PRODUCTION OF BIO-DIESEL USING PALM KERNEL OIL

By
ZIBABO EBIYE AYAOKPO
UG/07/0783

A RESEARCH PROJECTED SUBMITTED TO THE DEPARTMENT OF

CHEMICAL ENGINEERING
FACULTY OF ENGINEERING
NIGER DELTA UNIVERSITY
WILBERFORCE ISLAND BAYELSA STATE

NOVEMBER 2018
Biofuel Research Journal 4 (2014) 134-138
Original Research Paper
Production and characterization of biodiesel using palm kernel oil; fresh
and recovered from spent bleaching earth

1Department of Chemistry, University of Ilorin, P.M.B 1515, Ilorin,

Nigeria. 2Department of Chemical Engineering, University of Ilorin,
P.M.B 1515, Ilorin, Nigeria.

HIGHLIGHTS

 Utilization of agricultural residue; cocoa pod ash, in place of KOH

catalyst for biodiesel production.  Palm kernel oil was recovered from
spent bleaching earth.  Cocoa pod ash as catalyst led to higher yields
of methyl esters from palm kernel oil and spent bleaching earth oil.


ABSTRACT
Keywords: Palm kernel oil Spent bleaching earth Agricultural residues
Cocoa pod ash Novel basic catalyst Biodiesel
Palm kernel oil (PKO) was recovered from spent bleaching earth with a
yield of 16 %, using n-hexane while the fresh oil was extracted from
palm kernel with n-hexane and a yield of 40.23% was obtained. These
oils were trans-esterified with methanol under the same reaction
conditions: 100oC, 2 h reaction time, and oil-methanol ratio of 5:1 (w/v).
The cocoa pod ash (CPA) was compared with potassium hydroxide
(KOH) as catalyst. The percentage yields of biodiesel obtained from
PKO catalysed by CPA and KOH were 94 and 90%, respectively. While
the yields achieved using the recovered oil catalysed by CPA and KOH
were measured at 86 and 81.20 %. The physico-chemical properties of
the biodiesel produced showed that the flash point, viscosity, density,
ash content, percentage carbon content, specific gravity and the acid
value fell within American Society for Testing and Materials (ASTM)
specifications for biodiesel. The findings of this study suggest that
agricultural residues such as CPA used in this study could be explored as
alternatives for KOH catalyst for biodiesel production.

1. Introduction

Fossil fuel depletion, concern for the environment and unstable crude oil
prices have led to intensified search for alternative non-fossils fuels. Oil
(PK)recovered from spent bleaching earth (SBE) and palm kernel has
been found to be an alternative source of energy (Knothe et al, 2005).
These oils cannot be used directly in internal combustion engine due to
two main reasons: low volatility and high viscosity (Knothe et al, 2005;
Atabani et al.,
Aladetuyi et al. / Biofuel Research Journal 4 (2014) 134-138
 Please cite this article as: Aladetuyi A., Olatunji G.A., Ogunniyi D.S.,
Odetoye T.E. Production and characterization of biodiesel using palm
kernel oil, fresh and recovered from spent bleaching earth. Biofuel
Research Journal 4 (2014) 134-138.
.

.
2012). To overcome these problems, vegetable oils or animals fats are
reacted with simple alcohol (methanol, ethanol, propanol) to produce
fatty acid methyl esters (FAME), fatty acid ethyl esters (FAEE) and fatty
acid propyl esters (FAPE) which are also known as biodiesel. The
methods to achieve such conversion include pyrolysis, micro-emulsion
and trans-esterification (Knothe et al, 2005). Among them, trans-
esterification was found to be the best route with minimal engine
complication (Knothe et al, 2005; Gupta et al, 2007; Shahid and Jamal,
2011). Biodiesel is found to be the best substitute for petro-diesel, not
only because of its comparable calorific value but also for its several
other advantages such as: low toxic emissions, biodegradability, high
flash point, excellent lubricity and environmental compatibility (Balat
and Balat, 2010; Knothe et al, 2005). Biodiesel has been promoted and
reported as a promising long term renewable energy source which has
the potential to address net emission of carbon dioxide (CO2) to the
atmosphere, security concerns and the fluctuating prices of fossil fuels
(Alamu et al., 2007a, 2007b ; Balat and Balat, 2010). Triglycerides used
for the production of biodiesel come from various sources: edible oils,
non-edible oils, waste/used oils, animal fats and from microorganisms
(Meng, et al; 2009). However, there is an economic sense in the use of
waste oil feedstocks such as recovered oil from SBE or PK. Bleaching
earth is used in vegetable oil refinery to remove colouring matters, soap,
gums, metal (iron, nickel), oxidized compounds and polymers.
Bleaching earth retains 20 – 40 % of oils and importantly, the adsorbed
oil represents a considerable part of the bleached oil (Ong, 1983;
Nursulihatimarsyila et al., 2010). It is estimated that about 600,000
metric tons or more of bleaching earth are utilized worldwide in the
refining process based on the worldwide production of more than 60
million tons of oils (Kaimal et al., 2002). SBE is usually disposed as
waste by dumping in landfills without any attempts to recover the oil. Its
disposal by incineration, inclusion in animal feeds and concrete
manufacturing are sometimes practiced. Overall, SBE due to the
substantial oil content in the earth, poses a serious threat to the
environment by causing fire and releasing pollution hazards. Hence, it
has been suggested that the oil in SBE be recovered and re-used as an
alternative energy source which could also reduce the cost associated
with refining processes (Nursulihatimarsyila et al., 2010). Palm kernel
oil (PKO) in its fresh form or recoverd from SBE can be used as
biodiesel. Various studies have been carried out on the conversion of
PKO and oil recovered from SBE to biodiesel using conventional
homogenous catalysts (i.e. sodium hydroxide or potassium hydroxide) or
heterogeneous catalysts e.g. calcium oxide through the trans-
esterification reaction (Alamu et al., 2007a; Boey et al., 2009; Huang
and Chang, 2010). In the present work, we report the use of cocoa pod
ash (CPA) as catalyst in the trans-esterification of PKO and oil
recovered from SBE to obtain biodiesel.

2. Materials and methods

2.1. Materials

The two types of oil used included oil recovered from SBE and neat
PKO. The SBE was obtained from Unilever Nigeria Plc., Agbara, Ogun
State, Nigeria while the palm kernel seeds used were purchased from the
Ajebamidele market at Odo-Oro Ekiti in Ikole local government area,
Ekiti State, Nigeria. All solvents including n-hexane, methanol and
ethanol were of analytical grade and purchased from Sigma Aldrich
(England). The KOH catalyst used for the conversion of the oils to
biodiesel was a commercial product obtained from BDH Chemical
Limited, Poole, England. Cocoa pod was sourced for in a local cocoa
farm at Odo-Oro Ekiti, Ekiti State, Nigeria and was subsequently
converted to CPA.
2.2. Methods
2.2.1. Cocoa pod ash (CPA) preparation
The cocoa pods were washed with distilled water, air dried and burnt.
The burnt cocoa pods were converted into ash in a muffle furnace at a
temperature of 550oC for 50 min. The ash obtained was sieved to obtain
a fine powder. The ash was analysed for its mineral content using an
atomic absorption
spectrometer (AAS) at International Institute of Tropical Agriculture
(IITA) laboratory, Ibadan, Nigeria.
2.2.2. Oil extraction

The oil was recovered from the bleaching earth by cold-extraction with
nhexane solvent. One kg of fresh SBE was extracted with 2 L of n-
hexane in a 4-L extracting jar, i.e. 2 L of n-hexane was poured into a 4-L
jar containing 1kg of fresh SBE. The jar was covered and allowed to
stay at room condition for a period of 72 h. After which the resulting
solution was decanted off the jar and filtered using Whatman filter
paper. The filtrate (oil + n-hexane) was then concentrated by distillation
with the aid of a vacuum pump at room temperature to recover the SBE
oil. 160 g of oil was recovered from the 1kg SBE giving an oil yield of
16%. Fresh n-hexane solvent was used for the extraction. The solvent
recovered could be re-used, but in this work it was not re-used since the
extraction was a one-batch experiment. In the same way, dried PK was
mechanically ground to fine granules. Then, 1.2 kg of the ground sample
was cold-extracted with 2 L of n- hexane for 3 d; this was then filtered
and concentrated in-vacuo to give 482.67 g palm PKO i.e. 40.23 %
extraction yield.
2.2.3. Determination of total alkali in the ash

Determination of the total alkali in the CPA was achieved by titration

with acid solution. 0.1M HCl acid solution was firstly standardized
using 0.1M Na2CO3. The standardized 0.1M HCl acid solution was also
titrated against 0.1M KOH as a reference basic solution. The
standardized 0.1M HCl acid solution was then titrated against the CPA
solution. Hence, the molar concentration of equivalent alkali in the CPA
which corresponds to that of 0.5 g potassium hydroxide (KOH) used for
the conversion catalyst was determined by stoichiometry. 2.2.4.
Transesterification procedure

The method described by Alamu et al. (2007a) was adopted with some
modifications. Fifty g of the oil recovered from SBE was heated for 20
min at 45oC in a 100 ml, two-neck quick-fit round bottom flask on a
water bath. Then, 0.5 g KOH, dissolved in 14 mL methanol was added
through the second neck to the heated oil. The reaction mixture (oil-
methanol ratio of 5.62:1 mol/mol (5:1 w/v)), was refluxed and stirred at
100oC for 2 h. Preliminary experiments indicated poor yields at lower
temperatures (especially below 60°C)(data not shown). Therefore, trans-
esterification was carried out under reflux at 100 °C that was higher than
methanol boiling point. The reaction product was transferred into a
separating funnel and allowed to stand for 12 h. After glycerol
separation, the obtained FAMEs were washed three times with water and
then dried over anhydrous MgSO4. While using CPA as catalyst, 1.09 g
of CPA (equivalent amount of alkali) was leached in 14 mL of methanol,
filtered with Whatman filter paper and also added through the second
neck of the flask to the heated oil to produce biodiesel from SBE as
described above. Similarly, the same procedure was followed as of PKO.
The experiments were carried out in triplicates and the average methyl
ester yield was determined. Biodiesel yield was estimated using the
following equation (Eq. 1):

Y = Vp/Vs × 100 Eq. 1

Where, Y is the yield (%), Vp represents the volume of product obtained

(ml) and Vs is the volume of starting material (ml).
2.2.5. Biodiesel fuel characterization

The fuel-related properties of the extracted oil from the SBE, PKO and
their corresponding biodiesel products, obtained with KOH and CPA
catalysts, were determined according to ASTM standard methods.
Comparisons were also made considering the European biodiesel
standard EN14214, commercial petroleum diesel, and the ASTM
specification for pure biodiesel (B100). The viscosity and specific
gravity measurements were made using the Ostwald viscometer
thermostatted at 40oC and thermal-Hydrometer apparatus following the
ASTM standards D445 and D1298, respectively. All