Beruflich Dokumente
Kultur Dokumente
Research Article
Heterogeneous Transesterification of Luffa aegyptiaca
Oil to Biodiesel
*Oche S. Gabriel1,5, Adamu T. Jummai2, David I. Dahutu3 and Gambo H. Peace4
1,2,3,4
Bioresources Development Centre, National Biotechnology Development Agency, Federal Ministry of Science and
Technology, Jalingo, Taraba state, Nigeria.
5
Department of Chemistry, School of Pure and Applied Science, Modibbo Adama University of Technology, Yola, Nigeria
In the continuous desire to find suitable alternative, renewable and biodegradable source of oil
for commercial diesel Luffa aegyptiaca oil was converted into biodiesel through
transesterification reaction using heterogeneous hydrotalcite particles from MgO/Al 2O3/Kaolin
clay as catalyst and methanol as solvent at controlled reaction conditions. The characterization
results of pure Luffa aegyptiaca oil and biodiesel samples was obtained and compared: moisture
content 0.0045 %-0.0034 %, ash content 0.00 %-0.02 %, saponification value 194.5 - 61.43, acid
value 9.65-0.144, freezing point 5.00 - 30.00 min, pour point 5.00-3.00 min, density 0.969 g/mL-
0.889 g/mL, while the flash point gave 349 k-345 k, specific gravity 0.865 g/mL-0.851 g/mL, and
viscosity 34.95 Nsm-2- 5.82 Nsm-2 accordingly. The catalyst sample (MgO/Al2O3/Kaolin clay) after
characterized using X-Ray Diffractometer, showed promising surface activity and selectivity on
both the calcined and uncalcined catalyst. The optimum transesterification reaction conditions
was obtained at 333 k, 6 hours reaction time and 6% catalyst concentration. The reaction
conditions had direct effect on percentage yield of the biodiesel product with maximum yield of
79.61 % obtained for untreated oil but 81.27 % for treated oil at 333 k, 3 hours reaction time and 2
% catalyst concentration. FT-IR spectra analysis of biodiesel oil revealed decrease in frequency
band of the hydroxyl group (O-H) between 1780 cm-1 and 1700 cm-1 and its subsequent absence
at 1730 cm-1. The Gas Chromatography-Mass Spectrophotometer composition for pure Luffa
aegyptiaca oil and Biodiesel oil showed that free fatty acid was converted to fatty acid methyl
esters. Thus, transesterification of Luffa aegyptiaca oil sample using MgO/Al 2O3/Kaolin clay
heterogeneous catalyst was a success.
Keywords: Biodiesel, Luffa aegyptiaca, transesterification, heterogeneous catalyst, kaolin clay/Al2O3/MgO, Calcined
INTRODUCTION
A great number of plants part from jatropha, cotton, luffa, self-reliance are some of the driving forces of our
soya, etc, are all of domestic and medicinal importance, economic policy. In the development, exploitation and
hence they are called economic plants. Seeds are utilization of raw materials, only natural renewable and
fertilized ovules with embryo and can germinate into new degradable ones should be encouraged, because of the
plants, seeds contain the greatest concentration of protein, global constant demand for energy and alternative raw
fats and oils present in plants (Njerum, 1997). materials for fossils as well as for wide variety of industrial
product (Clasen and Kulicke, 2001).
The evaluation of raw material requirement in Nigeria
indicates that past effect have been concentrated on the *Corresponding Author: Oche S. Gabriel, Bioresources
exploration and exploitation of petroleum to some extent, Development Centre, National Biotechnology
metallic mineral resources. Today the uses and diversity Development Agency, Federal Ministry of Science and
in the application of catalyst or crystal structures in the Technology, Jalingo, Taraba State, Nigeria. E-mail:
research and processing of plant derived products have ochesundaygabriel80@gmail.com
assumed significant dimensions. The local sourcing of raw Co-Author 2Email: jummaiadamu76@yahoo.com
materials in order to conserve foreign exchange, 3
Email: didahutu@yahoo.com
promotion of industrial development and thrust for national 4
Email: gambopeace9@gmail.com
Fats and oil are carboxylic esters (trimesters) derived from ml), separating funnels (250 ml and 500 ml), test tubes,
glycerol and are known as glycosides or triglycerides. In desiccator, burette, pipette, retort stand, electronic
chemical technology, transesterification process is now weighting balance, filter paper, soxhlet, distiller, sampling
used to convert seed oils as raw materials to biofuels via bottles and tubes, spatula, magnetic stirrer, corks, funnels,
catalytic means. In homogenously catalyzed stop watch, hand gloves, nose mask, mortar and piston
transesterification process, whether an acid or base (ceramic and metal), sieve (100 µm), foil paper, indicator
catalyzed, suffers some drawbacks in terms of process (phenolphthalein), petri dish, crucibles, clamps, oil bath,
integrity (Dae-Won et al., 2009): The corrosion of the water bath, steam bath, pH meter, muffle furnace, oven
reactor and pipelines by dissolved acid/base species, (523 k, 1273 k), refrigerator, Gas Chromatography and
impossibility of catalyst recovery from the reactant-product Mass Spectrophotometer, Fourier Transform Infrared, X-
mixture resulting to environmental pollution when ray diffractometer, viscometer, centrifuge (8,000 rpm).
disposed, lastly is the limitation in establishing a
continuous process. Reagents
Thus, heterogeneously catalyzed process, especially Methanol, hexane, sulphuric acid (H2SO4), sodium
those involving solid base catalysts, has been suggested hydroxide (NaOH), potassium hydroxide (KOH), kaolin
and studied continuously by academia and industry clay (Al2S2O4(OH)4), hydrated Al2O3, hydrated MgO and
(Ogunkunle et al., 2017). sodium trioxocarbonate (Na2CO3), distilled water and urea
were obtained from the department of chemistry, School of
This work is aimed at investigating the heterogeneous Pure and Applied Science, Modibbo Adama University of
transesterification of Luffa aegyptiaca oil to biodiesel using Technology, Yola, Nigeria, while Luffa aegyptiaca oil was
kaolin clay/Al2O3/ MgO solid base catalyst and possibly extracted using sohxlet distiller from Luffa aegyptiaca seed
explain an expected high yield of biofuel from the catalytic gathered from surrounding of the institution and diesel oil
transesterification process adopted in this research work. from Nigerian National Petroleum Cooperation depot, Yola
The specific objectives of the research are to: Depot.
(i) Evaluate the particle size and the crystalline nature of
solid catalyst mixture. METHODS
(ii) Extract Luffa aegyptiaca oil from the seeds of Luffa
aegyptiaca plant. Experimental procedure
(iii) Produce biodiesel from Luffa aegyptiaca oil using
kaolin clay/Al2O3/MgO as solid catalyst. This investigation was carried out in Abti American
(iv) Study the physicochemical characteristics, functional University (AAU), Petroleum Technology laboratory, using
groups and fatty acid composition of Luffa aegyptiaca non-edible vegetable oil from Luffa aegyptiaca plant for
oil and biodiesel. production of biodiesel as illustrated by Hirata et al.,
(v) Explain the efficiency of the heterogeneous (2007). The uniqueness of this investigation is the
transesterification process based on the effect of heterogeneous system created to investigate the
molar ratio of methanol to oil, water content, reaction production of biodiesel. It involves the use of
time, temperature and mass of catalyst to oil ratio. heterogeneous base catalyst Clay/Al2O3/MgO.
At present, instead of the use of catalyst in petroleum and Determination of fatty acid composition in the oil
some metallic resources, more interest has been focused
in the use of catalyst from natural raw materials to catalyze Calculation of molecular weight of Luffa aegyptiaca.
seed oil for production and use as biodiesel that are more
environmentally friendly, acceptable and biodegradable. If 56.1 × 1000 × 3
𝑀= Equation (1)
possible, explain the effect of molar ratio of methanol to oil, 𝑆𝑉−𝐴𝑉
water content, reaction time and mass ratio of catalyst to
oil stating what can be done to ascertain the acceptability Where AV is the acid value (mg KOH/g oil) and SV is the
of the empirical relationship. saponification value (mg KOH/g oil) as shown by Hawash
et al., (2011).
In the reaction, the catalyst was weighted out using The viscometer was washed and dried. The sample was
electronic weighing balance, poured into the methanol and sucked into it and then immersed into the circulatory bath
dispersed with mechanical stirring (about 600rpm). Then set at 303 k. The time of flow of sample from upper mark
the above pretreated oil was added into the mixture and to lower mark of the viscometer was recorded using a stop
heated to 333 k by water bath for 6-9 hours. After reaction, watch. The experiment was repeated thrice and average
excessive methanol was distilled off under a vacuum flow time recorded. This was carried out on oil before and
condition (evaporation) and the two phases (glycerol and after transesterification.
biodiesel) were separated out using a separating funnel
and the catalyst was recovered by filtration using filter The instrumental constant was obtained from the
paper. viscometer thus viscosity of the sample was calculated
using the formula below:
Catalyst dosage variation
Viscosity (V) = K T, Equation (2)
The amount (%wt) of the catalyst from the range of 1% -
9% for the base Clay/Al2O3/MgO catalyst was varied and Where K = Instrumental constant
the corresponding yield of methyl ester at a temperature of D =Density of the sample
333 k for 9 hours with methanol to oil ratio of 3:1 and 600 T = Efflux time (sec)
rpm was observed.
Specific gravity determination
Variation of molar ratio of methanol to oil
For many liquids, specific gravity is used as the ratio of the
The next investigation was the variation of molar ratio of mass of a given volume to the mass of an equal volume of
methanol to oil, the rate of ratio chosen was from 3:1 – water. Therefore, specific gravity is dimensionless.
12:1, using the base Clay/Al2O3/MgO catalyst Specific gravity decreases with increasing temperature
consecutively under these reaction conditions; 333 k, and decreases as viscosity decreases. Specific gravity
atmospheric pressure, 9 hours under a catalyst dosage of was determined according to the standard method
1-9% w/v and 600 rpm. contained in ASTM D5002 (ASTM, 1998). The sample oil
was poured into a vertical glass cylinder and a hydrometer
Variation of reaction time on methyl ester yield was placed in the oil and allowed to be stable. The value
of the specific gravity was taken from the marking on the
Another very important investigation under this work is the stem of the hydrometer at the surface of the oil.
variation of reaction time to observe the % yield of the
Heterogeneous Transesterification of Luffa aegyptiaca Oil to Biodiesel
Oche et al. 083
Dc = k ((α/β). Cos θ) Scherer equation. Equation (5) Equation (7): nucleophilic attack of the alkoxide at the
carbonyl group of the triglyceride generates a tetrahedral
Where intermediate,
Dc = is the average particle size = 5.1 nm
K = is the Scherer constant = 0.89
α = is the X – ray wavelength, (CuKα) = 0.1541 nm
β = is the full width at half maximum (FWHM) = 0.026261
nm
θ = is the diffraction angle = 13.31200
At 9% (w/v) of kaolin hydrotalcites the biodiesel yield Comparation of kaolin clay/MgO/Al2O3 with different
decreased, which was possible due to a mixing problem catalyst models such as;
involving reactants, products and solid catalyst. Na2CO3/Al2O3/MgO, Urea/Al2O3/MgO and KOH on
Furthermore, when excessive catalyst was used, the treated oil.
transesterification process was easily emulsified and
resulted in difficulties during separation of products (Deng The activity of the catalyst prepared was compared with
et al., 2011). different catalyst models keeping the temperature, catalyst
dosage, time and methanol/oil ratio constant. Figure 8
Effect of molar ratio of methanol to oil showed values obtained were 81.26 %, 93.64 %, 91.72 %
and 87.51 % for Kaolin, Na2CO3, Urea and KOH
Theoretically raising the molar ratio of methanol to Luffa respectively (Hawash et al., 2011).
aegyptiaca oil favors the reaction (Hawash et al., 2011) i.e.
stoichiometrically, 3 mole of methanol were required for Effect of temperature on the viscosity of PLO, BD1 and
each mole of Luffa aegyptiaca oil. However, practically CD
methanol/oil molar ratio should be higher than that of
stoichiometry in order to drive the reaction towards The effect of temperature on the viscous flow of PLO,
completion and production of more methyl esters. BD1and CD as represented in Figure 9, was determined
Moreover, Figure 5 showed that methanol can increase in order to obtain a suitable temperature of the biodiesel
the dissolution of Luffa aegyptiaca oil, intermediates and (BD1) compared to the commercial diesel (CD) was
biodiesel resulting in the wastage of the materials. When represented in Figure 10.
the ratio increased from ratio 6/1 to 9/1, the yield of methyl
ester increases gradually from 63.41% to 69.44%. But it Fourier Transform Infra-Red Analysis
was observed that at molar ratio above 9/1, excessive
methanol had no significant effect on the yield (Deng et al., A more suitable blend ratio of biodiesel/commercial diesel
2011). was obtained at 303 k and 313 k with viscosity of 5.25
Nsm-2 and 4.23 Nsm-2 respectively and blend ratio of
Effect of reaction time 20:80. Table 2 showed that the PLO peaks were seen to
have bands at 585, 722, 1163, 1375, 1461, 1655, 1745,
Because it was a heterogeneous reaction, the mass 2679, 2853, 2923, 3005 and 3473 cm-1. While those of the
transfer tends to be slow at 1 hour with biodiesel yield of BD1 were seen at 512, 722, 1170, 1362, 1462, 1655,
42.17%, but at 3 hours the biodiesel yield increased 1743, 2363, 2854, 2925, 3005 and 3461 cm-1 along with
drastically to 62.07% which further increased to 73.68% at their expected functional groups. These spectral bands are
6 hours reaction time. Finally, an increase in biodiesel yield displayed in Figures 11, 12 and 13 respectively which are
was observed at 9 hours reaction time with 73.97% discussed according to the regions obtained in the FTIR
biodiesel production. These phenomena showed in Figure spectra. This data suggests that, the biodiesel samples
6 agreed with previous research findings which stated that indicated proof of successful transesterification.
longer time was required for the subsequent separation
stage because the separation of the esters layer from The region (3700–3200) cm-1
glycerol was difficult due to the fact that methanol with one
polar hydroxyl group could emulsify product (Deng et al., This region is characterized by hydroxyl (O-H) group of
2011). alcohol and phenol, amine (N-H) and methyl (C-H)
stretching bonds. The appearance of the frequency band
Effect of reaction temperature 3473 cm-1 PLO sample spectra is an indication of the O-H
stretching vibrations. However, the decreased stretching
Reaction temperature was also an important factor that frequency at 3473–3461 cm-1 in the hydroxyl of the
influences the biodiesel yield in this research. Each biodiesel samples spectra showed proof of biodiesel
experiment was run for 3 hours with 3% (w/v) catalyst and synthesis. Thus, justified with increase in the absorption
3/1 molar ratio of methanol/oil content. The result indicated 1655 cm-1 is an indication of the C=C stretching band of
in figure 7 showed that biodiesel yield was low at a low alkenes (Pavia et al., 2001).
temperature with only 34.79% yield at 313 K for 6 hours
which increased at constant time of 6 hours to 58.35% The region (3200–2800) cm-1
yield at 318 k and then to 60.26% yield at 323 k, 67.15%
was obtained at 328 k with a highest of 73.68% yield This region is characterized by the presence of O-H
obtained at a temperature of 333 k, slight decrease of carboxylic acid, vinyl C-H, aryl C-H, sp3 alkyl (C-H) and C-
59.10% yield at 338 k was then observed (Deng et al., H aldehyde. The frequency band 2923 cm-1 in PLO sample
2011). spectra depict the C-H stretch associated with oil. The
spectra of biodiesel sample also showed the presence of
C=C stretching bands of the biodiesel samples with 2925
cm-1 (Pavia et al., 2001).
The region (2800–2200) cm-1 namely; oleic acid (18:1) 22.37%, linoleic acid (18:2)
50.19%, palmitic acid (16:0) 11.20%, stearic acid (18:0)
This region comprises of alkynes C≡C, nitriles C≡N and 7.70% and arachidonic acid (18:1) 2.40% methylesters
carboxylic acid O-H absorption band. The PLO sample was obtained (Xie et al., 2006; Barakos et al., 2008).
spectra in Figure 11 revealed the absorption band at 2679
cm-1, while the biodiesel samples showed its reduction to
2363 cm-1 (Pavia et al., 2001) . CONCLUSION
The region (1850 – 1100) cm-1 In the current investigation, it was confirmed that Luffa
aegyptiaca oil can be used as resources to obtain
This region is mainly dominated by the carbonyl group biodiesel. The experimental results showed that
(C=O) of esters, ketones, aldehyde, carboxylic acids and heterogeneous catalyzed transesterification reaction is a
amides. The study of hemicelluloses and lignin reveal that promising area of research for the production of biodiesel
absorption lines situated between 1510 and 1600 cm-1 is in a large scale. Effect of different parameters such as
caused by lignin while the absorption band at 1730 cm-1 is temperature, time, reactant ratio and catalyst
caused by hemicelluloses, thus, the C=O stretch in concentration on the biodiesel yield was analyzed. The
conjugated ketones, esters and carbonyls groups are best combination of the parameter was found at 6:1 molar
proved. ratio of methanol to oil, 6 % kaolin clay/ MgO/Al2O3 base
catalyst, 333 k reaction temperature and 6 hours of
Interestingly, the biodiesel samples spectra have shown reaction time. The optimum condition yielded
evidence of transesterification with increased absorption, approximately 80% of biodiesel. From the characterization
high yield and enhancement of 1645 cm-1, 1730–1650 cm- of the biodiesel, the physical properties of the biodiesel
1 C=O stretching, 1350–1400 cm-1 which is C–H bond in – from Luffa aegyptiaca oil with methanol were found to be
O(C=O)–CH3 group. All esters give rise to three strong within the ASTM specified limit. Also, the characterization
infrared bands that appear at approximately 1700 cm-1, of the kaolin clay/ MgO/Al2O3 base catalyst showed good
1300 cm-1 and 1200 cm-1, known as the rule of three catalyst activity after calcination at 773 k. The viscosity and
(Bodirlau and Teaca, 2009). . density of Luffa aegyptiaca oil reduced substantially after
transesterification and it’s comparable to petrol diesel.
The region (1000–400) cm-1
Dae – Won L, Young-Moo P, Kwan-Young L (2009). Pavia DL, Lampman GM, Kriz-jr GS (2001). Introduction
Heterogeneous Base Catalysts for Transesterification to Spectroscopy. 3rd edn. Victoria, Australia:
of Biodiesel Synthesis. J. Catal. Surv. Asia, 13:63 – 77. Thompson Learning.
Dean DA (1999). Nuclear targeting of plasmid DNA in Ponaruselvam S, Panneerselvam C, Murugan K, Arthi N,
human corneal cells. Current eye research. 19 (1): 66- Kalimuthu K, Thangamani S. (2001). Synthesis of silver
75. nanoparticles using leaves of Catharanthus roseus L.
Deng X, Fang Z, Liu YH. (2011). Ultrasonic G.Don and their antiplasmodial activities. Asian Pacific
transesterification of Jatropha curcas L. oil to biodiesel J. of Tropical Biomedicine, 574-580.
by a two-step process. J. of Energy Conversion Schuchardt U, Serchelia R, Vargas RM. (1998).
Management, 51:2802-7. Transesterification of vegetable oils: a review, J. of
Hargreaves JSJ (2016). Some considerations related to Brazil Chemistry. Soc, 9:199.
the use of the Scherer equation in powder X-ray Xie W, Peng H, Chen LJ. (2006). Calcined Mg-Al
diffraction as applied to heterogeneous catalyst. J. Cat. hydrotalcites as solid base catalysts for methanolysis of
Structure and reactivity, 2: 33-37. soybean oil. J. Molecular Catalyst Applied Chemistry.
Hawash S, El-Diwani G, Adel K. (2011). Optimization of 246:24.
biodiesel production from jatropha oil by
heterogeneous based catalyzed transesterification.
Sodium removal decontamination and requalification
3(6).
Hirata K, Satake K, Yamaki S, Tanioka Y, Yamanaka Y.
(2007). Examination based on the northeast edge of the
1952 Tokachi-oki earthquake tsunami. Published
report, zisin 2, 60:21-42.
Liu X, He H, Wang Y, Zhu S. (2007). Transesterification of Accepted 4 May 2020
soybean oil to biodiesel using SrO as a solid base
catalyst. J. Catalysis communications, 8:11007-111. Citation: Oche SG, Adamu TJ, Dahutu ID, Gambo HP
Liston BJ (1993). Biodegradation/Biobased lubricants and (2020). Heterogeneous Transesterification of Luffa
greases. Int. J. of Bioengineering, 5:40-48. aegyptiaca Oil to Biodiesel. International Research Journal
Njerum PN (1997). Characterization of seed oils (B.Tech) of Biochemistry and Biotechnology, 6(1): 080-091.
chemistry dissertation. Federal University of
Technology, Yola, Nigeria.
Odebunmi EO, Ismaeel RO. (2012). GC-MS
Characterization of Nigerian Gulf Heavy Crude Oil
Fractions. J. of Elixir Org. Chem. 42: 6472-6477. Copyright: © 2020 Oche et al. This is an open-access
Ogunkunle O, Oniya OO, Adebayo AO. (2017). Yield article distributed under the terms of the Creative
Response of Biodiesel Production from Heterogeneous Commons Attribution License, which permits unrestricted
Catalysis of Milk Bush Seed (Thevetia peruviana) Oil. use, distribution, and reproduction in any medium,
J. of Energy and Policy Research, 4: 21-28. provided the original author and source are cited.
APPENDIX
Figure 2: X-Ray Diffraction of Calcined MgO/Al2O3/Kaolin Figure 6: Effect of Time of Reaction on Yield
Catalyst
Figure 15: Gas Chromatography- Mass Spectrograph of Luffa aegyptiaca Biodiesel (BD1)