PREPARATION AND CHARACTERIZATION STUDY ON

TRANSESTERIFICATION OF WASTE BLEACHED OIL

DERIVED FROM SPENT BLEACHING EARTH (SBE) FOR
BIODIESEL PRODUCTION USING SBE SUPPORTED CATALYST

Name: Thivya a/p Keasavan

Supervisor: Dr. Wan Abdullah binti Wan Abdullah
Co-supervisor: Dr. Nur Farhana binti Jaafar
 Outlines

Problem
Introduction Objectives Methodologies
Statement

S E
Results & List of
Conclusion publications Acknowledgement
Discussion
&
conferences
 INTRODUCTIO
N
greater biodegradability, biodiesel produces fewer
higher combustion NOx gases and emissions
efficiency, and lower sulfur less
and aromatic content
1 2

Biodiesel

less toxic and easy to store helps to reduce pollution

4 3 and may reduce the effects
of global warming
 What is transesterification?
01
To reduce oil viscosity and prevent serious
03
damage to the biodiesel, vegetable oils and
animal fats must undergo transesterification
Transesterification is a process where
triglycerides will be converted into fatty
acid methyl ester (FAME) in the presence
of methanol or ethanol and a catalyst ( acid
or base) with glycerol as a by-product
Triglycerides
02 • could be transformed to biodiesel by
transesterification, pyrolysis (thermal
cracking), dilution and micro-
emulsification
SPENT BLEACHING EARTH

1
type of industrial waste created by
the bleaching of crude oil in the
vegetable oil refining sector
2
SBE consist of MgO which has
potential to act as catalyst in
biodiesel production
3
SBE produced high percentage of
oil ( 20- 40%) and it can also help
to reduce the cost of biodiesel
production
 Problem Statement

01 02 03 04
Due to dwindling SBE is a type of Heterogeneous base Large amount of
fossil fuel reserves waste from catalysts can’t be wastewater is
and growing air industries where recovered and generated during the
pollution caused by there has a problem reused. production of
the continued use of in managing and biodiesel, hence cause
petroleum-based disposing of the environmental
fuels, many waste problem
countries have
stimulated research
into the use of
renewable biofuels
OBJECTIVES

To synthesize the SBE-supported catalysts for the

transesterification of bleach oil.
.

To study the optimum condition for oil extraction and

optimize the performance of catalysts in transesterification
reaction under hydrothermal condition.

To characterize the physicochemical properties of

the potential catalyst using several characterization
techniques.

To study reaction kinetics and thermodynamics of

transesterification of bleached oil derived from SBE.
 Methodologies

Extraction of oil from SBE Synthesis of SBE/KOH 500

catalyst

20 g SBE
8 g of cal SBE
SBE: n-hexane 8 g of KOH
(1:4 mol ratio) 100 ml water

Dried at 65 ℃ Reflux using n-hexane Dried at 60 ℃ Calcined at 600 ℃

for 24 hr at 65 ℃ for 6 hr for overnight for 2 hr

Bleached oil Rotavapor at 40 ℃ Calcined at 500 ℃ Dried at 70 ℃ Reflux at 65 ℃

at 80 rpm for 2 hr for overnight for 3 hr

Soxhlet extraction method Wet impregnation method

 Methodologies

Transesterification of oil into biodiesel

5 g of bleached oil
1 wt.% catalyst Optimization condition
(SBE/KOH 600)
Oil: methanol
(1:16 mol ratio)
Hydrothermal reaction Centrifuged at
(80 ℃ for 2 hr) 3500 rpm for Upper layer: Biodiesel
15 min

Hydrothermal method

Biodiesel
 Methodologies

Evaluation on
Verification method
SBE/KOH 600 catalyst for biodiesel
Characterization of production
catalysts, oil, and
Kinetic and biodiesel
thermodynamic
Catalyst reusability studies
study S T EP 4
S T EP 3
S T EP 2
S T EP 1
Results & Discussion

Optimization condition for

extraction of bleached oil

Parameters Biodiesel yield, %

Mass of SBE increases
(20 g → 30 g → 40 g)
Molar ratio of SBE to solvent Optimum condition
(SBE:n-hexane) mass of SBE = 40decreases
g
molar ratio = 1:4
(1:4 → 1:5 → 1:6) time = 6 hr
Reaction time increases
(4 hr → 5 hr → 6 hr)
Results & Discussion
Optimization study for
transesterification reaction

Parameters Biodiesel yield, %

Type of catalysts increases
(SBE → SBE NaOH → SBE KOH)
Calcination temperature of the catalyst, ℃ increases decreases
(500 → 600 → 700) Optimum condition
calcination temperature = 600 ℃
Molar ratio of oil to MeOH molar ratio = 1:20increases decreases
(1:16 → 1:18 → 1:20 → 1:22) catalyst loading = 2 wt.%
time = 2 hr
Catalyst loading, wt.% temperature = 80 ℃ increases decreases
(1 → 2 → 3 → 4)
Reaction time, hr increases decreases
(1 → 2 → 3)
Reaction temperature, ℃ increases decreases
(60 → 80 → 100 → 120 → 140)
Characterization of
catalysts
Fourier-transform infrared (FTIR)
SBE 600

Wavenumber Functional groups

(cm-1)
2953 Stretching vib, CH3
2845 Stretching vib, CH2
1656 Stretching vib Si=O
1038 Si-O-Si
468 Si-O

SBE/KOH 500, SBE/KOH 600, SBE/KOH 700

Wavenumber Functional groups

(cm-1)
3550 Stretching vib, Si-O-H
1656 Stretching vib Si=O
468 Si-O
 X-ray Fluorescence (XRF)

Elemental C O Na Mg Al Si Ca Fe K
compositions
SBE 600 25.0 46.7 0.02 0.86 2.58 10.2 5.68 4.45 1.04 • K is higher in SBE/KOH 600 catalyst
SBE/KOH 600 2.79 46.8 0.17 2.40 5.38 17.0 4.24 6.39 11.7

Oxide C O2 Na2O MgO Al2O3 SiO2 CaO Fe2O3 K2O

• K2O in SBE/KOH 600 catalyst is compositions
higher due to its higher basic strength SBE 600 27.8 19.7 0.03 1.46 4.99 22.4 8.15 6.64 1.30
• the catalytic performance is higher in
SBE/KOH 600 SBE/KOH 600 - - 0.25 4.42 11.5 41.9 7.38 11.6 17.1
 Thermogravimetric SBE/KOH catalyst
1
Analysis (TGA) b) 100
0

98

Derivative weight, %
−1 Derivative weight
Weight

Weight, %
96
−2

94
−3
SBE catalyst SBE/NaOH catalyst
1 −4 92
2
a) 100
0 c) 100
−5 90 0
−1
−2 98
Derivative weight, %

Derivative weight
95 200 400 600 800

Derivative weight, %
−2 Weight Temperature, °C −4

Weight, %
96
Derivative weight

Weight, %
−3
90 −6 Weight
94
−4
−8

−5 85 92
−10

−6 −12 90
80
−7 −14
88
200 400 600 800 −16
Temperature, °C 200 400 600 800
Temperature, °C
 Field Emission Scanning Electron Microscopy- Energy
Dispersive X-ray (FESEM/EDX) analysis

SEM images (SBE/KOH 500) SEM images (SBE/KOH 700)

SEM images (SBE/KOH 600) SEM images (Reuse SBE/KOH 600)

Elemental composition by EDX analysis

C O Na Mg Al Si Ca Fe K

SBE/KOH 500 24.29 42.65 0.12 1.63 2.88 7.38 4.82 0.58 5.03

SBE/KOH 600 7.99 40.22 0.04 1.80 3.28 8.84 14.83 17.98 15.65

SBE/KOH 700 10.82 45.19 0.22 2.30 5.89 15.57 1.67 13.70 7.31

Reuse 14.67 28.69 1.82 0.94 2.86 2.28 4.81 12.35 11.04
SBE/KOH 600

• K element higher in SBE/KOH 600

• K reduces when reuse SBE/KOH 600 was used
• only a small amount of K leach out during initial stage of the reaction
 Temperature Programmed Desorption- NH3
(TPD-NH3)

0.14 Weak acid sites Moderate acid Strong acid

sites sites Catalyst Amount of acidity (mmol/g) Total acidity
0.12 at each region (mmol/g)
0.10 Weak Moderate Strong
TCD signal (a.u.)

SBE 600
0.08 SBE/KOH 500 SBE 600 97.46 107.95 355.27 560.68
SBE/KOH 600

0.06
SBE/KOH 700
SBE/KOH 500 53.71 20.01 1141.07 1214.79

0.04
SBE/KOH 600 0.75 111.38 238.08 350.21
SBE/KOH 700 10.30 118.35 45.13 173.78
0.02

0.00

−0.02
0 200 400 600 800 1000

Temperature (°C)
 Temperature Programmed Desorption- CO2
(TPD-CO2)

0.12 Weak basic sites Moderate basic Strong basic

Catalyst Amount of basicity (mmol/g) Total basicity
sites sites at each region (mmol/g)
0.10
Weak Moderate Strong
TCD Signal (a.u.)

0.08 SBE 600 SBE 600 0.12 0.24 4.04 4.40

SBE/KOH 500
SBE/KOH 600
SBE/KOH 700 SBE/KOH 500 0.12 0.15 7.18 7.45
0.06
SBE/KOH 600 0.05 0.37 1.15 1.57
0.04
SBE/KOH 700 0.22 1.40 3.44 5.06
0.02

lower basicity of SBE/KOH 600 was probably

0.00
caused by higher concentrations of Fe and Ca.
0 200 400 600 800 1000
Temperature (°C)
 X-ray Diffraction Analysis (XRD)

a) SBE based catalyst

SBE 500 SBE 600

2500
SBE 700 Compound 2θ Compound 2θ
Montmorillonite
SBE 600
SBE 500 Quartz
2000 SiO2 20.85, 26.63, SiO2 20.87, 26.65,
36.82, 39.47 36.07, 39.48
Montmorillonite 29.44 Montmorillonite 29.46
1500
Intensity

1000
SBE 700

Compound 2θ
500 SiO2 20.83, 26.61,
36.51, 39.40

0
10 20 30 40 50 60 70 80 90
2-Theta (degree)
 b) SBE/NaOH based catalyst

3500
SBE/NaOH 700 Quartz SBE/NaOH 500 SBE/NaOH 600
3000 SBE/NaOH 600
SBE/NaOH 500 Na2O
Compound 2θ Compound 2θ
2500 SiO2 20.87, 26.66 SiO2 20.86, 26.65

Na2O 29.46 Na2O 29.45

2000
Intensity

1500
SBE/NaOH 700
1000
Compound 2θ
500 SiO2 20.89, 26.67

0
10 20 30 40 50 60 70 80 90
2-Theta (degree)
 c) SBE/KOH based catalyst

SBE/KOH 500 SBE/KOH 600

SBE/KOH 700 Quartz Compound 2θ Compound 2θ

5000 K 2O
SBE/KOH 600
SBE/KOH 500 Orthoclase SiO2 20.95, 26.73, SiO2 20.85, 26.63,
39.58 39.47
4000
K2O 29.53 K2O 29.45

3000 Orthoclase 27.55 Orthoclase 27.46

Intensity

2000
SBE/KOH 700
1000 Compound 2θ

SiO2 20.89, 26.65,

0 39.50
K2O 29.43
10 20 30 40 50 60 70 80 90
2-Theta (degree)
Brunauer- Emmett- Teller (BET) analysis

Catalysts BET surface area (m2/g) Pore volume (cm3/g) Pore width (nm)

SBE 500 6.02 0.019 11.99

SBE 600 3.77 0.022 21.60
SBE 700 2.88 0.014 15.45
SBE/NaOH 500 11.69 0.070 24.44
SBE/NaOH 600 8.87 0.054 26.27
SBE/NaOH 700 7.90 0.050 28.04
SBE/KOH 500 2.71 0.010 15.69
SBE/KOH 600 22.62 0.098 21.05
SBE/KOH 700 20.15 0.096 14.58
Characterization of oil and
biodiesel
 Fourier Transform Infrared Spectroscopy (FTIR)

180
Biodiesel
160 Bleached oil

Wavenumber (cm-1) Functional groups

140
2912 Stretching vib, CH3
Transmittance, %

120
2849 Stretching vib, CH2
100
1748 Stretching vib C=O
80
1461 C-O
CH3
1375
60
CH2
1375 Bending vib, CH3
C-O
2849 1461
40 CH3 CH2
1154 Bending vib, CH2
C=O
2912 1748 1154

20
4000 3500 3000 2500 2000 1500 1000 500

Wavenumber, cm-1
 Gas Chromatography- Mass Spectrometry
(GC-MS) Analysis

17.37
19.43 17.38
19.45

16.76

16.78
18.56
18.86
20.98
13.98 21.01
26.06 13.99 26.08

Ret time, min Fatty acid composition Ret time, min Fatty acid composition

13.98 Myristic acid 13.99 Methyl myristoleate

16.76 Hexadecanoic acid 16.78 Methyl hexadecanoate
17.37 Heptadecanoic acid 17.38 Methyl heptadecanoate
18.56 Linolenic acid 18.86 Methyl linoleate
19.43 Oleic acid 19.45 Methyl oleate
20.98 Eicosenoic acid 21.01 Methyl eicosenoate
26.06 Squalene 26.08 Squalene
 REUSABILITY TESTING FOR SBC/KOH 600 CATALYST

100

Retest 1 Retest 2 Retest 3

90
• There were not much difference on the repeatability test
80 for the biodiesel sample, indicating the accuracy of the
analysis performed.
Biodiesel yield, %

70 • There was some loss of catalyst in each cycle due to

leaching during the washing stage.
60
• Since the catalytic performance of the SBE/KOH 600
50 catalyst does not significantly change after the first
transesterification reaction, it can be recycled and used
40 again.

30

20
1 2 3 4
Cycles
Kinetic studies

Rate constant of the transesterification process was

determined at various temperatures.
( X FAME )
First order : 1 − X FAME =e
− kt
( selected )¿ Second order : =k [ TG ]0 t
( 1− X FAME )

80 °C
0.66 80 °C
y = -0.0026x + 0.5088 4.0 y = 0.0371x - 0.5196
R2 = 0.9996
R2 = 0.977
0.60
90 °C
y = -0.001x + 0.3935 90 °C
0.54 3.5 y = 0.0103x + 1.3522
R2 = 0.9819

XFAME/ (1- XFAME)

R2 = 0.9884
0.48 100 °C
1- XFAME

y = -0.0007x + 0.4258 100 °C

R2 = 0.9992
3.0 y = 0.0054x + 1.2794
0.42 R2 = 0.9961

0.36
2.5
0.30

0.24 2.0

0.18
1.5
60 70 80 90 100 110 120
60 70 80 90 100 110 120
Time, min
Time, min
The Arrhenius equation was expressed as shown in
equation below −2

−3
k=A
−4 y= 10.83x - 35.37
R2= 0.9433

ln k
−5

−6
The values of activation energy, Ea and pre-exponential
factor, A can determine by plotting graph of ln k against −7
1/T.
−8
2.66 2.68 2.70 2.72 2.74 2.76 2.78 2.80 2.82 2.84
Ea = - 90.06 kJ mol-1 1000 * 1/T (K-1)
A = 4.37 ×10-16 min-1
Thermodynamic studies

k bT G
−10.0
k= exp(− ) where, G is ΔH-TΔS
h RT
−10.4

k ΔH kb ΔS
ln
T
= - ( RT) + [ ln κ + ln h
+ R
] −10.8
ln (k/T)= -0.0832 (1/T) + 18.775

ln (k/T)
−11.2
A graph of ln (k/T) versus 1/T was plotted
−11.6
ΔH = 6.92 × 10 kJ/mol (endothermic)
-4

ΔS = -0.0414 kJ/mol K −12.0

ΔG = 15.443 kJ/mol (endothermic)
−12.4
350 355 360 365 370 375
1/T (1/K)
 Conclusion

It was found that SBE/KOH 600
catalyst demonstrated the highest
activity at 80 ºC of reaction
temperature, 2 wt.% of catalyst
loading, 1:20 of oil to methanol
molar ratio and 2 hr of reaction time
with 80.26 % of biodiesel production.
The results of the study showed
that all the properties of the
biodiesel produced were within
the ASTM standard limits, with
1.08 mg KOH/g, 0.80 kg/L of
density, -27 ℃ of pour point and
0.75 mm2 /s of kinetic viscosity
The kinetic study on the
production of biodiesel from SBE
oil by KOH-supported SBE-based
catalyst showed that the activation
energy was 90.06 kJ mol-1

In this study, a series of catalysts SBE/KOH 600 catalyst The kinetic model of this
including SBE, SBE doped KOH was stable and can be reaction at different times
and SBE doped NaOH based recycled up to 4 and temperatures
catalysts were successfully successive runs. revealed
synthesized and calcined with that the reaction followed
different calcination temperatures first order kinetics
Lists of Publications Keasavan, T., Loh, S. K., Jaafar, N. F., &
Abdullah, W. N. W. (2023). Synthesis of
Biodiesel from Residual Oil Extracted from Spent
Bleaching Earth using Spent Bleaching Earth-
Supported Catalyst. Chemical Engineering
Research and Design, 200, 716–728

Keasavan, T., Radzi, N.M., Abdullah, Keasavan, T., Khairi, A.D., Rosid, S.J.M.,
W.N.W., Rosid, S.J.M., Shukri, N.M., Yahaya, Shukri, N.M., Abdullah, W.N.W. (2023).
N. (2023). Transesterification of Low-Grade Catalytic Conversion of Coconut Pulp into
Palm Cooking Oil to Biodiesel using Spent Biodiesel through Transesterification using
Bleaching Clay Catalyst. Malaysian Journal Calcium Oxide-Based Catalysts. Malaysian
of Analytical Sciences. Journal of Chemistry, 25 (4), 123-134.
LIST OF PRESENTATIONS
Production of Biodiesel from Low-Grade Cooking
Oil through Transesterification using Spent
Bleaching Earth Waste Supported Catalyst. The
8th International Conference for Young Chemists 01
(ICYC 2022)

Transesterification of the Low-Grade Palm

Cooking Oil to Biodiesel using Spent Bleaching
02 Clay Catalysts. The 35th International Conference
of Analytical Sciences 2023 (SKAM35)

Transforming Industrial Waste for Beneficial

High-Grade Diesel. Poster presented at SIRIM
Invention, Innovation & Technology Expo 2023,
03
SIRIM Kulim, Kedah.

Production Of Euro V Diesel by Descads

Technology. Poster presented at International
04 Innovation, Invention and Creation Exhibition
(IIICE) 2023, Universiti Teknologi MARA.
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 Acknowledgement
Dr. Wan Nazwanie Dr. Nur Farhana Binti
Wan Abdullah Jaafar

This work was supported by

Universiti Sains Malaysia,
Special (Matching) Short-
Term Grant with Project No:
304/PKIMIA/6315704. Dr. Loh Soh Kheang

Thank you