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Mimi Fazzlinda Mohsin1, Nur Asyida Mohd Asyrul1, Muhammad Arif Afif Amran1,Noraini Razali1
1
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.
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
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
Temperature at maximum
(C)
189.5
463.9
205.9
481.5
188.7
459.8
400
500
600
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
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
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)
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
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
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.)
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%
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
(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
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
120
97.67
100
80
79.32
60
48.08
40
20
0
6:01
9:01
12:01
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
90
80
70
60
50
40
30
20
10
0
78.00
68.11
48.08
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
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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Faculty of Chemical Engineering, Universiti Teknologi MARA (Terengganu) Bukit
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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
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