EJERS, European Journal of Engineering Research and Science

Simplified Rate Expression for Palm Kernel Oil (PKO)

and Methanol Alkali Catalyzed Transesterification
Reaction
Okewale A.D, Abowei M.F.N, Agbogun F.O, Owabor C.N

aspect of developing a feasible rate mathematical model that

Abstract—The need for the development of simplified
kinetics rates expression (-RA) for Vegetable Oils Alkali
Catalyzed Transesterification processes to enhance biodiesel
production motivated this study. The study, therefore aimed at
proposing unified simple rate expression that may be a useful
prelude to design various reactor types for Alkali Catalyzed
Transesterification of palm kernel oil (PKO) and Methanol
reactions. The kinetics rate expression is proposed using simple
explicit algebraic technique with the consideration that alkali
catalyzed transesterification reaction of palm kernel oil and
methanol is a reversible bimolecular reaction. The proposed
kinetic reaction rate expression is developed as a function of
conversion (XA), reactants and products concentration and
reaction rate constants (k1 and k2). The kinetics reaction rate
expression obtained is further evaluated on the basis of
reactants and product molar masses and densities. The
developed models were simulated using Matlab codes
programming techniques. The results for kinetic reaction rates
(-RA & -RA) decreases with decrease in fractional volume
change () and increase in fractional conversion at constant
reaction time. The results were quite compatible with those of
inferential laboratory physicochemical characterization
reported.
could be used to design various industrial scale reactor types
seems impassive. Therefore, this work shall appraise
quantitatively and qualitatively the development of feasible
unified disappearance kinetic rate expression for alkali
catalyzed transesterification of palm kernel oil and methanol
reactions in the production of biodiesel. In other to establish
the basis for the development of the unified rate expression,
it is relevant to assess the extent of some previous works
reported on palm kernel oil, methanol and biodiesel
chemistry.
II. CHEMISTRY OF PALM KERNEL OIL, METHANOL AND
BIODIESEL
A. Palm Kernel Oil (PKO)
Palm kernel oil is edible oil obtained from the palm tree
whole physical appearance is presented in Fig. 1. Palm
kernel oil is widely produced in the world and essentially
through extraction processes [1].

Index Terms—Simplified, Kinetic Rate Expression, Alkali

Catalyzed Transesterification, Palm Kernel Oil Methanol
Biodiesel.

I. INTRODUCTION
Researchers [1-4] globally have resolved unequivocally in
tackling the high potential environmental perturbation
problems resulting from utilization of non-renewable energy
sources for industrial and domestic use. These
environmental perturbation problems have led to increased
awareness search for alternative renewable energy sources
such as biogas and bio-fuels production. This renewable
energy sources are expected to elevate global economy and
minimize global environmental problems that were derived
from the conventional fossil fuels [1]. Hence this work
intensified on the development of Biodiesel from alkali
catalyzed transesterification of palm kernel oil and methanol
reaction which has great concern to engineers and scientist.
Actually, a great deal of novel research works [5-12] have
been carried on biodiesel production via alkali catalyzed
transesterification of vegetable oil types and various alcohol
groups reaction, notably in methanol/ and ethanol processes.
Those studies provided information on the chemistry, uses,
reaction mechanisms and kinetics evaluation based on
inferential laboratory data analysis procedures. The
Fig. 1. Palm Kernel Fruit [1-2]
Interestingly PKO is widely used as Biodiesel production,
Cooking and frying oil, Margarines production, Shortenings,
Non-dairy creamers, whipping creams; As cocoa butter
substitute, In manufacture of soaps, Oleochemicals, In
cosmetics, personal care products as skin conditioner,
Viscosity increasing agent and Solvent. In addition, the cake
residue obtained after extracting the oil is used as a feed for
livestock and other medical functions due to its antidotes
capabilities for poisoning and as surface protestant for minor
wounds. Its structure, physical and chemical properties are
presented below;
1) Chemical Structure

Published on May 28, 2020. Fig. 2. Palm Kernel Chemical Structure [1-2]

DOI: http://dx.doi.org/10.24018/ejers.2020.5.5.1901 Vol 5 | Issue 5 | May 2020 599

 EJERS, European Journal of Engineering Research and Science

2) Properties Relative density 0.79 – 0.80 (20oC)

Relative density of saturated
1
TABLE I: PHYSICAL AND CHEMICAL PROPERTIES OF CRUDE PALM KERNEL gas/air mixture
OIL [9-11] Specific gravity / density 790 – 800 kg/m3 (20oC)
Properties Values Molecular mass 32.04g/mol
Solubility Soluble in water: 100g/100ml (20oC)
Density at 40/25oC[kg/m3] 898
Log Pow -0.77 (Experimental value)
Kinematic viscosity at 40oC[mm2/s] 30.1
455Oc (1013 hPa, DIN 51794; Self –
Free fatty acid(lauric) 1.189 Auto-ignition temperature
ignition Temp)
Odour Burnt smell Viscosity, dynamic 0.544 – 0.59 mPa –s (25oC)
Colour Burnt brown Explosion limits 5.5 – 36.5 vol %
Solubility Soluble in non-polar solvent
Iodine value [mm iodine/g oil] 19.3
Saponification value [mm KOH/g oil] 250 C. Biodiesel
Refractive index 1.453
Biodiesels is a chemical species whose production is
Pour point 20oC
Saponification Value (mgKOH/g) 280.5±56.1 drive from renewable energy sources and otherwise called
Acid value (mgKOH/g) 2.7±0.3 methyl esters or transformer oil. Its chemical structure,
Free fatty (FFA) (mgKOH/g) 1.35±0.15 relative chemical and physical properties and uses are
Ester value (mEq/kg) 277.8±56.4 highlighted herein. Biodiesel is used mainly as; Vehicular
Peroxide value (mEq/kg) 14.3±0.8
use and manufacturer acceptance, Railway usage, Cleaning
Iodine value (mgKOH/g) 15.86±4.02
Specific Gravity value (S.G) 0.904 oil spills, Biodiesel in generator, Transformer oil and
Refractive index 1.412o General heating oil. The structure is presented as;
Inorganic materials (%) 1.05% 1) Chemical Structure

B. Methanol
Methanol, also known as methyl alcohol, wood alcohol,
wood naphtha or wood spirits, is a chemical compound with
chemical formula CH3OH. Its uses entail fuel, denaturant for
ethyl alcohol, biodiesel production via transesterification
reaction, solvent for shellac and varnishes, automobile
radiator anti-freeze, denaturing additive to ethyl alcohol and
Denaturing poisons the ethyl alcohol. The structural formula Fig. 4. Biodiesel Structure [2]
of methanol is:
2) Physical and Chemical Properties

TABLE III: PHYSICAL PROPERTIES OF BIODIESEL AND ASTM DIESEL FUEL

[11-12]
Properties Value
Pale Yellow Liquid mild odour
0.871
Colour and Odour 2.99
Fig. 3. Methanol Structure [2] Density at 30°C (kg/m3 or g/gL) 0.875
Viscosity at 40°C 155
Specific gravity (kg/m3 or gm/mL) 06
1) Properties Flash point °C 7.5
Methanol physical properties were extrapolated from Pour point 0.31
Cloud point 15.35
Material Safety data sheet (MSDS) as sited in the reports of
Acid value (mg NaOH/g) 165
Fibow Petroleum & Environmental Engineering Consult on Iodine value 0.02
methanol disposal analysis by Abowei M.F.N. [14] Saponification value (mg NaOH/g) 0.03
Ash content (%) 54.57
TABLE II: PHYSICAL AND CHEMICAL PROPERTIES OF METHANOL [14] Water content (%) 38.6
Properties Values Octane Number >220
Appearance Liquid H. value (MJ/Kg) >200oC
Colour Colourless Autoignition Temperature <2
Characteristic odour Mild Pleasant Vapour Pressure mm Hg Insoluble
Odour
odour Alcohol Volatiles: % by Volume <1
Melting Point -97.8oC Solubility in H2O, % by Volume * Stable and hazardous
Latent Heat of Vaporization 37.43kJ/mol Evaporation Rate Butyl Acetate =1 * Strong Oxidizing agents
Refractive Index 1.32652 Stability and relativity * highly Combustible produces
Heat of Combustion 726.1 kJ/mol CO2 & * CO along with thick
Boiling Point 64.7oC (1013 hPa) smoke
Critical temperature 240oC <1
Critical pressure 79547 hPa
Flash point 9.7oC
Relative evaporation rate 4.1 D. Sodium Hydroxide
Relative evaporation rate 6.3 Sodium hydroxide is one of the most common inorganic
Vapor pressure 128 hPa (20oC)
Vapor Pressure at 50OC 552 hPa bases or alkalis. It is also called caustic soda or lye and it is
Relative vapor density at 20oC 1.1 a white solid ionic compound consisting of sodium cations

DOI: http://dx.doi.org/10.24018/ejers.2020.5.5.1901 Vol 5 | Issue 5 | May 2020 600

 EJERS, European Journal of Engineering Research and Science

Na+ and hydroxide anions OH−. Its structure is simply

Na+OH- and pictorially as presented in Fig. 4 and its uses
encompasses; Alkali Catalyzed Transesterification process,
Chemical pulping, Tissue digestion, Dissolving amphoteric
metals and compounds, Esterification and transesterification
reagent, Food preparation, Cleaning agent, Water treatment
Fig. 6. Glycerol Structure [2]
as pH, regulation, In cement mixes, mortars, concrete,
grouts, Flavonoids, Summer-winter heat storage, paper TABLE V: PHYSICAL AND CHEMICAL PROPERTIES OF GLYCEROL [14]
industry, petroleum industry, textiles industry, manufacture Properties Value
of soaps and detergents and Bayer process of aluminum Formula C3H8O3
Density 1.26 g/cm3
production. Molar mass 92.09382 g/mol
1) Chemical Structure Boiling point 290 OC
IUPAC ID Propane – 1,2,3

III. KINETIC EVALUATION OF PALM KERNEL OIL AND

METHANOL SYNTHESIS
Series of research works have been reported [9] in the
alkali catalyzed triglycerides and alcohol transesterification
Fig. 5. Na+OH Crystal Structure [14] process with respect to reaction kinetics in laboratory scale.
The stoichiometry and kinetics evaluation of this study were
TABLE IV: CHEMICAL AND PHYSICAL PROPERTIES OF NAOH
reported as;
Properties Value
Chemical Formula NaOH A. Stoichiometry of Reaction
Molar mass 39.9971g mol-1
Appearance White, waxy, opaque crystals The stoichiometry of the reaction is presented thus;
Odor Odorless
Density 2.13g/cm3
Melting point 323oC (613oF; 596k)
Viscosity 78 mPa.s
Boiling point 1,388oC (2,530 oF; 1,661K)
418g/L (0oC) 1000g/L (25oC) 3370 g/L
Solubility in Water
(100oC)
Soluble in glycerol negligible in ammonia
Solubility insoluble in ether slowly soluble in
propylene glycol
Solubility in methanol 238 g/L
Solubility in ethanol <<139 g/L And the overall reaction for the transesterification is
Vapor pressure <2.4 kPa (at 20 oC)
Basicity (pKb) -0.56 (NaOH(aq) = Na+ + OH-)
summarized thus;
Magnetic susceptibility (X) -15.8 10-6 cm3/mol (aq.)
Refractive index(nD) 1.3576 𝑘1
Heat Capacity (C) 59.5 J/mol K Triglyceride + 3R`OH ⇌ 3 R`COOR3 + Glycerol (1)
Std Molar entropy (So 298) 64.4 J.mol-1 . K-1 𝑘2
Std enthalpy of formation
-425.8 KJ.mol-1
(fH298)
Gibbs free energy (fGo) -379.7KJ/mol B. Kinetic Evaluation
Similarly, the kinetics describing the reaction mechanism
E. Glycerol is limited and is hypnotically presented as follows;
Glycerol is a simple polyol compound. It is a colorless, 𝑘1
odorless, viscous liquid that is sweet-tasting and non-toxic. 𝑇𝐺 + 𝑅𝑂𝐻 ⇌ 𝐷𝐺 + 𝐸 (2)
The glycerol backbone is found in those lipids known as 𝑘2
glycerides. Due to having antimicrobial and antiviral
properties it is widely used in FDA approved wound and 𝑘3
burn treatments. Other applications include; Food industry, 𝐷𝐺 + 𝑅𝑂𝐻 ⇌ 𝑀𝐺 + 𝐸 (3)
Botanical extracts, Electronic cigarette liquid, Antifreeze, 𝑘4
Chemical intermediate, Vibration damping, Niche uses, 𝑘5
Film industry, Ultrasonic couplant, & Bubble Mixture and 𝑀𝐺 + 𝑅𝑂𝐻 ⇌ 𝐺𝐿 + 𝐸 (4)
Internal combustion fuel. 𝑘6
1) Chemical Structure
The overall reaction was now
The chemical structure of Glycerol is presented as;
𝑘7
𝑇𝐺 + 3𝑅𝑂𝐻 ⇌ 𝐺𝐿 + 3𝐸; (5)
𝑘8

Where TG = glyceride (PKO), ROH = methanol, E =

DOI: http://dx.doi.org/10.24018/ejers.2020.5.5.1901 Vol 5 | Issue 5 | May 2020 601

 EJERS, European Journal of Engineering Research and Science

ethyl ester, DG = diglyceride and MG = monoglyceride. From the reaction stoichiometry as in (14), a unified
The researchers [8-12] in their work proved second-order empirical kinetic rate can be mathematically, thus;
reaction rate constant and arrived at the governing equations
−𝑑𝐶𝐴
characterizing the stepwise reactions for transesterification −𝑅𝐴 = = 𝐾1 𝐶𝐴 𝐶𝐵 − 𝐾2 𝐶𝑅 𝐶𝑆 (15)
𝑑𝑡
of triglycerides:
𝑑𝑇𝐺
Where –RA = Disappearance rate, K1 & K2 = reaction rate
= −𝐾1 𝑇𝐺. 𝐴 + 𝐾2 𝐷𝐺. 𝐸 − 𝐾7 𝑇𝐺. 𝐴3 + 𝐾8 𝐺𝐿. 𝐸 3 (6) constants; CA, CB, CR & CS are concentrations of PKO,
𝑑𝑡
NaOH, Glycerol & Methyl Ester respectively.
𝑑𝐷𝐺
= 𝐾1 𝑇𝐺. 𝐴 − 𝐾2 𝐷𝐺. 𝐸 − 𝐾3 𝐷𝐺. 𝐴 + 𝐾4 𝑀𝐺. 𝐸 (7)
𝑑𝑡 C. Simplified Kinetics Rate (-RA) Model
𝑑𝑀𝐺 In-case, for Isothermal situation as typical of reversible
= 𝐾3 𝐷𝐺. 𝐴 − 𝐾4 𝑀𝐺. 𝐸 − 𝐾5 𝑀𝐺. 𝐴 + 𝐾6 𝑀𝐺. 𝐸 (8)
𝑑𝑡 bi-molecular reaction status, noting that;
𝑑𝐺𝐿
= 𝐾5 𝑀𝐺. 𝐴 − 𝐾6 𝐺𝐿. 𝐸 + 𝐾7 𝑇𝐺. 𝐴3 − 𝐾8 𝐺𝐿. 𝐸 3 (9) 𝐶𝐴𝑂 = 𝐶𝐴𝑂 (1 – XA) (16)
𝑑𝑡

𝑑𝐸
= 𝐾1 𝑇𝐺. 𝐴 − 𝐾2 𝐷𝐺. 𝐸 + 𝐾3 𝐷𝐺. 𝐴 − 𝐾4 𝑀𝐺. 𝐸 + 𝐾5 𝑀𝐺. 𝐴 (10) Then, Equations (16) and (15) combined give;
𝑑𝑡

−𝐾6 𝐺𝐿. 𝐸 + 𝐾7 𝑇𝐺. 𝐴3 − 𝐾8 𝐺𝐿. 𝐸 3 (11) −𝑅𝐴 = 𝐾1 (𝐶𝐴𝑂 − 𝐶𝐴𝑂 𝑋𝐴 )(𝐶𝐵𝑂 − 𝐶𝐴𝑂 𝑋𝐴 ) − 𝐾2 (𝐶𝑅𝑂 +
𝐶𝐴𝑂 𝑋𝐴𝑂 )(𝐶𝑆𝑂 + 𝐶𝐴𝑂 𝑋𝐴 ) (17)
𝑑𝐴 𝑑𝐸
=− (12)
𝑑𝑡 𝑑𝑡 Further application of simple factorization techniques to
Where K1 to K8 are reaction rate constants, TG, DG, MG, (17) gives;
GL, A and E are the concentrations in weight percent of 𝐶𝐵𝑂 𝐶𝑅𝑂
−𝑅𝐴 = 𝐾1 [𝐶𝐴𝑂 (1 − 𝑋𝐴 )𝐶𝐴𝑂 ( − 𝑋𝐴 )] − 𝐾2 [𝐶𝐴𝑂 ( +
triglyceride, triglyceride, monoglyceride, glyceride, 𝐶𝐴𝑂 𝐶𝐴𝑂
𝐶𝑆𝑂
methanol and ester respectively. in addition, the kinetic 𝑋𝐴 ) 𝐶𝐴𝑂 ( + 𝑋𝐴 )] (18)
𝐶𝐴𝑂
analysis as presented in (1) to (12) where summarized based
on matrix transformation module as thus; 2 (1 𝐶𝐵𝑂 2 𝐶𝑅𝑂
−𝑅𝐴 = 𝐾1 [𝐶𝐴𝑂 − 𝑋𝐴 ) ( − 𝑋𝐴 )] − 𝐾2 [𝐶𝐴𝑂 ( +
𝐶𝐴𝑂 𝐶𝐴𝑂
𝐶𝑆𝑂
𝑎11 𝑎12 𝑎13 𝑎14 𝑎15 𝑎16 𝑎17 𝑎18
𝐾1 𝐷1 𝑋𝐴 ) ( + 𝑋𝐴 )] (19)
𝐶𝐴𝑂
𝑎21 𝑎22 𝑎23 𝑎24 𝑎25 𝑎26 𝑎27 𝑎28 𝐾 2 𝐷 2

. . . . . . . . . . 2 𝐶𝐵𝑂 𝐶𝑅𝑂
= (13) −𝑅𝐴 = 𝐶𝐴𝑂 {𝐾1 [(1 − 𝑋𝐴 ) ( − 𝑋𝐴 )] − 𝐾2 [( +
. . . . . . . . . . 𝐶𝐴𝑂 𝐶𝐴𝑂
𝑎𝑛8 ] 𝐾7 . 𝐶𝑆𝑂
[𝑎𝑛1 𝑎𝑛2 𝑎𝑛3 𝑎𝑛4 𝑎𝑛5 𝑎𝑛6 𝑎𝑛7 𝑋𝐴 ) ( + 𝑋𝐴 )]} (20)
(𝐾8 ) (𝐷𝑛 ) 𝐶𝐴𝑂

𝐶𝐵𝑂 𝐶 𝐶
From (13) obviously, there is need to develop a feasible Putting 𝑀 = ⁄𝐶 ; 𝑁 = 𝑅𝑂⁄𝐶 and 𝑃 = 𝑆𝑂⁄𝐶
𝐴𝑂 𝐴𝑂 𝐴𝑂
unified kinetic rate equation that can be used for various
into (20) resulting;
industrial reactor types design as this has seem not critical
looked into. 2 {𝐾 [(1
−𝑅𝐴 = 𝐶𝐴𝑂 − 𝑋𝐴 )(𝑀 − 𝑋𝐴 )] − 𝐾2 [(𝑁 + 𝑋𝐴 )(𝑃 +
1
𝑋𝐴 )]} (21)
IV. MATERIALS AND METHODS
1) Reaction time (t) evaluation
A. Materials Also, from (15) and (21); it is possible that;
The Materials exploited in this work encompassed mainly
𝑑𝑋
2 {𝐾 (1
desk top research component such as; Laptop, Mathlab −𝑅𝐴 = 𝐶𝐴𝑂 𝐴 = 𝐶𝐴𝑂 1 − 𝑋𝐴 )(𝑀 − 𝑋𝐴 ) −
𝑑𝑡
software, work spreadsheet and other associated 𝐾2 (𝑁 + 𝑋𝐴 ) (𝑃 + 𝑋𝐴 )} (22)
computational tools for the simulation of the developed
unified kinetic rate models. At equilibrium situation with restrictions that 𝐶𝐴𝑂 = 𝐶𝐵𝑂
𝑑𝐶𝐴𝑂⁄
B. Development of Kinetic Reaction Rate (-RA) and 𝐶𝑁𝑂 = 𝐶𝑃𝑂 = 0; 𝑑𝑡 = 0; Hence from (22) we
Coupled simple algebraic and induction principle establish the fractional conversion of A at equilibrium
technique is exploited in the development of the unified conditions to be;
kinetic rate expression. In this work consideration is based (𝑁+ 𝑋𝐴𝐸 )(𝑃+𝑋𝐴𝐸 )
on the fact that the reaction mechanism as (1) demonstrated 𝐾𝐶 = (1−𝑋𝐴𝐸 )(𝑀+𝑋𝐴𝐸 )
(23)
reversible bi-molecular reaction of second-order
𝐾1
magnitude.[13] Now putting A = PKO, B = NaOH, R = Where 𝐾𝐶 = (24)
𝐾2
Glycerol and S = Methyl Ester; then equation can be
rewritten as; Equation (22) to (24) can re-written as;
𝑘1 1 𝑑𝑋𝐴
= 𝐶𝐴𝑂 [𝐾𝐶 (1 − 𝑋𝐴 )(𝑀 − 𝑋𝐴 ) − (𝑁 + 𝑋𝐴 )(𝑃 + 𝑋𝐴 )] (25)
𝐾2 𝑑𝑡
𝐴 + 3𝐵 ⇌ 𝑅 + 𝑆 (14)
𝑘2
Substituting (23) into (25) gives

DOI: http://dx.doi.org/10.24018/ejers.2020.5.5.1901 Vol 5 | Issue 5 | May 2020 602

 EJERS, European Journal of Engineering Research and Science

1 𝑑𝑋𝐴 (𝑁+𝑋 )(𝑃+𝑋 ) This shows that the reaction is exothermic and the kinetic
= 𝐶𝐴𝑂 [ (1−𝑋 𝐴𝐸)(𝑀+𝑋𝐴𝐸 ) [(1 − 𝑋𝐴 )(𝑀 − 𝑋𝐴 )] −
𝐾2 𝑑𝑡 𝐴𝐸 𝐴𝐸 rate model as developed in (32) and (33) needs to be
(𝑁 + 𝑋𝐴 )(𝑃 + 𝑋𝐴 )] (26) inculcated with the exothermic concept resulting;
𝐶2
Further simplification of (26) gives; 𝐴𝑂
−𝑅𝐴 = (1−0.5𝑋 2
[𝐾1 (1 − 𝑋𝐴 )(𝑀 − 𝑋𝐴 ) − 𝐾2 (𝑁 + 𝑋𝐴 )(𝑃 + 𝑋𝐴 )] (35)
𝐴)
1 𝑑𝑋𝐴 (𝑁+𝑋𝐴𝐸 )(𝑃+𝑋𝐴𝐸)(1−𝑋𝐴 )(𝑀−𝑋𝐴 )−(1−𝑋𝐴𝐸)(𝑀+𝑋𝐴𝐸 )(𝑁+𝑋𝐴 )(𝑃+𝑋𝐴 )
= 𝐶𝐴𝑂 [ ] (27)
𝐾2 𝑑𝑡 (1−𝑋𝐴𝐸)(𝑀+𝑋𝐴𝐸) And,
Equation (27) upon adoption of induction and algebraic 𝑑𝑋𝐴 𝐶 𝐴𝑂 𝑑𝑋𝐴
[𝑘1 (1 − 𝑋𝐴 )(𝑀 − 𝑋𝐴 ) −
= (1−0.5𝑋
manipulations with subsequent integrations resulting to; 𝑑𝑡 𝐴) 𝑑𝑡
𝐾2 (𝑁 + 𝑋𝐴 )(𝑃 + 𝑋𝐴 )] (36)
𝑋𝐴 −(2𝑋𝐴𝐸 −1)𝑋𝐴 1
𝐼𝑛 ( ) = 2𝐾1 ( − 1) 𝐶𝐴𝑂 𝑡 (28) Equation (35) and (36) are the Abowei et al modified rate
𝑋𝐴𝐸 − 𝑋𝐴 𝑋𝐴𝐸
expression for the bimolecular reversible palm kernel oil
And and methanol transesterification reaction in the production
1 𝑋𝐴 − (2𝑋𝐴𝐸 −1)𝑋𝐴 of biodiesel and glycerin. These simplified rate of
𝑡= 1 𝐼𝑛 ( ) (29) disappearance (-RA) and reaction time (t) developed can be
2𝐾1 ( −1)𝐶𝐴𝑂 𝑋𝐴𝐸 − 𝑋𝐴
𝑋𝐴𝐸
used to model all reactor types.
Where XA & CAO = PKO Fractional conversion and
concentration respectively.
V. COMPUTATIONAL METHOD FOR KINETIC RATE
Interestingly, from the reaction stoichiometry as in (1) ANALYSIS
and (14), alkali catalyzed transesteristication of PKO and
methanol reaction shows exothermic and therefore voidage Simulative parameters such as molar mass, concentration
() term can be inculcated into (17) as; of reactant and product species and computational algorithm
are formulated;
𝐶𝐴𝑂 −𝐶𝐴𝑂 𝑋𝐴 𝐶𝐵𝑂 −𝐶𝐴𝑂𝑋𝐴 𝐶𝑅𝑂 +𝐶𝐴𝑂 𝑋𝐴 𝐶𝑆𝑂 +𝐶𝐴𝑂 𝑋𝐴
−𝑅𝐴 = 𝐾1 (
1+𝜀𝐴 𝑋𝐴
)(
1+𝜀𝐴 𝑋𝐴
) − 𝐾2 (
1+𝜀𝐴 𝑋𝐴
)(
1+𝜀𝐴 𝑋𝐴
) (30) A. Molar Mass (MW)
1−𝑋𝐴
Atomic weights of C = 12, 0 = 16 and H = 1; and coupled
Where; 𝐶𝐴 = 𝐶𝐴𝑂 ( ) with stochiometric coefficient are exploited for the
1+𝜀𝐴 𝑋𝐴
Equation (30) is factorized to give; computation of reactant and product species molar masses
using (1) thus;
𝐶2 𝐶𝐵𝑂 𝐶𝑅𝑂 𝐶𝑆𝑂
−𝑅𝐴 = (1+𝜀𝐴𝑂 2 [𝐾1 (1 − 𝑋𝐴 ) ( − 𝑋𝐴 ) − 𝐾2 ( + 𝑋𝐴 ) ( + For A = PKO; B = CH3OH; R = Biodiesel; and S =
𝐴 𝑋𝐴 ) 𝐶𝐴𝑂 𝐶𝐴𝑂 𝐶𝐴𝑂
Glycerol; then
𝑋𝐴 )] (31)
𝑀𝑊𝐴 = (12 𝑋 6) + (16 𝑋 6) + (1 𝑋 14) = 182𝑔/𝑚𝑜𝑙
𝐶𝐵𝑂 𝐶𝑅𝑂 𝐶𝑆𝑂
Again putting 𝑀 = ;𝑁 = ; 𝑃= into (31) 𝑀𝑊𝐵 = (12 𝑋 3) + (16 𝑋 3) + (4 𝑋 3) = 96 𝑔/𝑚𝑜𝑙
𝐶𝐴𝑂 𝐶𝐴𝑂 𝐶𝐴𝑂
(37)
results in; 𝑀𝑊𝑅 = (12 𝑋 6) + (16 𝑋 6) + (18 𝑋 1) = 186 𝑔/𝑚𝑜𝑙
𝐶2
𝑀𝑊𝑆 = (12 𝑋 3) + (16 𝑋 3) + (8 𝑋 1) = 92 𝑔/𝑚𝑜𝑙
−𝑅𝐴 = (1+𝜀𝐴𝑂 2
[𝐾1 (1 − 𝑋𝐴 )(𝑀 − 𝑋𝐴 ) + 𝐾2 (𝑁 + 𝑋𝐴 )(𝑃 + 𝑋𝐴 )] (32)
𝐴 𝑋𝐴 )

B. Concentrations CAO, CBO, CRO & CSO

Conversely the reaction time for transesterification
process can be calculated as; Applying dimensional analysis approach, concentration is
computed as;
2
𝑑𝑋𝐴 𝐶𝐴𝑂
−𝑅𝐴 = 𝐶𝐴𝑂 = [𝑘 (1 − 𝑋𝐴 )(𝑀 − 𝑋𝐴 ) 𝐷𝑒𝑛𝑠𝑖𝑡𝑦
𝑑𝑡 (1 + 𝐴 𝑋𝐴 )2 1 𝐶𝑜𝑛𝑐 = 𝑀𝑜𝑙𝑠 ⁄𝑉𝑜𝑙𝑢𝑚𝑒 = (38)
𝑀𝑜𝑙𝑎𝑟 𝑀𝑎𝑠𝑠
− 𝐾2 (𝑁 + 𝑋𝐴 )(𝑃 + 𝑋𝐴 )]

𝑑𝑋𝐴 𝐶𝐴𝑂
And from Table I to V; 𝜌𝐴 ≅ 0.904 𝑔⁄𝑐𝑚3 ; 𝜌𝐵 ≅
= (1+ [𝑘1 (1 − 𝑋𝐴 )(𝑀 − 𝑋𝐴 ) − 𝐾2 (𝑁 + 𝑋𝐴 )(𝑃 + 𝑋𝐴 )] (33)
𝑑𝑡 𝐴 𝑋𝐴 )2 0.8 𝑔⁄𝑐𝑚3 ; 𝜌𝑅 ≅ 0.875 𝑔⁄𝑐𝑚3 ; 𝜌𝑆 ≅ 1.263 𝑔⁄𝑐𝑚3
Hence substituting these parameters and those in (37) into
Equation (32) and (33) are the Abowei et al modified rate (38) gives;
expression for the bimolecular reversible palm kernel oil
and methanol transesterification reaction in the production 𝐶𝐴𝑂 = 0.904⁄182 = 0.00496 𝑚𝑜𝑙𝑠 ⁄𝑐𝑚3
of biodiesel and glycerin.
𝐶𝐵𝑂 = 0.800⁄96 = 0.00822 𝑚𝑜𝑙𝑠 ⁄𝑐𝑚3 (39)
Now considering the coefficients of the transesterification
reaction as in (1), thus; 𝐶𝑅𝑂 = 0.875⁄186 = 0.00470 𝑚𝑜𝑙𝑠 ⁄𝑐𝑚3
Σ𝑃−Σ𝑅
𝐶𝑆𝑂 = 1.263⁄92 = 0.01372 𝑚𝑜𝑙𝑠 ⁄𝑐𝑚3
𝜀= (34)
ΣR
Conversely, from n (39) it is possible that;
Where Σ𝑃 𝑎𝑛𝑑 Σ𝑅 are coefficients of product and
reactants respectively; then
𝐶𝐵𝑂
Σ𝑅 = 4, Σ𝑃 = 2 and upon substitution into (34) gives; 𝑀= ⁄𝐶 = 0.00822⁄0.00496 ≅ 1.657
𝐴𝑂
𝐶
𝜀=
2−4
= − 1⁄2 𝑁 = 𝑅𝑂⁄𝐶 = 0.00470⁄0.00496 ≅ 0.947 (40)
4 𝐴𝑂

DOI: http://dx.doi.org/10.24018/ejers.2020.5.5.1901 Vol 5 | Issue 5 | May 2020 603

 EJERS, European Journal of Engineering Research and Science

𝐶𝑆𝑂
𝑃= ⁄𝐶 = 0.01372⁄0.00496 ≅ 2.766 results obtained are presented in Table VII:
𝐴𝑂
A. Results
TABLE VI: SUMMARY OF OPERATING PARAMETERS
S/No. Parameter Value Reference TABLE VII: SIMULATED RESULTS OF –RA, RA AND T AS FUNCTION OF
1. K1 1.61 X 10-3 m3/mols.min Ahiekpor etal 2010 FRACTIONAL CONVERSION
2. K2 1.0 X 10-5 m3/mols.min Ahiekpor etal 2020 -RA, mols/m3. RA, Time t, 1 + AXA,  = -
3. CAO 4.96 mols/m3 Calculated XA
min mols/m3.min min 0.5
4. CBO 8.22 mols/m3 Calculated 0.1 0.0548 0.0557 69.87 0.95
5. CRO 4.70 mols/m3 Calculated 0.2 0.0453 0.0461 69.87 0.90
6. CSO 13.74 mols/m3 Calculated 0.3 0.0367 0.0374 69.87 0.85
7. M 1.657 Calculated 0.4 0.0288 0.0297 69.87 0.80
8. N 0.947 Calculated 0.5 0.0218 0.0229 69.87 0.75
9. P 2.766 Calculated 0.6 0.0155 0.0170 69.87 0.70
10.  0.05 Calculated 0.7 0.0100 0.0119 69.87 0.65
0.8 0.0053 0.0077 69.87 0.60
C. Algorithm Formulation 0.9 0.0013 0.0043 69.87 0.55
We herein formulated computational algorithm simulate
the disappearance kinetic rate of reaction exploiting the B. Discussions
developed models in (21), (29) and (32) using the data in
1) Effect of Fractional Conversion on Reaction Kinetic
tale six for isothermal and non-isothermal conditions. The
Rates
summarized algorithm outline flow chart computation
model is given in Fig. 8. Graphical relationship is established to ascertain the
Flow Chart of Programme for Isothermal –RA, Non- effect of fractional conversion (XA) on reaction kinetic rates
Isothermal -RA and t at isothermal and non-isothermal cases. The results
generally depicts dependency relationship of fractional
conversion and reaction kinetic Rate as in Table VI and Fig.
9. The kinetic Rate as in (-RA) is inversely proportional to
the fractional conversion in both isothermal and non-
isothermal cases. This means that at higher fractional
conversion, the kinetic reaction rate (-RA) is very small in
the alkali catalyzed esterification process of PKO and
methanol synthesis.
0,0600

0,0500
(-RA) (-REA)
0,0400
Reaction Rate

0,0300

0,0200

0,0100

0,0000
0 0,2 0,4 0,6 0,8 1
Fractional Conversion (XA)
Fig. 9: Graph of Reaction Rates against Fractional Conversion

The results also show approximately quadratic functional

feature reflecting the analysis of the model in (21) and (32).
Thus, Case I for isothermal condition; (21) is reduced to the
form;

−𝑅𝐴 = 22 [𝐾1 (1 − 𝑋𝐴 )(1.65 − 𝑋𝐴 ) − 𝐾2 (0.947 +

𝑋𝐴 )(2.766 + 𝑋𝐴 )] (41)

And upon the substitution of the K1 and K2 values as in

Table VI into (41) gives;

−𝑅𝐴 = 22 [1.6 𝑋 103 (1 − 𝑋𝐴 )(1.65 − 𝑋𝐴 ) −

1 𝑋 10−5 (0.947 + 𝑋𝐴 )(2.766 + 𝑋𝐴 )] (42)
Fig. 8. Summarized Algorithm outline Flow Chart Computational Model.
Case II for non-isothermal condition: thus;

VI. RESULTS AND DISCUSSION 2

𝐶𝐴𝑂
−𝑅𝜀𝐴 = [𝐾1 (1 − 𝑋𝐴 )(1.65 − 𝑋𝐴 ) − 𝐾2 (0.947 +
The formulated kinetic disappearance rate models were 1+𝜀𝐴 𝑋𝐴

simulated using Matlab codes programming techniques and 𝑋𝐴 )(2.766 + 𝑋𝐴 )] (43)

DOI: http://dx.doi.org/10.24018/ejers.2020.5.5.1901 Vol 5 | Issue 5 | May 2020 604

 EJERS, European Journal of Engineering Research and Science

Conversely with the introduction of the K1, K2 &  = -0.5 80

Values into (43) resulting to; 70
60

Reaction time, min.

22 50
−𝑅𝜀𝐴 = [𝐾1 (1 − 𝑋𝐴 )(1.65 − 𝑋𝐴 ) − 𝐾2 (0.947 +
1−0.5𝑋𝐴
40
𝑋𝐴 )(2.766 + 𝑋𝐴 )] (44)
30 -RA
20
2) Fractional Conversion & Reaction Time Effect 10
Fractional conversion XA and reaction time (t) at 0
equilibrium condition was studied and presented in Fig. 10. 0,0010,0090,0180,0260,0340,042 0,05 0,0580,066
The result shows linear independent relation with fractional Kinetic reaction Rate mol/m3.min
conversion. Reaction time (t) exhibited same uniformity as Fig. 11. Kinetic rate versus reaction
conversion increases.
4) Fractional Volume change Versus Conversion
80 Alkali catalyzed transesterification of PKO and methanol
reaction process demonstrated exothermic status with
60
fractional volume change or voidage  = -0.5 as in (34).
reaction time t, min

Fractional volume change increases with decrease in

40
fractional conversion as show in Fig. 12.
20

0
0,1 0,2 0,3Conversion
0,4 0,5XA0,6 0,7 0,8 0,9
Fig. 10. Fractional Conversion versus Reaction time effect

In other words, kinetic reaction time (t) is independent of

fractional conversion in the alkali catalyzed
transesterification of PKO and methanol reaction process.
This relationship is authenticated with the analysis of (29)
recalling. Thus;

1 𝑋𝐴 − (2𝑋𝐴𝐸 −1)𝑋𝐴
𝑡= 1 𝐼𝑛 ( ) (29) Fig. 12. Fractional volume change versus Fractional Conversion
2𝐾1 ( −1)𝐶𝐴𝑂 𝑋𝐴𝐸 − 𝑋𝐴
𝑋𝐴𝜀
Interestingly, fractional volume change (1+ n XA)
Now putting XA = 0 as with restrictions that CAO = CBO decreases with decrease in kinetic reaction rate (-RA) for
and CRO = CSO; then; both isothermal and non-isothermal conditions but increase
in fractional conversion XA.
𝑡=
1
𝐼𝑛(−2) This observation is very feasible as presented in Table
−2𝐾1 𝐶𝐴𝑂 VII as well.
1 1
𝑡= 𝐼𝑛 ( ) (45)
−2𝐾1 𝐶𝐴𝑂 2
0.346
𝑡= , 𝑚𝑖𝑛 VII. CONCLUSION AND RECOMMENDATION
𝐾1 𝐶𝐴𝑂

Generally, the results of simulation obtained for kinetic

Upon further substitution of the parameters K1 and CAO
values gives t = 69.87 70min.
3) Kinetic Reaction Rates versus and Reaction Time
Kinetic rates and time show linear independency as in
Fig. 11. Kinetic reactions rates at both isothermal and non-
isothermal conditions show decrease with increase in
fractional conversion at constant reaction time frame. This
analysis is also well depicted in Table VI.
reaction rate for both isothermal equilibrium and non-
isothermal conditions demonstrated dependable
functionality with reaction time, fractional volumetric
change voidage () and fractional conversion (XA). Results
for kinetic reaction rates (-RA & -RA) decreases with
decrease in fractional volume change () and increase in
fractional conversion at constant reaction time. The results
obtained were obvious and comparable with similar works,
demonstrating at least the novel realities of the formulated
models. Therefore, the models can be exploited for the
design of hypothetical reactor types for alkali
transesterification of PKO and methanol reaction process in
the production of biodiesel (transformer oil).

DOI: http://dx.doi.org/10.24018/ejers.2020.5.5.1901 Vol 5 | Issue 5 | May 2020 605

 EJERS, European Journal of Engineering Research and Science

NOMENCLATURE [10] Ahiekpor, J. C and Kuwornoo, D.K (2010): Kinetics of Palm Kernel
Oil and Ethanol Transesterification International Journal of energy
Symbol Description Unit and Environment vol.1 issue 6, pp1097 – 1108.
PKO Palm Kernel Oil N/A [11] Igbokwe, J and Nwafor M. (2014): Synthesis and Characterization of
TG Glycerol N/A biodiesel from Nigeria Palm Kernel Oil: American Journal of
MG Monoglyceride N/A Engineering Research: 3(3) pp264 – 266
E ethyl ester N/A [12] Igbum O.G; Asemave K and Ocheme, P.C (2012) “Evaluation of
DG Diglyceride N/A Biodiesel Potential in Palm Kernel Oil” International Journal of
K1,K2,K3,K4 2nd Order Reaction Rate Vol/mols.m Natural Products Research (3) 57 – 60.
na11 – an8 Matrix Components N/A [13] Levenspiel Octave (2006): Chemical Reaction Engineering; John
A PKO N/A Wiley & Sons (Asia) Pte. Ltd., Singapore.
B NaOH N/A [14] Abowei M.F.N (2009): Modeling for Disposal of 1000gallons of
R Glycerol N/A Spent Acid/methanol Waste Type: Dowell Schlumberger Nigeria
S Methyl ester N/A Limited. Data source.
CAO Concentration mols/m3
CBO Concentration mols/m3 Professor M.F.N Abowei (MNSE, MAMS France,
CRO Concentration mols/m3 FRHD, FIIA, FNSE, FIMC, FIOGRHS) was born 1st
CSO Concentration mols/m3 December, 1959, M.Tech (1986) Chemical/
XA Fractional Conversion N/A Petrochemical Engineering Rivers State University of
-RA, RA Kinetic Reaction Rate mols/m3.min Science and Technology Port Harcourt His thirst for
M,N&P Constants N/A excellence and personal development led him to
KC Equilibrium Constant N/A pursue a Ph.D degree in Chemical Engineering in the
 Fractional volume Change N/A famous and renowned University of Lagos (1991)
XAE Equilibrium conversion N/A
NWA, NWB, NWR NWS Molar Mass Mols/g
Dr. Okewale A.D (Ph.D, CREN) was born 26
March 1982 Tech., M. Eng., Ph.D at Nnamdi
Azikiwe University, Awka, in the Department of
REFERENCES Chemical Engineering and currently Head of
[1] Tollefson, J. (2018): Can the World Kick its Fossil Fuel Addiction Department At Federal University of Petroleum
fast enough? Nat. 2018 5567702 Resources Effurun, Warri, Delta State.
[2] Balasubriamanian, N and Steward, K.F (2019): Subbstantia: An
International Journal of the History of Chemistry 3 (2) Suppl, 1, pp57-
71.
[3] Olatunji, O M; Akor A.J Abowei M.F.N and Akintayo, C.O (2011):
Transesterification for the Preparation of Biodiesel from Crude Oil of Dr. Owabor C.N (Ph.D, CREN) was born 6
Milk Bush: Research Journal of Environmental and Earth Sciences December 1969 B.Sc, (1990) & M.Engr.(1995),
Vol.3 Issue 4, pp 350 – 357. Biochemistry University of Benin Edo State, Ph.D
[4] Olatunji M.O, A.J Akor and Abowei M.F.N (2012): Modelling the (2008) at University of Lagos in the Department of
Chemical Kinetic of Milk bush (The vetia Peruviana) Oil Chemical Engineering and currently Dean of Faculty
Transesterification process for Biodiesel production Continental J. of Engineering At Federal University of Petroleum
Eng. Science 7, pp 40-48 Resources Effurun, Warri, Delta State
[5] Encinar, J.M; Pardal, A; Sanchez, N & Nogales, S. (2018): Biodiesel
by Transesterification of Repressed Oil using Ultrasound: A Kinetic
Study of Based – Catalyzed Reactions Energies, II, 22229, pp 1-13.
[6] Leevijit, T; Wisutmethangoon, W; Prateepchaikul, G; Tongurai, C Agbogun F.O. was born 15 April 1997
and Allen M. (2006): Design and Test of a Continuous reactor for undergraduate Research Student in the Department of
Palm Oil Transesterification. Journal Sci. Technol vol. 8 No.4 pp 791- Chemical Engineering, Federal University of
802. Petroleum Resources, Effurun, Warri, Delta State.
[7] Ved, K and Padam, K. (2013): Study of Physical and chemical
Properties of Biodiesel from Sorghum Oil: Research Journal of
chemical Sciences, vol 3(9) pp 64-68.
[8] Anusi, M.O; Umenweke, G.C; Nkuzinna, O; Igboko, N and Njoku
C.N (2018): Kinetics of Alkali Catalyzed Transesterification Reaction
of Palm Kernel Oil and Physicochemical Characterization of the
Biodiesel Product: American Journal of Engineering Research
(AJER) vol. 7. Issue 2 pp 73 – 82.
[9] Amira, P; Babalola, O.O and Oyediran, A.M (2014): Physiochemical
Properties of Palm Kernel Oil; Current Research Journal of Biological
Sciences 6(5); 205 – 207.

DOI: http://dx.doi.org/10.24018/ejers.2020.5.5.1901 Vol 5 | Issue 5 | May 2020 606