American Journal of Organic Chemistry 2019, 9(2): 25-27

DOI: 10.5923/j.ajoc.20190902.01

Comparison of Various Feedstocks for the

Microwave-Assisted Synthesis of Biodiesel
C. Villot1, M. E. Howard, K. W. Kittredge*

Department of Chemistry, Virginia Wesleyan University, 5817 Wesleyan Dr., Virginia Beach, VA

Abstract The microwave-assisted acid catalyzed synthesis of biodiesel from various feedstocks are reported. The
feedstocks consist of vegetable, canola, olive, avocado, corn, cottonseed and soybean oils and also were compared to a
commercial biodiesel sample that was prepared from a mixture of varying oils by GC-MS. All oils gave biodiesel in excellent
yields (<85%). Combustion analysis gave heats of combustion between 40.75 to 43.45 kJ/g, similar to literature values.
Keywords Microwave-Assisted Synthesis, Biodiesel

The esters are synthesized in a transesterification reaction

1. Introduction between various glycerides and alcohols such as methanol
or ethanol. The product esters are fatty acids methyl ester
(FAME) or fatty acids ethyl esters (FAEE), depending on
which alcohol was used in their synthesis. [2] Their
synthesis is controlled by the acid and base catalyzed
equilibrium shown in Figure 2. To increase the formation of
the fatty acid ester an excess of the alcohol is usually used.
[9]
In the commercial production of biodiesel two catalytic
approaches are used; acid catalysts such as sulfuric acid or
p-toluenesulfonic acid and base catalysts such as
sodium/potassium hydroxide. One of the shortcomings from
using alkali base catalysts is these tend to cause equipment
Figure 1. Structure of biodiesel deterioration and undesired side reactions whereas acidic
reaction conditions do not cause similar equipment
The rapid consumption of petroleum fuels and their deterioration. [2] Also, by using acid catalysts oils with high
increasing prices have come to worldwide attention. Due to free-acid and water content can be more easily processed.
their future environmental and economic impacts. [1] This Waste vegetable oil tends to have higher free-acid content
worldwide ecological and economical movement has and more water than its virgin counterpart, and therefore
resulted in the search for alternative fuel sources. [2] acid-catalyzed transesterification is better suited for these
Biodiesel is one potential fuel aimed at reducing the usage reaction conditions. [1] In this work we used
of petroleum fuels. [3] Unlike petroleum fuels, biodiesel p-toluenesulfonic acid as the acid catalyst in all reactions.
fuels can be nontoxic and biodegradable. [2]. Their We chose this catalyst for its ease of use and high conversion
production and consumption is a closed carbon cycle and (>95%) in the transesterification reaction. Some advantages
CO2 emissions may be reduced by as much as 78%. [4-5] of using microwave heating over conventional heating
Biodiesel is commonly produced from waste vegetable oil include energy conservation and shorter reaction times.
and consists of fatty acid esters of various lengths (Figure [10] We have previously shown that the combination of
1), however other oils may be substituted in place of p-toluenesulfonic acid and microwave heating produced
vegetable oil. [6-8] biodiesel from vegetable oil in high yields. [11]
* Corresponding author:
[email protected] (K. W. Kittredge) 2. Materials and Methods
Published online at http://journal.sapub.org/ajoc
Copyright © 2019 The Author(s). Published by Scientific & Academic Publishing Materials and Equipment
This work is licensed under the Creative Commons Attribution International
License (CC BY). http://creativecommons.org/licenses/by/4.0/
26 C. Villot et al.: Comparison of Various Feedstocks for the Microwave-Assisted Synthesis of Biodiesel

Figure 2. Reaction scheme for the synthesis of biodiesel from vegetable oil

All transesterification trials were carried out using vacuum filtration and the methanol was removed in vacuo by
p-toluenesulfonic acid (Fisher) and methanol (Fisher) and rotary evaporation. The biodiesel was used as is in the
were used as received. A CEM Mars 6 microwave reactor combustion analysis.
was used for the microwave-assisted reactions. The Heats of Combustion
synthesized biodiesel product was identified and
The temperature was recorded during the calorimetry runs
characterized by GC-MS using standard literature methods.
as two readings per second over a typical 1000 second run.
[12-15] Percent conversions were determined by GC-MS.
After calibration of the stainless steel temperature probe and
[15] The GC-MS was an Agilent 5977A Extractor XL MSD
calibration of the bomb calorimeter with benzoic acid, 1.0 g
with a chemical ionization detector. Split injections with a
samples of synthesized biodiesel fuel (or commercially
100:1 split ratio. The GC was fitted with an HP-5 (5% phenyl:
purchased diesel fuel) were combusted. A minimum of five
95% methyl silicone) column (dimensions: 30 m x 0.32 mm;
trials for each sample were done.
flow rate:1.64 mL/min; Injector temperature: 250°C; Oven
temperature: 150°C; Detector temperature: 290°C). A Parr
Instruments 1341 Oxygen Bomb Calorimeter with an 1108
Oxygen Combustion Bomb was used to measure the heats
3. Results and Discussion
of combustion for the synthesized biodiesel and the Bomb calorimetry was used to quantify the difference
commercially available petroleum diesel. Temperature in quality of the biodiesel products and as well as compare
changes were measured and recorded using a stainless steel to a commercially available petroleum diesel sample.
temperature probe connected to a Vernier LabPro interface Calorimetric combustion studies of biodiesel were found to
running LoggerPro v3.10.1. be between 40.75 to 43.45 kJ/g (Table 1) and are similar to
General Procedures those reported in the literature. [12] These values are 5-10%
Reaction Solutions: All reactions were done in a 200 mL lower than the heat of combustion for a commercial
round bottom flask equipped with a teflon coated magnetic petroleum diesel sample (45.52 kJ/g). All oils gave a high %
stir bar and a reflux condenser. The solution was refluxed by conversion, the lowest being for avocado oil (87%) and the
setting the heating temperature to 65°C for 1 h. Each reaction highest for vegetable oil (97%).
solution was prepared using 15 mL oil, 5 g (30 mmol) of Table 1. Summary of % conversion and combustion analysis for the
p-toluenesulfonic acid, and 25 mL of methanol. various oils to biodiesel
Phase Separation of the Biodiesel and Glycerol Heat of Combustion
Oil % Conversion
After completion of the reaction, the mixture was allowed (ΔHC0), kJ/g
to cool, gravity filtered through filter paper to remove the Avocado 87 40.75
acid catalyst and separated into two layers. The top layer, Canola 91 41.50
lighter in color, was the biodiesel; and the bottom layer, Corn 92 42.23
darker in color, was the glycerol. The biodiesel layer, which Cottonseed 94 41.18
also contained some unreacted methanol, was collected and Olive 88 43.45
the methanol was removed in vacuo by rotary evaporation.
Soybean 90 42.95
Purification of the Biodiesel Vegetable 97 42.25
Into the biodiesel fraction were added 25 g of magnesium Commercial --- 45.52
sulfate and 100 mL of methanol. The suspension was swirled
occasionally and then cooled on ice for an additional 5 Table 2 lists the chemical composition of the biodiesel
minutes. The solid magnesium sulfate was removed by fractions produced from the various oils. They are
 American Journal of Organic Chemistry 2019, 9(2): 25-27 27

determined as percentages of the methyl ester product as corresponding carboxylic acids after hydrolysis of the
determined by ratio from the integration of the peak areas in triglyceride. These compounds are what are listed as major
GC-MS. The three major components for all oils, except components, either on their labels or from the USDA
cottonseed, are methyl palmitate, methyl linoleate and database.
methyl oleate. These methyl esters are derived from their
Table 2. Summary of chemical composition of the biodiesel fractions from the various oils. Reported as percentages of the methyl ester product. [11,12]

Compound Avocado Canola Corn Cottonseed Olive Soybean Vegetable

methyl hexadecanoatea 35.0 25.0 36.8 55.0 44.5 36.0 37.0
methyl (9Z,12Z)-9,12-octadecadienoateb 17.8 29.0 46.6 45.0 11.7 34.4 37.5
c
methyl (9Z)-9-octadecenoate 41.5 39.1 16.6 32.5 14.9 17.8
methyl (9Z,12Z, 15Z)-9,12,15-octadecatrienoated 0.9
methyl octadecanoatee 5.7 6.9 11.3 13.8 7.7
a b c d e
methyl palmitate. methyl linoleate. methyl oleate. methyl linolenate. methyl stearate.

4. Conclusions design and technological assessment. Bioresource Tech., 89,

1-16.
We report the acid catalyzed microwave-assisted
[7] Wang, Y., Ou, S., Liu, P., Xue, F., Tang, S., 2006,
synthesis of biodiesel from various oils. We found no Comparison of two different processes to synthesize
significant difference in the combustion analysis between the biodiesel by waste cooking oil. J. of Molecular Catalysis A:
oils, but all were lower than that for commercial diesel. In the Chemical, 252, 107-112.
chemical composition of the different biodiesel products
[8] Lopez, D. E., Goodwin, J. G., Bruce, D. A., Lotero, E., 2005,
showed that all the oils contained the same three major Transesterification of triacetion with methanol on solid acid
components, with the exception of cottonseed oil. The source and base catalysts. Applied Catalysis A: General, 295,
of oil for the production of biodiesel is shown to be wide 97-105.
ranging and not limited to exclusively vegetable oil.
[9] Hoydonckx, H. E., De Vos, D. E., Chavan, S. A., Jacops. P.
A., 2004, Esterification and transesterification of renewable
chemicals. Topics Cat., 27, (1-4), 83-86.
ACKNOWLEDGEMENTS
[10] Leadbeater, N. E., Stencel, L. M., 2006, Fast, easy
This work was supported by the National Science preparation of biodiesel using microwave heating. Energy
Foundation (CHE-1429247). and Fuels, 20, 2281-2283.
[11] Gauza, L., Blair, S., McElhoney, K., Kittredge, K. W., 2015,
The Evaluation of Microwave-Assisted and Conventional
Heating in the Acid-Catalyzed Synthesis of Biodiesel from
Vegetable Oil. International J. Adv. Res. Chem. Sci., 2,
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