1.

0 INTRODUCTION
1.1 Background of Study
Biodiesel is a renewable clean fuel derived from vegetable oil and animal fat. It can be used as a
possible alternative to petroleum diesel. Currently, almost all commercial process for production of
biodiesel uses first generation feedstock (edible vegetable oils) as raw material. The cost of biodiesel
from this process is about 1.5 – 3 times higher in cost than the cost of petroleum diesel (Endalew et
al., 2015). One way of reducing the biodiesel production cost is to use less expensive second and third
generation feedstock such as non- edible oils. Allamanda cathartica L. (Yellow Bell, Golden Trumpet)
seed bears oil that is non edible oil. According to Egwim et al (2015) no much attempt has been
documented on this plant oil for biodiesel synthesis.

Research has shown that transesterification of biodiesel with secondary alcohol can be used for the
production of biolubricant. Appreciable number of studies have been documented on the production
of biodiesel and biolubricants from different vegetable oil. Homogeneous alkaline transesterification
has been known to be the most viable way for commercial production of biodiesel. This method is
associated with several drawbacks (Zanette et al., 2014). Solid heterogeneous catalytic
transesterification is an alternative process that offers simplification and economy of catalyst removal
and more eco-friendly (Vyas et al., 2009). Clay are interesting catalytic materials due to their low cost
and environmentally friendly. Kaolinite is a group clay that can be used as catalyst (Nascimento et al.,
2011). The catalytic activity of metakaolinite in the transesterification reaction of waste cooking oil
with methanol was reported to give high biodiesel yields. Metakaolinite catalyst can be reused because
it exhibited only a slight loss of activity even after eight consecutive reaction cycles (Ramirez - Ortiz
et al., 2012). The obvious environmental advantages of using clay as catalyst are also complemented
by the fact that kaolin is fairly inexpensive, readily available worldwide and even after the exhaustion
of catalytic activity, it can be used as a raw materials for cement, ceramics or other industries (Zatta et
al., 2014). However, the catalytic activity of kaolinite, remains poorly studied (Nascimento et al.,
2011). This is study report of the preparation, characterization and catalytic tests of functionalized
metakaolin from indigenous kaolin as a heterogeneous catalyst for transesterification of allamanda
seed oil.
1.2 PROBLEM STATEMENT
The application and use of pure plant oil as fuel and lubricant is characterized by low thermal and
oxidation stability, poor low temperature properties and viscometric properties. Hence the need
for chemical modification via transesterification. The use of first generation feedstock (edible
oils) for biodiesel and bio-based lubricant synthesis in the developing economy like Nigeria is not
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very feasible since the nation cannot satisfy the food requirements of these oils. Hence the need to
study the potential of available non edible oil for biodiesel and bio lubricant production. The
Response Surface Methodology (RSM) optimization and kinetics of biodiesel and bio-lubricant
production through transesterification with ethylene glycol using functionalized kaolin have not
been documented in literature.

1.3 AIM AND OBJECTIVES

The purpose of this work is to study the synthesis of biodiesel and biolubricant from allamanda oil
seed using functionalized kaolin as heterogeneous. This aim can be actualized through the realization
of the following objectives.

To characterize the raw and thermally treated kaolin.

To extract and characterize the oils (physic-chemical properties, oxidation stability, thermal
stability and fatty acid compositions).

To optimize the transesterification of the oil to biodiesel using the functionalized kaolin studying
the effect of process variables

To characterize the biodiesel produced for its fuel properties, cold flow behaviour, fatty acid
compositions, oxidation stability and thermal stability.

To optimize the transesterification of the biodiesel to biolubricant using the functionalized

kaolin studying the effect of process variables.

To characterize the biolubricant for its lubricating properties.

1.4 SCOPE OF STUDY

The purview of this research will limited to optimization, characterization, kinetics of biodiesel and
biolubricant synthesis from alamanda seed oil.

1.5 JUSTIFICATION OF STUDY/ RELEVANCE TO OIL AND GAS INDUSTRY

Biodiesel production from plant seed oil is an attempt to integrate the agricultural sector with the
downstream petroleum industry. Increasing usage of bio-based products will lead to reduction in
petroleum consumption. Bio based fuel and lubricants are very renewable and eco- friendly
products that exhibit better performance characteristic than mineral oil derivatives.

Bio based lubricant will find wide application in offshore drilling where its operation requires
contact with water bodies.

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The research is expected to be one of the very first attempts to generate data to facilitate the design
of an integrated pilot plant for the production of biodiesel, and bio- based lubricant from non -
edible oil seed.

This will provide a platform for the construction of a pilot plant which eventually shall be scale
up to a full plant in the long run for the production of commercially competitive biodiesel and bio-
lubricant from non-edible oilseed in Nigeria. The completion of this research will help in
actualizing the Nigeria National Petroleum Corporation (NNPC) 2005 Renewable Energy
Initiative and it will also serve as a prompt response to the Energy Commission of Nigerian long
term (2016- 2025) plan on the nation’s energy requirement which intends to develop energy from
biomass in the nearest future.

2.1 Material
Oilseed and Kaolin will be locally sourced. Potassium hydroxide, methanol, acetic acids,
phenolphthalein solution, isopropyl alcohol will be obtained from or local chemical supplier.
2.2 Method

2.2.2. Characterization of Kaolin and Metakaolin

The pore size, pore volume and average specific superficial area will be determined by the Brunauer–
Emmett–Teller (BET) method while the average porous diameter will be obtained using the BJH (Barret,
Joynere, Halenda) technique and Energy dispersive x-ray spectrometry would be used to determined
elemental composition of catalyst (Zanette et al., 2011). The surface morphology of the catalyst would be
determined by scanning electron microscope (SEM) analysis as reported by Zanette et al., 2014. Fourier
Transform Infra Red (FT-IR) to show the surface functional group attached to the catalyst surface. X-ray
diffractions will be obtained using a diffractometer, using the powder method Thermal analysis
(thermogravimetry (TGA) and differential thermal analysis (DTA)) measurements were
performed in 150 μL alumina crucibles with a thermoanalyzer under a 50 mL min−1 oxygen flow.
The heating rate of 10 °C min−1 will be employed and the temperature range was 30–1000 °C.

2.2.3 Thermal treatment of kaolin

Kaolin will be thermally activated to form the metakaolinite phase. The phase transformations that
occur when kaolin is calcined at high temperatures. The calcination will performed under static air
in a programmable furnace for 10 h at 800°C, with a heating rate of 10°C/min from room
temperature to the calcination temperature (Ramirez - Ortiz et al., 2012). The metakaolin samples
were then activated at 90 °C for 1 h with different concentration of tetraoxosulphate (iv) acid

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solutions and then washed with distilled water, dried at 120 °C for 12 h and calcined at 400 °C for
an additional 2 h. The kaolin will be further impregnated with potassium hydroxide/calcium oxide
at different mass ratio (Potassium hydroxide/ calcium oxide: Kaolin) ranging between 1:2-1:6,
this was done using a reflux condenser, at 60°C for 24 hours with continuous stirring. A muffle
furnace will be used to calcine the catalyst at a temperature of 400 °C for 5 hours.

2.2.4 Oil Extraction and Characterization

The oil extraction and characterizations shall determine according to work of Bilal et al., 2013.

2.2.5 Biodiesel and biolubricant production

Prior to the experiments, the catalysts were activated at 130 °C in an oven for 90 min. The catalytic
tests were performed using a PARR 4843 reactor. In a typical experiment, The oil will be heated
at 100 °C to remove solids and water respectively. The oil will be mixed with methanol and
different concentration of the solid catalyst (based on the oil weight), time according to the
experimental design. The reaction mixture will be kept under constant stirring (700 rpm). After
completion of the reaction, the solid catalyst will be separated by filtration. The percent of
conversion of the oil into its biodiesel was estimated by measuring the yield of the product. The
catalyst shall recycled until it activity is reduced. The production of biolubricant will be carried
out according to the work of Arbian and Salimon (2011).

2.2.6 Characterization of the biodiesel and biolubricant

The biodiesel produced shall be characterized using the American Standard for Testing and
Measurement (ASTM) biodiesel standard for its fuel and low temperature properties, storage and
thermal stability. The fatty acid composition and functional group present shall be determined.

3.0 EXPECTED RESULTS

Oil yield and its characteristics (physic-chemical properties and fatty acid compositions.
Optimized conditions of kaolin functionalization as heterogeneous catalyst
Optimized conditions of biodiesel synthesis
Fuel properties of biodiesel
Optimized conditions for bio based lubricant synthesis.
Lubricating characteristic of the biolubricant

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 4.0 SCHEDULE OF WORK

OCT- NOV 2017

2018
DEC,17 – JAN
FEB - MARCH

APR – MAY
JUN - JULY

AUG – SEPT

OCT- NOV
2019
DEC – JAN,

FEB – MARCH
APR - MAY

JUN - JULY
AUG - SEPT

OCT- NOV
2020
DEC – JAN,
FEB - MARCH

APR – MAY
JUN - JULY
2020
AUG – SEPT,
Activities

Review Literature
Sample collection
Proposal defence
Catalyst Preparation and Characterization
Biodiesel Production
Biodiesel Characterization
Biolubricant Production and Characterization
Discussion of results.
Submission of thesis to supervisor
Internal Examination
External Examination
Submission of corrected copy for senate approval.
Attending research conferences
5.0 REFERENCES
Arbain Noor Hafizah and Jumat Salimon (2011). The Effects of Various Acid Catalyst on the Esterification
of Jatropha Curcas Oil based Trimethylolpropane Ester as Biolubricant Base Stock. Journal of Chemistry.
8(S1), S33-S40.

Bilal S, Mohammed-Dabo I., Nuhu M, Kasim, S. A, Almustapha I. H and Yamusa Y. A (2013). Production
of biolubricant from Jatropha curcas seed oil. Journal of Chemical Engineering and Materials Science. Vol.
4(6), 72-79.

Bugaje I.M. and Mohammed I.A, (2008) “Biofuels Production Technology” Science and Technology Forum
(STF), Zaria. 1-109.

Endalew .A.K, Kiros .Y and Zanzi .R (2015) “Inorganic heterogeneous catalysts for biodiesel production from
vegetable oils: Review” Biomass and Bioenergy, 35: 3787 – 3809.

Egwims, E.C., Shuaibu, A., and Sam, O.K (2015) Biodiesel production from Allamamda seed oil ,
International Journal of Applied Science 51 (2011) 267–273.

Nascimento, L.A.S., Rômulo S. Angélica, Carlos E.F. da Costa, José R. Zamian, Geraldo N. da Rocha Filho
(2011) Comparative study between catalysts for esterification prepared from kaolins, Applied Clay Science,
51, 267–273.

Ramirez-Ortiz, J., Merced Martinez, Horacio Flores (2012) Metakaolinite as a Catalyst for
Biodiesel Production from waste cooking oil, Front. Chem. Sci. Eng. 2012, 6(4): 403–409

Veljokovic, V., Stamenkovic, O.S., Zoran B. Todorovic , Miodrag L. Lazic , Dejan U. Skala, (2009).
Kinetics of sunflower oil methanolysis catalyzed by calcium oxide, Fuel, 88, 1554-1562.

Vyas Amish P., Jaswant L. Verma, N. Subrahmanyam (2010). A review on FAME production processes,
Fuel 89 (2010) 1-9.
Zanette Andréia. F, Rodrigo A. Barella , Sibele B.C. Pergher , Helen Treichel , Débora OliveiraMarcio A.
Mazutti , Edson A. Silva a J. Vladimir Oliveira (2014). Screening, optimization andkinetics of Jatropha curcas
oil transesterification with heterogeneous catalysts, Renewable Energy, 36, 726-731.
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