically NaOH or KOH. The general fatty acid chains
reaction as an alternative to GC. denoted as R1, R2, and R3 vary in identity and percent
composition depending upon the triglyceride source (see Table
Experimental Section 1 for soybean oil composition). Plant oils generally contain a
The progress of the transesterification reaction between soybean high percent of unsaturated fatty acid chains, where R1, R2, and
oil and methanol was monitored by the extraction of aliquots from R3 would be oleic, linoleic, and linolenic acid chains. The high
a batch reaction at given time intervals. The extent of the reaction percent of unsaturated fatty acid chains results in plant-derived
was determined by 1H NMR analysis of the aliquots. Batch reactions triglycerides having a liquid physical state (oil) at moderate
were carried out at different temperatures and with different temperatures. The alcohols (R′OH) used in the transesterification
catalysts. of triglycerides are normally methanol or ethanol, with methanol
Batch Reactions. The batch reactions were performed with a being the most common because of the low cost, low reaction
stoichiometric molar ratio (3:1) of methanol/soybean oil. A 200 temperatures, fast reaction times, and higher quality methyl ester
mL two-necked round-bottom flask was charged with 2.50 mmol product.9,14
of catalyst (0.100 g of NaOH or 0.140 g of KOH) and 9.40 mL
(0.232 mol) of methanol. A magnetic stir bar was added, and with
Typical 1H NMR spectra of soybean oil and methyl ester
continuous stirring on a magnetic stir plate, the catalyst was product resulting from transesterification with methanol are
completely dissolved in about 15 min. Once the catalyst was in presented in Figures 2 and 3. The corresponding 1H resonance
solution, 80 mL of soybean oil (0.077 mol based on an average assignments are presented in Figure 4. It is interesting to note
molar mass of 895.9 g/mol from percent composition data) was that the presence of polyunsaturated fatty acids can be readily
added and the rate of stirring increased to approximate a homo- detected by the appearance of a resonance at 2.72 ppm from
geneous system. The batch reactions were performed in an ice bath the methylene group between two double bonds of a linoleic,
(10 °C) and in an oil bath (35 and 46 °C) to obtain the temperature- linolenic, or higher polyunsaturated fatty acid chain. The
dependent data for the reaction. The oil and alcohol/catalyst splitting pattern for the protons in the glyceride moiety is an
solutions were allowed to equilibrate at the desired temperature ABX pattern because of the chemical-shift inequivalence of the
prior to mixing and initiation of the reaction. A reflux condenser
was employed at the higher temperatures to prevent the alcohol
glyceride methylene protons at 4.21 ppm, and the measured
from evaporating. coupling constants are Jab ) 12 Hz, Jax ) 6 Hz, and Jbx ) 4
Aliquot Removal. Aliquots (1.0 mL) were removed from the Hz for the system represented by R1OCHaHbC(OR2)HxCHaHb-
batch reaction using an autopipet with disposable tips. The OR3.13 In this system, there is a plane that runs along the
maximum rate of aliquot extraction was one sample every 10-30 carbon-carbon bond and the Ha protons are on the same side
s using this method. The aliquots were immediately transferred into of this plane as the -OR2 group, while the Hb protons are on
1352 Energy & Fuels, Vol. 20, No. 4, 2006 Morgenstern et al.
Figure 2. Typical 1H NMR spectrum of soybean oil (CDCl3, Varian 200 MHz NMR).
Figure 3. Fatty acid methyl ester product from soybean oil alcoholysis with methanol.