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Production of FAME using Characterized KNO3/OPKS Heterogeneous Catalyst

Mimi Fazzlinda Mohsin1, Nur Asyida Mohd Asyrul1, Muhammad Arif Afif Amran1,Noraini Razali1
1

Faculty of Chemical Engineering


University Teknologi MARA (Terengganu) Bukit Besi Campus, 23000 Bukit Besi, Dungun,
Terengganu

ABSTRACT
Activated carbon or also known as activated charcoal is a form of carbon processed to have small low-volume
pores that increase the surface area available for adsorption or chemical reaction. The primary raw material used
of activated carbon is any organic material with high carbon content such as coal, peat, coconut shell, wood and
palm kernel shell. Nowadays, the availability of palm kernel shell from palm oil industry has gain more
attention. These renewable agricultural wastes are cost effectives alternatives. Therefore, development of
activated carbon as catalyst support has been studied. Oil palm kernel shell supported by potassium nitrate,
KNO3 was developed through impregnation method to be used as heterogeneous solid catalyst. The catalysts
were prepared in different factor such as different temperature (400C, 500C, 600C), metal loading (5%, 10%,
15%), time (3 hour, 4 hour, 5 hour) and concentration (0.5 M, 1.0 M, 1.5 M). The developed catalysts were
characterized using chemisorption and thermogravimetric analysis (TGA). Based on the chemisorption analysis,
comparison of surface area between calcination temperature and metal loading are been obtained. The results
showed the greatest surface area of catalyst is at temperature 500C on calcination temperature and at 15% metal
loading on calcination metal loading. While based on TGA, the characterization of catalyst between calcination
concentration and time. The results showed the better developing catalyst at concentration 1.5M on calcination
concentration and at 6 hour on calcination time. Then, sample of catalyst were used for production of FAME
with ratio oil methanol to oil 12:1 for 4 hour through tranesterification process and were analyzed using GCMS
analysis. The high production of FAME yield are at 12:1 for 97.67% by using a catalyst at 1% as suitable
temperature for 65C based result that has been obtained.

KEYWORDS: Heteregenous Catalyst, Characterization, Potassium Nitrate, activated carbon , Calcination.


INTRODUCTION
There are many energy resources in Malaysia such as oil, natural gas, coal and renewable energies such as
biomass, solar and water. In 2009, 94.5% of electricity is generated by using fossil fuel such as natural gas, coal,
diesel oil and fuel oil. Malaysia stills a net energy exporter until now. In this regard, renewable energy resources are
becoming eye-catching for sustainable energy development in Malaysia because renewable sources of energy are
abundant in Malaysia and the major source is biomass[1]. Investigation of various renewable energy is the
environmental issues related with this energy[2]. The review of current usage of renewable energy sources and also
its potential implementation are evaluated to provide solution for the national [3].One of the renewable energy
sources is biodiesel.

Corresponding Author: Mimi Fazzlinda Mohsin, Nur Asyida Mohd Asyrul, Muhammad Arif Afif Amran,
Faculty of Chemical Engineering, Universiti Teknologi MARA (Terengganu) Bukit
Besi Campus, 23200 Bukit Besi, Dungun, Terengganu, Malaysia, Email: mimi.mohsin@gmail.com,
asyidasyrul94@gmail.com, arifafif423492@yahoo.com.my

Figure 1Malaysia Renewable Energy Consumption


Biodiesel is a clean burning renewable fuel made using natural vegetable oils and fats [4]. Biodiesel is
made through a chemical process which is catalyzed transesterification reaction where the oils or fats will react with
alcohol and produced fatty acid methyl esters (FAME)[5]. In addition, biodiesel is intended to be used as a
replacement for petroleum diesel fuel, or can be blended with petroleum diesel fuel in any proportion as well as it is
biodegradable [6, 7]. Biodiesel also has reduced exhaust emissions and has lower toxicity compared to petroleum
diesel fuel [8]. It is safer to handle compared to petroleum diesel fuel. Hence, to produce biodiesel, the
transesterification process has been used.
Transesterification process involved the reaction of oil or fat with alcohol such as methanol [9]. Methanol
is commonly used in transesterification reaction because it is easy to discover and economic[10]. Methyl esters will
be formed if methanol is used but if ethanol is used, ethyl esters will be formed. Both compounds are biodiesel fuels
but have different chemical combinations. In the chemical reaction alcohol replaces glycerin. Transesterification
reaction can be completed either using homogeneous catalyst or heterogeneous catalyst[5]. The function of catalyst
is to speed up the transesterification reaction. So, most research is interested in developing of catalyst.

Figure 2Transesterification process


The trend of research significant interest in the development of heterogeneous catalyst due to the broad
application of catalyst is being explored in many types of industry areas. The way of catalyst assisting the reaction
either factor or produce a quality product. In modern chemical and petroleum refining industries, new processes lie
on catalytic mechanisms are more than 90% and the massive majority of industrial catalyst are solids[11]. The
increasing rates of chemical reaction by catalysts are significant in industrial development to enable industries to
manufacture their products faster thus reduce the manufacturing costs. Once, many industries used homogeneous
catalyst instead of heterogeneous catalyst until there is problem in homogeneous catalyst[12]. According to [13],the
development of solid catalysts capable to replace the liquid homogeneous catalysts because they are less corrosive,
easier to handle and separate, ecological and producing less amount of toxic wastes. The other application in
industries that used heterogeneous catalysts is performance of CO hydrogenation [14, 15]Therefore, applicable
solution to reduce the problems related with homogeneous catalysts by developing a new solid catalyst[4].

Corresponding Author: Mimi Fazzlinda Mohsin, Nur Asyida Mohd Asyrul, Muhammad Arif Afif Amran,
Faculty of Chemical Engineering, Universiti Teknologi MARA (Terengganu) Bukit
Besi Campus, 23200 Bukit Besi, Dungun, Terengganu, Malaysia, Email: mimi.mohsin@gmail.com,
asyidasyrul94@gmail.com, arifafif423492@yahoo.com.my

Catalysts are divided into two which are homogenous and heterogeneous catalyst. Heterogeneous catalyst
can supply green and recyclable catalytic activities compared to homogenous catalyst [16, 17]. It often involves a
solid catalyst with the reactants as either liquids or gases. Most solid catalysts are metals or the oxides, sulfides, and
halides of metallic elements and of the semi metallic element boron, aluminum, and silicon [17-19]. Besides, solid
catalysts are normally detached in other substances recognized as catalyst support [6]. Utilization of wastes an
alternative material as catalyst supports for heterogeneous catalyst growth[5].
Research interests in the transferring waste to the useful product for production of solid catalyst. There are
many types of biomass resources in the form industrial waste, municipal solid waste, forestry waste and agricultural
waste[20]. One of the agricultural wastes is palm oil which is the main biomass in ASEAN countries. In year 2000,
Malaysia and Indonesia are the two major palm oil productions countries in the world and there were 30 M ton and
8.2 M ton of palm oil wastes (empty fruit brunch, fiber, and palm oil shell) have been generated and spectacular
pace with the quick expanding off food and manufacturing trades are increased[21]. Besides, using wastes as raw
materials for synthesis of catalyst could remove the wastes and at the same time produced the high cost effectiveness
catalyst [5]. This proved that waste is commonly used for production of solid catalyst nowadays. In this study, the
production of solid catalyst will be developing using potassium nitrate and oil palm kernel shell as catalyst support.
This catalyst will be used in biodiesel production.
METHOD AND MATERIALS
Preparation of catalyst support. The oil palm kernel shell (OPKS) used in this study was obtained from Kilang
Kelapa Sawit Risda AMBS. Then, OPKS has been washed to eliminate impurities and dries into oven to remove the
moisture content for 3 hours and at 120C. Then, the OPKS was located on the furnace for carbonize for 3 hours at
600C. Lastly, activated carbon was crushed and sieved to the 1-2 mm of size [5].
Preparation of active catalyst. The impregnation process has been chosen. The support (OPKS) are been
impregnated with aqueous solution of potassium nitrate (KNO 3) compounds. The amount of KNO3 and amount of
water used was calculated according to Appendix A to gain the required amount of transition metal loading in the
calcined catalyst. The mixture was impregnated for 24 h to ensure KNO 3 diffused and detached thoroughly on the
surface of support. The two components are been mixed and stirred under constant heating on hot plate, next it will
dried in oven for 120C for 2 hour until it evaporated and remain as solid. After impregnation, the product through
calcination process to make heterogeneous catalyst. The calcination parameter is different to analyze the catalyst
properties. Table 1 shows the list of parameter used in calcination process in this study.
Table 1 Parameters for calcination process used in this study
Manipulated
Constant
Calcination temperature : 400C, 500C, 600C
4 hour, 1.0M KNO3, 10 wt% metal loading
Metal loading: 5%, 10%, 15%
4 hour, 1.0M KNO3, 500C
Impregnation concentration: 0.5M, 1.0M, 1.5M
4 hour, 500C, 10 wt% metal loading
Calcination time: 4hour, 5hour, 6hour
1.0M KNO3, 500C, 10 wt% metal loading
Preparation of FAME. The catalyst that has been produced is used in the transesterification process. In this
process, methanol will be mix with fresh cooking oil with different ratio methanol to oil. Then transesterification
mixture will be heated for 65C for different reaction time. Next, the excess methanol is distilled off in a rotary
evaporator. The sample then was centrifuged to separate FAME from the mixture. Usually there will be three layers
of the sample in the tube which is catalyst layer at the bottom, by-product (glycerol) in the middle, and FAME at the
upper layer. After that, FAME was separated using dropper and was put in the glass bottles. The sample of FAME is
analysing using GC-MS method. FAME need to be diluted using hexane before it can be analysed by using 5:1 ratio
of hexane to FAME. Table 2 shows the list parameters used for transesterification process in this study.
Corresponding Author: Mimi Fazzlinda Mohsin, Nur Asyida Mohd Asyrul, Muhammad Arif Afif Amran,
Faculty of Chemical Engineering, Universiti Teknologi MARA (Terengganu) Bukit
Besi Campus, 23200 Bukit Besi, Dungun, Terengganu, Malaysia, Email: mimi.mohsin@gmail.com,
asyidasyrul94@gmail.com, arifafif423492@yahoo.com.my

Table 2 Parameters for transesterification process used in this study


Manipulated
Constant
Transesterification time: 4hour, 5hour, 6hour
65 C, catalyst ratio: 1%
Transesterification molar ratio methanol to oil: 6:1, 9:1,
12:1
Product analysis. The catalyst samples were analyzed by chemisorption (Micromeritcs) and Thermogravimetric
analysis. The chemisorption or chemical adsorption analysis techniques offer information required for example
active metal surface area, size of active particles and surface activity of catalytic materials. The helium gas was flow
at 10.09cm3 STP/min to identify the number of peak sample. Thermogravimetric analysis is a technique in which the
mass of a substance is monitored as a function of temperature or time as the sample is subjected to a controlled
temperature ranges in a controlled atmosphere. This simplify as TGA concept is it measures a samples weight as it
is heated or cooled in a furnace. The mass of the sample is monitored during the experiment. This gas may be inert
or reactive gas that flows over the sample and exits through the exhaust.Sample collected from the transesterification
reaction was analyzed using GC-MS analysis method. The purpose of this analysis is to observe the percent yield of
FAME produced from the reaction. GC-MS analysis is an analytical technique for identification and quantization of
a wide variety of volatile and/or semi-volatile organic compounds in a mixture.
RESULTS AND DISCUSSIONS
EFFECT OF CALCINATION TEMPERATURE (MIMI FAZZLINDA MOHSIN)
The catalytic activities on effect of calcination temperature for production KNO3/OPKS catalyst are
obtained using chemisorption (TPD) at different temperatures which are 400C, 500C and 600C has been
determined. Results were obtained in the graph consists of 2 peaks from different temperature. The peak adsorption
of H2 is determined from this graph. In calcination temperature, 2 peaks has been determined at different
temperature which for temperature 400C are 189.5C and 463.9C, for temperature 500C are 205.9C and 481.5C,
and for temperature 600C are 188.7C and 459.8C. To determine the effect calcination temperature of catalyst,
[17]stated different calcination temperature presented different catalytic activity and selectivity under the similar
reaction condition of catalyst that has been obtained.
The area for all the three different calcination temperature was tabulated in Table 3. The corresponding of
the different calcination temperature has been done. According [16], the alteration in catalytic activity equivalent
varied of calcination temperature of the yield. The highest area is 1.19919 was determined at 188.7C on calcination
temperature at 600C but the lowest area is 0.46700 was determined at 481.5C on calcination temperature 500C. It
showed the increasing the area of particle, the higher the potential of active site for absorption of H2 because
catalytic reaction is depends on calcination temperature. So, the sample of catalyst was exposed with zero activity
basically when the sample which calcined at lower temperatures was less active[12].
Figure 3(b) show the smallest area on the graph is 0.46700 was obtained at 481.5C on calcination
temperature 500C. The main reason is the active site cannot hold with high temperature. The pattern on the Figure 3
has been shown. The pore walls of the support cannot resist the growing internal stresses that main of pore failure
and the resulting loss of surface area known as crystallization developments cause the support to crystallize affected
by higher temperature [22]. The temperature exerted is increases, the area of active site is decreases and vice versa.
Hence, the higher of pore size and volume of the catalyst due to calcination temperature decreases. In follow up
study, [12]found the calcination temperature increased, the reduction ability of the catalyst is decreased.
Thus, the best calcination temperature for catalytic reaction at 600C. This is because the area of active site
1.19919 is the highest compared to other calcination temperature at lowest temperature at 188.7C. In addition, the
higher the calcination temperature makes the area of active site of the catalyst become larger on the lower
temperature.
Corresponding Author: Mimi Fazzlinda Mohsin, Nur Asyida Mohd Asyrul, Muhammad Arif Afif Amran,
Faculty of Chemical Engineering, Universiti Teknologi MARA (Terengganu) Bukit
Besi Campus, 23200 Bukit Besi, Dungun, Terengganu, Malaysia, Email: mimi.mohsin@gmail.com,
asyidasyrul94@gmail.com, arifafif423492@yahoo.com.my

Table 3 Different active site at different calcination temperature


Calcination temperature
(C)

Temperature at maximum
(C)
189.5
463.9
205.9
481.5
188.7
459.8

400
500
600

TCD Signal (a.u.) vs. Time

Area

Peak height

1.17822
0.67163
1.12778
0.46700
1.19919
0.61962

0.08404
0.03667
0.06156
0.03129
0.08121
0.03188

TCD Signal (a.u.) vs. Time

TCD Signal (a.u.) - TPD

TCD Signal (a.u.) vs. Time

TCD Signal (a.u.) - TPD

TCD Signal (a.u.) - TPD


0.34

0.32

189.5

188.7

205.9

0.34

0.33

0.31

0.33

0.32

0.32
0.30
0.31

0.30

463.9

TCD Signal (a.u.)

TCD Signal (a.u.)

TCD Signal (a.u.)

0.31

481.5

0.29

0.30

459.8

0.29

0.28

0.29

0.28

0.28
0.27
0.27

0.27

0.26
0.26

0.26

10

15

20

25

30

35

40

45

50

10

15

20

25

30

35

40

45

50

55

10

15

20

25

30

35

(c)
(a)
(b)
Figure 3 Graph of calcination temperature of active site (a) at 400C (b) at 500C (c) at 600C
Time (minutes)

Time (minutes)

Time (minutes)

EFFECT OF METAL LOADING (MIMI FAZZLINDA MOHSIN)


Effect of metal loading also affected the area of catalyst. The result was obtained using Chemisorption
(TPD) at different percentage of metal loading of potassium, K which are 5%, 10% and 15%. In a study conducted
by [23], it was shown that independent techniques and chemisorption has different methods have been suggested in
the literature conferring to the given agreement between the values found for the determination of the average metal
particles size. Results are obtained in this graph indicates the area of the active site of the different percentage of
metal loading for 5% are 181.1C, 242.6C and 487.9C, for 15% metal loading are 182.0C, 454.9C and 483.6C,
and for temperature 10% metal loading consists of 2 peak only which are 205.9C and 481.5C. In 2002, [19] noted
increasing the average cluster size by higher the loading or exchanging to decreases surface area supports with the
same loading can improve the percentage of reduction obtained.
In Table 4, the area for the all different of metal loading has been stated. The area of the different metal
loading has been compared. On metal loading of 10%, the highest area was determined is 1.12778 at 205.9C but the
on metal loading 5%, the lowest area was determined is 0.14536 at 181.1C. From the figure 4 , it show the
increasing of metal loading, the increasing the area of active site for absorption of H2.The linear relationship
between experimental values and metal loading, for the two sets of values, the particle size larger with higher
reduction temperature [23]. The amount of hydrogen adsorbed on the supported particles decreases with temperature
because the equilibrium shifts toward hydrogen in gas phase. Even at low temperature, the weakly bound hydrogen
can react definitely with other adsorbates at which aggressive reaction pathways main to byproducts are inhibited
[24].
Corresponding Author: Mimi Fazzlinda Mohsin, Nur Asyida Mohd Asyrul, Muhammad Arif Afif Amran,
Faculty of Chemical Engineering, Universiti Teknologi MARA (Terengganu) Bukit
Besi Campus, 23200 Bukit Besi, Dungun, Terengganu, Malaysia, Email: mimi.mohsin@gmail.com,
asyidasyrul94@gmail.com, arifafif423492@yahoo.com.my

40

45

50

The smallest area among this graph is on metal loading 5% is 0.14536 at 181.1C has been showed in
Figure 4(a). This is because the less amount of the metal loading affects the area of active site become smaller. Even
though, higher temperature was exerted the area of active site still lower. It differs with graph for metal loading 10%
and 15%. [23] observed the when metal dispersion with metal loading decreases, the observation barely and
elimination of hydrogen adsorption can be concluded. Hence,the higher the percentage of metal loading, the larger
the area of active site. Thus, the impregnation of K into catalyst lower the reduction temperature of optimal catalyst
discovered by TPR study [18].
Consequently, the best of metal loading is 10% because the highest area of active site which is 1.12778 at
lowest temperature at 181.1C. The higher the metal loading the larger the area of active site on the lower
temperature applied.
Table 4 Different active site at different metal loading
Temperature at maximum
(C)
181.1
242.6
487.9
205.9
481.5
182.0
454.9
483.6

Metal loading (%)


5
10
15
TCD Signal (a.u.) vs. Time

Area

Peak height

0.14536
0.17177
0.22753
1.12778
0.46700
0.75958
0.34358
0.25064

0.01598
0.01406
0.01243
0.06156
0.03129
0.04230
0.02514
0.02591

TCD Signal (a.u.) vs. Time

TCD Signal (a.u.) - TPD

TCD Signal (a.u.) vs. Time

TCD Signal (a.u.) - TPD

TCD Signal (a.u.) - TPD

0.305
0.32
0.278

205.9

181.1

0.300

182.0

242.6

0.276

0.31
0.295

487.9
0.274

0.290

0.30

0.270

0.268

0.285
TCD Signal (a.u.)

TCD Signal (a.u.)

TCD Signal (a.u.)

0.272

481.5

0.29

454.9

483.6

0.280

0.275

0.28

0.270

0.266
0.27

0.265
0.264

0.260

0.26
0.262

10

15

20

25

Time (minutes)

(a)

30

35

40

45

50

10

15

20

25

30

Time (minutes)

35

40

45

50

55

0.255
0

10

15

(b)

20

25

30

35

Time (minutes)

(c)

Figure 4 Graph of metal loading of active site (a) at 5% (b) at 10% (c) at 15%

EFFECT OF IMPREGNATION CONCENTRATION (MUHAMMAD ARIF AFIF AMRAN)


The results on the effect of concentration of Potassium Nitrate impregnated into OPKS activated carbon
can be observed in the figures below. The experimental conditions involved are constant metal loading
concentrations and constant calcination time and temperature for 10%, 4 hours and 500C respectively.
Corresponding Author: Mimi Fazzlinda Mohsin, Nur Asyida Mohd Asyrul, Muhammad Arif Afif Amran,
Faculty of Chemical Engineering, Universiti Teknologi MARA (Terengganu) Bukit
Besi Campus, 23200 Bukit Besi, Dungun, Terengganu, Malaysia, Email: mimi.mohsin@gmail.com,
asyidasyrul94@gmail.com, arifafif423492@yahoo.com.my

40

45

50

55

Concentration of Potassium Nitrate during the impregnation process is labeled m which stands for Molar
concentration while h equals to hours of calcination time and C equals to calcination temperature in degree
Celcius.
The Figure 5 shows two steep slopes which indicate major mass loss to the catalyst at the corresponding
temperatures. Initially all of the three samples show major mass loss at temperature range of room temperature to
200C at most. The next slope or mass loss occurs at 750C to 840C temperature range for 1.0M 4H 500C sample.
While the 1.5M 4H 500C samples second slope occurs at 600C to 720C range and the 2.0M 4H 500C sample
marked at temperature range of 630C to 790C for its second slope. All samples were heated to 998.5C and their
final mass is measured. At the end of the analysis, the final mass of the samples which are 1.0M 4H 500C, 1.5M
4H 500C and 2.0M 4H 500C are 63.71%, 72.11%, and 64.34% of their initial mass. This result shows that, at
1.5M of Potassium Nitrate concentration, the resulting catalyst has the best performance, in terms of thermal

stability compared to the other samples, in


maintaining its initial mass when it is utilizes
at elevated temperature. This is important as the mass loss can
be due to the catalyst being degraded or losing its adsorbed chemicals and causes it to has drop in performance.
(a)

(b)

(c)

Figure 5 Graph of impregnation concentration of active site (a) at 1.0M (b) at 1.5M (c) at 2.0M
EFFECT OF CALCINATION TIME (MUHAMMAD ARIF AFIF AMRAN)
Figure 6 below shows the effect of calcination time on OPKS/KNO3 biodiesel catalyst. The controlled
parameters are 1.0M of Potassium Nitrate loading concentration, 10% metal loading, and 500C of calcination
temperature. Based on the Figure 6 longer calcination time shows that the catalyst is able to maintain its mass when
it is utilized at elevated temperatures. On all the three graphs, two major steep slopes can be observed at room
temperature to 200C and 700C to 800C range. This slope indicates major mass loss of the catalyst at the
corresponding temperature range. TGA analysis shows that at 998.6C, 1.0M 6H 500C catalyst was able to
maintain 63.71% of its initial mass before the analysis was conducted. The 1.0M 5H 500C catalyst was able to hold
up to 65.84% of its initial mass at the end of the analysis, while 1.0M 6H 500C catalyst maintained its mass to
67.27% from its initial mass. Longer calcination time improves the catalyst resistant towards higher temperature
which causes it to maintain higher mass at the end of the analysis. Less mass loss indicates that the catalyst has
better thermal stability. In this case, 1.0M 6H 500C sample has the best performance in terms of thermal stability.
Thermal stability is important in industry as the mass loss is due to the catalyst is degrading or releasing its adsorbed
or impregnated chemicals. Degraded catalyst will cause drop in performance of the catalyst thus render the catalyst
to the state where it is no longer useful.

Corresponding Author: Mimi Fazzlinda Mohsin, Nur Asyida Mohd Asyrul, Muhammad Arif Afif Amran,
Faculty of Chemical Engineering, Universiti Teknologi MARA (Terengganu) Bukit
Besi Campus, 23200 Bukit Besi, Dungun, Terengganu, Malaysia, Email: mimi.mohsin@gmail.com,
asyidasyrul94@gmail.com, arifafif423492@yahoo.com.my

(a)

(b)

(c)

Figure 6 Graph of calcination time of active site (a) at 4hr (b) at 5hr (c) at 6h

EFFECT OF MOLAR RATIO METHANOL TO OIL (NUR ASYIDA MOHD ASYRUL)


Molar ratio methanol to oil is one of the significant features that affect the yield of FAME. The
suitable amount of methanol in transesterification reaction was analysed in terms of its molar ratio with
respect to the fresh cooking oil. In the existing study, with preoptimized reaction parameters, the methanol
to fresh cooking oil ratio was varied in the range of 6:1 to 12:1 and its stimulus on the FAME yield was
explored.
The effect of methanol to oil ratio on the FAME yield at the end of 4 hours of reaction time at 65
C was shown in Figure 7 where the highest conversion (97.67%) was showed at the ratio of 12:1. It can be
noticeably seen from the activity profile that the percent yield of FAME decline to 48.08% when the
transesterification ratio is 9:1. This is because the amount of methanol used is not adequate to complete the
conversion to methyl ester.
Stoichiometrically, the molar ratio of methanol to fresh cooking oil is 3:1 but in practice, this is
not sufficient to complete the reaction [9]. Furthermore, [2]proposed that higher molar ratio is required in
order to shift the equilibrium to FAME. According to [2], the molar ratio of methanol to oil is dependent on
the type of catalyst. It is believed that using KNO3 as catalyst, high amount of methanol required
completing the reaction. This is because the FAME yield will increase by increasing in methanol to oil ratio
as stated by [2]Besides, the adding of excess methanol drives the reaction towards the formation of FAME
since the transesterification reaction is a reversible reaction [7].
Based on the result obtained, the suitable molar ratio of methanol to oil is 12:1 to complete the
conversion to methyl esters and produced high percentage of yield.

Corresponding Author: Mimi Fazzlinda Mohsin, Nur Asyida Mohd Asyrul, Muhammad Arif Afif Amran,
Faculty of Chemical Engineering, Universiti Teknologi MARA (Terengganu) Bukit
Besi Campus, 23200 Bukit Besi, Dungun, Terengganu, Malaysia, Email: mimi.mohsin@gmail.com,
asyidasyrul94@gmail.com, arifafif423492@yahoo.com.my

Percent yield of FAME (%)

120
97.67

100
80

79.32

60

48.08

40
20
0
6:01

9:01

12:01

Transesterification ratio (methanol to oil)

Figure7 Percent yield of FAME for transesterification ratio

EFFECT OF REACTION TIME (NUR ASYIDA MOHD ASYRUL)


Reaction time is another factor that affected the conversion to methyl esters. The consequence of
change in reaction time, which most significantly influence the physicochemical characteristics including;
surface area and yield of the FAME was studied. In order to study the appropriate reaction time for
transesterification reaction, the reaction time was varied in the range of 4 to 6 hours with 1% of catalyst
loading and 65C of temperature.
The highest observable percentage yield was 78.00% and was achieved at an experimental
condition of 5 hours as shown in Figure 8. The result indicated that the percent yield of FAME decreased to
68.11% at 6 hours of reaction time. It was observed that KNO 3 catalyst was not capable to maintain activity
and FAME yield also got exaggerated after used the catalyst for long period of time.
This was because the alkali metal compounds dissolved in methanol, which reduced the active
ingredients and thereby decreasing FAME yield in the subsequent experiments [25]. Besides, increase of
time of activation resulted in more volatile component being lost, and hence decreasing percentage yield
[1]. Other than that, shorter reaction times was required to complete the transesterification process because
[5]stated that the influence of catalyst loading in increasing the FAME yields was attributed to the increase
in the amount the active catalytic component that led to improvement of the FAME selectivity. Moreover,
[1]also come to an agreement that the percent yield of FAME will upsurge as the reaction time increase.
In a nutshell, the suitable reaction time to perfectly complete the transesterification reaction as
well as produce high percent yield of FAME is at 5 hours.

Corresponding Author: Mimi Fazzlinda Mohsin, Nur Asyida Mohd Asyrul, Muhammad Arif Afif Amran,
Faculty of Chemical Engineering, Universiti Teknologi MARA (Terengganu) Bukit
Besi Campus, 23200 Bukit Besi, Dungun, Terengganu, Malaysia, Email: mimi.mohsin@gmail.com,
asyidasyrul94@gmail.com, arifafif423492@yahoo.com.my

Percent Yield of FAME (%)

90
80
70
60
50
40
30
20
10
0

78.00
68.11
48.08

Transesterification time (hours)

Figure 8 Percent yield of FAME for transesterification time


GC-MS Analysis
There are several types of fatty acid compositions produced through the transesterification reaction. The major fatty
acid compositions are lauric acid (dodecanoic acid), plasmatic acid, stearic acid (octadecanoic acid), oleic acid
((9Z)-octadec-9-enoic acid), linoleic acid ((9Z,12Z)-9,12-octadecadienoic acid),arachidic acid (icosanoic acid),
methyl stearate (methyl octadecanoate) and myristic acid (tetradecanoic acid). The fatty acids composition of fresh
cooking oil was determined by GC-MS analysis instrument and the result are shown in Table 5 and Table 6 based on
their parameter.
Table 5 Composition and percent yield of FAME for transesterification ratio
Compositon/component
Lauric acid
Palmitic acid
Stearic acid
Oleic acid
Linoleic acid
Arachidic acid
Methyl stearate
Myristic acid
Other
Percent yield of FAME (%)

Transesterification ratio (methanol to oil)


6:1
9:1
12:1
0.68
1.22
31.63
15.29
35.11
1.09
0.27
0.21
7.27
23.07
3.06
5.45
2.23
5.17
2.85
7.79
2.82
0.87
4.60
30.66
0.28
43.45
79.32
48.08
97.67

*Constant parameter: 1% metal loading, 65C of temperature, 4 hours

Corresponding Author: Mimi Fazzlinda Mohsin, Nur Asyida Mohd Asyrul, Muhammad Arif Afif Amran,
Faculty of Chemical Engineering, Universiti Teknologi MARA (Terengganu) Bukit
Besi Campus, 23200 Bukit Besi, Dungun, Terengganu, Malaysia, Email: mimi.mohsin@gmail.com,
asyidasyrul94@gmail.com, arifafif423492@yahoo.com.my

10

Table 6 Composition and percent yield of FAME for transesterification time


Transesterification time (hours)
4
5
6
Lauric acid
0.78
0.60
Palmitic acid
15.29
34.84
18.70
Stearic acid
0.27
0.43
Oleic acid
23.07
0.03
Linoleic acid
5.45
0.10
13.42
Arachidic acid
Methyl stearate
2.85
8.18
7.56
Myristic acid
0.87
4.48
3.59
Other
0.28
29.62
23.78
Percent yield of FAME (%)
48.08
78.00
68.11
*Constant parameter: 1% metal loading, 65C of temperature, 9:1 methanol to oil ratio
Compositon/component

CONCLUSIONS
Oil palm kernel shell and potassium nitrate are successful develop using impregnation method. This
catalyst can be used as an effective catalyst in transesterification reaction to produce high percent yield of FAME.
The transesterification reaction using this heterogeneous catalyst was studied under various conditions. In largescale production of biodiesel using KNO 3 catalyst prepared from OPKS, the reusability and stability are very
important criteria in order to produce more valuable biodiesel. Besides, t[14]he parameter given which are
calcination of temperature, metal loading, time and concentration was proven effect the surface area catalyst and
catalytic reaction. Based on the experimental result obtained, it can be determined, the oil palm kernel shell (OPKS)
could be used as an effective catalyst support to perform active catalyst after impregnated with active metal (KNO 3).
Nonetheless, future research on this catalyst is still looked-for broader range analysis of the parameters and other
possible parameters can be carried in the synthesis of the catalyst such as calcination time, ratio of support and
active metal loading, and impregnation time.

ACKNOWLEDGEMENT
The author would like to express their genuine gratitude to the Madam Noraini binti Razali and reviewer
for their invaluable comments and suggestions, which substantially improved the overall quality of the article.

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Corresponding Author: Mimi Fazzlinda Mohsin, Nur Asyida Mohd Asyrul, Muhammad Arif Afif Amran,
Faculty of Chemical Engineering, Universiti Teknologi MARA (Terengganu) Bukit
Besi Campus, 23200 Bukit Besi, Dungun, Terengganu, Malaysia, Email: mimi.mohsin@gmail.com,
asyidasyrul94@gmail.com, arifafif423492@yahoo.com.my

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Corresponding Author: Mimi Fazzlinda Mohsin, Nur Asyida Mohd Asyrul, Muhammad Arif Afif Amran,
Faculty of Chemical Engineering, Universiti Teknologi MARA (Terengganu) Bukit
Besi Campus, 23200 Bukit Besi, Dungun, Terengganu, Malaysia, Email: mimi.mohsin@gmail.com,
asyidasyrul94@gmail.com, arifafif423492@yahoo.com.my

12

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