Appl. Res. J. Sci. Technol.

International Institute for Applied Research

Vol 4(1&2), pp. 1-9, April, 2023 Skies Educational
DOI: 10.47721/ARJST20230401029
Article number: SE-J-ARJST-20230401001
ISSN 2695 1738
https://skies.education/arjst

Development of fatty acids as feedstocks for biofuels from

Gmelina arborea waste leaves
Haruna Ibrahim*1, Idris M. Bugaje2 and Patrick O. Nwosibe1
1
Department of Chemical Engineering, Kaduna Polytechnic, Kaduna-Nigeria.
2
National Board for Technical Education, Kaduna-Nigeria

*Correspondence to: ibrahimhauna@gmail.com ; 08133106608

Received: 23rd November 2022 Accepted: 28th March 2023 Published: 30th April 2023
Abstract: This work was aimed at; investigating a clean method of removing waste leaves from
the waste stream, converting them into fatty acids, biodiesel feedstock, or upgrading to
deoxygenated fuels for higher energy content. Waste leaves of Gmelina arborea were collected,
cleaned, and pulverized with ceramic mortar and pestle. A 50g of the pulverized leaves were
thermally hydrolyzed over 0.75g of H2SO4, NaOH, and ZnCl2 catalysts and 500mL distilled water
on a GallenKamp hot plate magnetic stirrer at 100oC for 30 minutes. The extracts were filtered
with a sheet cloth, dried with 0.2% anhydrous MgSO4 and weighed. Each extract was analyzed
with a gas chromatography and mass spectroscopy (GC-MS) machine to determine its components
and compositions. The quantities of fatty acids extracted over H2SO4, NaOH, and ZnCl2 were
228.30g, 184.30g and 118.43g respectively. The biodiesel estimated from the fatty acids extracted
was found to be 240.02g, 193.8g and 124.39g respectively. Also, the estimated bio-hydrogenated
gasoline (BHG) and bio-hydrogenated diesel (BHD) were found to be 192.27g, 154.97g and
87.37g respectively. The process yields more biodiesel than conventional seed oils. This process
would be more economical to achieve a biofuel economy than the use of lipids from oil seeds.
Keywords: biofuels, development, fatty acids, feedstocks, Gmelina arborea, waste leaves,

Introduction

As economic development is rising, the demand for energy keeps increasing but the petroleum
sources are declining. Even the petroleum price is on the increase due to an increase in demand.
The petroleum source is nonrenewable coupled with its environmental hazards (Hu et al., 2019).
The use of vegetable oils for fuel production has proved inadequate due to high energy demand as
the oil yield from these seeds is insufficient and also the production cost is too high. Biofuels
contain oxygen and unsaturated bonds which make them unsuitable due to their lower energy
content, poor chemical stability and high viscosity (Hu et al., 2019: Kochaputi., et al., 2019). The
focus of biofuel research is shifting to lignocellulose wastes which not only provide energy but
add value to waste. The biofuel feedstocks can be upgraded by eliminating the oxygen atoms and
Copyright © 2023 by Author(s) and Skies Educational
1
Haruna Ibrahim, Idris M. Bugaje and Patrick O. Nwosibe (2023): Development of Fatty Acids as Feedstocks for Biofuels from
Gmelina arborea Waste Leaves

hydrogenation giving rise to what is termed bio-hydrogenated gasoline and diesel (BHG & BHD)
(Kochaputiet al., 2019) and bio-hydrogenated gasoline (BHG) respectfully.
The plant is composed of mainly cellulose, hemicellulose and lignin in different
proportions depending on the type of wood. The leaf of Gmelian arborea is composed of 25%
cellulose and 18.5% hemicellulose (Omokanye et al. 2014) and a lignin of 27% (Prota4u, Accessed
22/06/2022). Cellulose is the polymer of hexoses such as glucose and fructose, hemicellulose is a
polymer of pentose and hexoses and lignin is a polymer of phenyl propane units (Ibrahim et al.,
2015). Extraction of Gmelina arborea leaves yields a variety of products depending on the catalyst
used, operating temperature, the length of time for the extraction and also the solvent is chosen.
In this study, waste Gmelina arborea leaves were collected, cleaned, pulverized and
extracted over three catalysts: sulphuric acid, sodium hydroxide and zinc chloride. The extracts
were filtered and dried with 0.2% magnesium sulphate. A 4g of each of the extracts was analyzed
with GC-MS. The components of fatty acids were identified and their biodiesel, bio-hydrogenated
gasoline and bio-hydrogenated diesel estimates were determined.

Materials and Method

The materials used for this study include ceramic mortar and pestle, sieve of 250µm, GallenKamp
hot plate magnetic stirrer, 1000mL conical flask, 1000mL separating funnel, 500mL beaker, and
top-loading balance, filter, and gas chromatography and mass spectroscopy (GC-MS) machine.
The chemical reagents used include sulphuric acid, sodium hydroxide, zinc chloride, anhydrous
magnesium sulphate and n-hexane.
The waste dry Gmelina arborea leaves were collected from the premises of Kaduna
Polytechnic, Kaduna-Nigeria. The leaves were cleaned and pulverized using ceramic mortar and
pestle and then sieved with a 250µm sifter. The 50g of the powder leaves was added to a mixture
of 0.75g sulphuric acid and 500 mL distilled water. This mixture was heated on the GallenKamp
hot plate magnetic stirrer to 100oC for 30 minutes. The process was repeated for sodium hydroxide
and zinc chloride catalysts. The extracts were filtered and then dried by adding a 0.2% anhydrous
magnesium sulphate shake and poured into a 1000mL separating funnel. The lower layer of
aqueous magnesium sulphate was tapped out. The dry upper layer was collected into a weighed
empty 500mL beaker. The extracts were weighed and recorded and 4g of each was taken to the
GC-MS machine for qualitative and quantitative analysis.

2
 Applied Research Journal of Science and Technology

Results and Discussion

The weights of the extracts over sulphuric acid, sodium hydroxide and zinc chloride were 428.17g
375.15g and 141g respectively. The GC-MS analysis revealed the following fatty acids in the
samples: sulphuric acid-catalyzed sample contained 4.34% 9, 12-octadecadienoic acid, 4.81% 9-
octadecenoic acid, 8.57% oleic acid, 18.6% hexadecanoic acid and 14.9% octadecanoic acid as
presented in Figure 1. The sodium hydroxide catalyzed sample contained 2.84% 9-octadecenoic
acid, 4.04% 9, 12-octadecadienoic acid, 8.57% oleic acid, and 18.8% hexadecanoic acid and 19.7%
octadecanoic acid as presented in Figure 2. The zinc chloride catalyzed sample contained 75%
oleic acid, 5.16% hexadecanoic acid and 3.54% linoleic acid as presented in Figure 3. Besides, the
fatty acids produced from the leaves by the extraction process, other chemicals such as furfural,
butanol, 5-hydroxymethyl furfural, stigmasterol, spathulenol and phytol were also produced.
The total percentage of fatty acids extracted from each sample were 51.22, 49.15 and 81.24,
while the total quantity of fatty acid extracted was 228.30g, 184.30g and 118.43g over sulphuric
acid, sodium hydroxide and zinc chloride respectively. To convert these fatty acids extracted over
sulphuric acid, sodium hydroxide and zinc chloride catalysts to biodiesel by the esterification
process, require 25.59g, 21.53g and 12.96g of methanol respectively. After successful isolation of
the fatty acids, they can be converted to biodiesel by esterification using methanol and sulphuric
acid. These will produce 240.02g, 193.80g, and 124.37g of biodiesel from the extracts of sulphuric
acid, sodium hydroxide and zinc chloride respectively by estimation.
On the other hand, with the recent discovery of converting fatty acids into alkanes, as
reported by Brenna et al. (2020), oleic acid and 9-octadecenoic acid can be broken into azelaic
acid and pelargonic acids as presented in the reaction Scheme 1. This reaction is termed as the
deoxygenation of renewable biofuel (Kochaputiet al., 2019). Decarboxylation of pelargonic acid
yields n-octane and n-nonane which are alkanes in the gasoline range (Sembiring et al., 2018) as
presented in the reaction Scheme 2. Hydrogenation of azelaic acid to pelargonic acid followed by
decarboxylation yields n-octane and n-nonane (Sembriring et al., 2018) as presented in Scheme 3.

3
Haruna Ibrahim, Idris M. Bugaje and Patrick O. Nwosibe (2023): Development of Fatty Acids as Feedstocks for Biofuels from
Gmelina arborea Waste Leaves

Scheme 1: Decomposition of oleic acid into pelargonic acid and azelaic acid.

Scheme 2: Decarboxylation of pelargonic acid to octane and nonane

Scheme 3: Conversion of azelaic acid into octane and nonane by hydrogenation followed
by decarboxylation.

Also, hexadecanoic acid can be converted to pentadecane in diesel range by hydrothermal

decarboxylation in an aqueous medium over Pt/C as reported by Edeh et al. (2019) as presented in
Scheme 4.

Scheme 4: Decarboxylation of hexadecanoic acid to pentadecane

Wu et al. (2016), reported the decarboxylation of octadecanoic (stearic) acid to heptadecane at

300oC reaction temperature for 1.5 hours reaction time over Ni/C catalyst with a conversion of
4
 Applied Research Journal of Science and Technology

80%, selectivity of 88% C10-C17 and 81% C17 as presented in Scheme 5 and 6. This reaction is not
restricted only to fatty acids but also triglycerides. Wu et al. (2016) also reported the
decarboxylation of triglycerin octadecanoate (tristearin) at 355oC for 6 hrs achieved the conversion
of 88% and selectivity of 70% C10-C17 and 40% C71. The two reactions are presented in Schemes
7.

Scheme 5: Decarboxylation of stearic acid to heptadecane

Scheme 6: Decarboxylation of stearic acid to a mixture of alkanes

Scheme 7: Decarboxylation of tristearin to heptadecane and glycerin

In Figures 1-3, the following abbreviations are used.

%A Percentage Fatty acid
T%A Total Percentage Fatty acid
MA mass of fatty acid
TMA total mass of fatty acids
MB mass of biodiesel estimate
MTB total mass of biodiesel estimate
MDF mass of deoxygenate fuel
MTDF total mass of deoxygenated fuel

5
Haruna Ibrahim, Idris M. Bugaje and Patrick O. Nwosibe (2023): Development of Fatty Acids as Feedstocks for Biofuels from
Gmelina arborea Waste Leaves

300
Hexadecanoic acid 9,12-Octadiecenoic acid 9-Octadecenoic acid Oleic acid Stearic acid
Quantity produced/estimated

250

200

150

100

50

0
%A T%A MA (g) TMA (g) MA (g) TMB (g) MDF (g) TMDF (g)

Biofuel types

Figure 1: Fatty acid produced & estimated of biofuels from Sulphuric acid catalyzed reaction

250
Hexadecanoic acid 9,12-Octadiecenoic acid 9-Octadecenoic acid Oleic acid Stearic acid
Quantity produced/estimate

200

150

100

50

0
%A T%A MA (g) TMA (g) MA (g) TMB (g) MDF (g) TMDF (g)

Biofuel types

Figure 2: Fatty acid produced & estimated biofuels from Sodium hydroxide catalyzed reaction

6
 Applied Research Journal of Science and Technology

140
Oleic acid Linoleic acid Hexadecanoic acid
Quantity produced/estimated (%/g)
120

100

80

60

40

20

0
%A T%A MA (g) TMA (g) MA (g) TMB (g) MDF (g) TMDF (g)

Biofuel types

Figure 3: Fatty acid produced & estimated biofuels from Zinc chloride catalyzed reaction

In the figures, mA mass of Fatty acids, TmA represents the total mass of Fatty acid, mA represents
the estimated mass of biodiesel, Df represents the mass of deoxygenated fuel and TmDF represents
the total mass of deoxygenated fuel. Using this process, biodiesel can be produced at a relatively
cheaper cost compared to the conventional use of oils.
Harnessing this process technology for fuel production may compete favourably well with
petroleum conventional processing as Gmelina can be grown everywhere. The conversion of
Gmelina arborea leaves to biodiesel and deoxygenated gasoline and deoxygenated diesel will go
a long way to reduce waste from the waste stream and provide cheaper fuel energy and chemicals
that could substitute those from petroleum sources.

Conclusion

Conversion of waste leaves to fuel energy will be an alternative treatment to conventional burning
that produces smoke and carbon particles which are pollutants. Pulverized leaves of Gmelina
arborea of size 250µm were hydrolytically extracted over 0.75g sulphuric acid, sodium hydroxide
and zinc chloride at 100oC for 30 minutes. The quantity of pulverized leaves hydrolyzed was 50g
and it yielded 228.30g, 184.30g and 118.43g fatty acids over sulphuric acid, sodium hydroxide

7
Haruna Ibrahim, Idris M. Bugaje and Patrick O. Nwosibe (2023): Development of Fatty Acids as Feedstocks for Biofuels from
Gmelina arborea Waste Leaves

and zinc chloride respectively. If these fatty acids were to be isolated and converted to biodiesel,
the estimated yields of 240.02g, 193.80 and 124.37g of biodiesel would be obtained from 50g of
powder leaves. Similarly, the estimated deoxygenated fuels were 192.27g, 154.97g and 87.37g
from sulphuric acid, sodium hydroxide and zinc chloride extract respectively. Therefore, the use
of Gmelina waste leaves as feedstock for biodiesel and deoxygenated fuels would be a better
alternative. It would serve as waste control as well as energy generation.

References

Brenna, E., Colombo, D., Lecce, G.D., Gatti, F.G., Ghezzi, M.C. Tentori, F., Tessaro, D. and Viola,
M. (2020). Conversion of Oleic Acid into Azelaic and Pelargonic Acid by a Chemo-
Enzymatic Route. Molecules, 25, 1882; doi: 10.3390/molecules25081882
Edeh, I., Overton, T. and Bowra, S. (2019). Renewable diesel production by hydrothermal
decarboxylation of fatty acids over platinum on carbon. Biofuels, DOI:
10.1080/17597269.2018.1560554 catalyst
Hu, W., Wang, H., Lin, H., Zheng, Y., Ng, S., Shi, M., Zhao, Y. and Xu, R. (2019). Catalytic
Decomposition of Oleic acid to fuels and Chemicals: Roles of Catalyst Acidity and Basicity
on the Product Distribution and Reaction Pathways. Catalysts MDPI, 9, 1063; doi:
10.3390/catal9121063.
Ibrahim H., Nwanya K.O., Ayilara S., Adegbola O., Nwakuba D.C., Tyoor A.D., Ba’are A.M, and
Shuaibu H. (2015). The potential of Earleaf Acacia (Acacia Auriculiformis) leaves for
Industrial Raw Materials. International Journal of Scientific Engineering and Applied
Science (IJSEAS) Vol. 1, ISSN 2395-3470, pp 462-467. Available at: www.ijseas.com
Kochaputi, N., Kongmark, C., Khemthong, P., Butburee, T., Kuboon, S., Worayingyong, A. and
Faungnawakij, K. (2019). Catalytic Behaviours of Supported Cu, Ni and CO phosphide
Catalysts for Deoxygenation of Oleic Acid. Catalysts, MDPI, 9, 715; doi:
10.3390/catal9090715.
Omokanye, A.T., Lamidi, O.S. and Oyeleke, L.S. (2014). Gmelina Arborea at Shika, Nigeria:
Nutritive Indices, Preference and Intake of Plant Parts by Yankasa Sheep. International
Journal of Research in Agriculture and Forestry Volume 1, Issue 2, PP 31-36, ISSN 2394-
5907.

8
 Applied Research Journal of Science and Technology

Prota 4U (accessed 22/06/2022). Gmelina arborea Roxb. ex Sm. Available at:

https://www.prota4u.org/database/protav8.asp?g
Sembiring, K.C., Aunillah, A., Minami, E. and Saka, S. (2018). Renewable gasoline production
from oleic acid by oxidative cleavage followed by decarboxylation. Renewable Energy,
602-607
Wu, J., Shi, J., Fu, J., Leidl, J.A., Hou Z. and Lu, X. (2016). Catalytic Decarboxylation of Fatty
Acids to Aviation Fuels over Nickel Supported on Activated Carbon. Scientific Reports |
6:27820 | DOI: 10.1038/srep27820