Characterization of Heterogeneous K/OPKS Catalyst for Biodiesel Production

Mirdza Farouk Murhan Mukhoyiddin, Norkamruzita Saadon

Faculty of Chemical Engineering

University Teknologi MARA (Terengganu), 23200 Bukit Besi, Terengganu, Malaysia

ABSTRACT

Catalyst is chemical substances that can faster the reaction rate of chemical process without changing the process
occur. There are many type of catalyst that can be used in a chemical processes. The common catalysts used are
homogeneous and heterogeneous. The needed for development of heterogeneous catalyst has arisen from the fact
that homogeneous catalyst has a lot of limitation and disadvantages. Thus, in this study is to synthesize the
heterogeneous catalyst of potassium/oil palm kernel shell at different ratio of weight percent of loading active
metal and oil palm kernel shell and to analyze the characterizations of the catalysts by using TGA. Firstly, OPKS
is collected from the nearby factory. Next, washed the OPKS several times using distilled water. After that, it
will be dried using oven for 3 hours at 200℃ and then it is placed in furnace for 3 hours at 500℃ to produce
activated carbon. The AC will be grinded and sieved with size between 45µm to 1000µm. Before the catalyst is
produced, potassium hydroxide solution needs to be prepared. To produce catalyst, the AC will be impregnated
with potassium hydroxide solution. The mass of AC needed will mixed with the measured volume of KOH
solution in the beaker. Then it will be heated on hot plate to dry the solution at 150℃ for several hours. After
that, it will undergo calcination process with range temperature of calcination between 450℃ and 650℃. The
parameters used in this study are ratio of wt % of loading active metal and OPKS, molarity of KOH solution and
the calcination temperature. As the conclusion, the catalysts are successfully synthesized. All the catalyst
produced is thermally stable and has the potential to be used in the production of biodiesel.
KEYWORDS: Activated Carbon, Biodiesel, Supported carbon, Heterogeneous catalyst, Homogeneous catalyst,
Thermo gravimetric analysis(TGA)

INTRODUCTION

Catalyst is chemical substances that can faster the reaction rate of chemical process without changing the
process occur. It works by creating an alternative pathway for the reaction to take place thus reducing the
activation energy and increasing the rate of reaction. Long ago, before chemists identified the existence of
catalysts, normal peoples had been using the process of the catalysis for many purposes such as making soap,
fermenting wine to create vinegar and for leavening bread. They were using these mechanisms in their daily life
without adequate the presence of the catalyst. Almost everything in our daily live count on the usage of catalyst:
cars for instance, Post-it notes, and laundry detergent [1]. Without catalyst, our life would be impossible [2].
There are two type of catalyst that generally been used that are homogeneous and heterogeneous catalyst.
Homogeneous catalyst is a sequence of reactions that involve a catalyst in the same phase as the reactants while
heterogeneous catalyst refers to the form of catalysis where the phase of the catalyst differs from that of the
reactants. In recently study, show that heterogeneous catalyst always been used in the biodiesel production due
to the fact that the catalyst is recyclable compared to homogeneous catalyst [3].
Therefore, this study has been done in order to synthesize the heterogeneous catalyst of potassium/oil palm
kernel shell at different ratio of weight percent of loading metal and oil palm kernel shell and to characterize the
catalyst produced in term of weight percent change as function of temperature by using Thermo Gravimetric
Analysis (TGA).
LITERATURE REVIEW

Catalyst
Generally, catalyst is chemical substances that can faster the reaction rate of chemical process without
changing the process occur and will increased the productivity of the desired product. It function is to increases
the rate of chemical reaction by decreasing the activation energy of a chemical reaction. Typically, the amount of
catalyst needed in a chemical reaction is extremely relying on the amount of the chemical reactant used. The
common types of catalyst that are been used for the biodiesel production are homogeneous catalyst and
heterogeneous catalyst. The catalyst can be either in the base, acid or enzyme form. Each types of the catalyst

Corresponding Author: Mirdza Farouk Murhan Mukhoyiddin, Faculty of Chemical Engineering, Universiti
Teknologi MARA (Terengganu), 23200 Bukit Besi, Terengganu, Malaysia, E-mail:
[email protected]
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have their own advantages and their advantages. Process of choosing types of catalyst used for research is
important in order to meet the characteristic of the catalyst required in a research.

Homogeneous Catalyst
In the production of biodiesel, homogeneous alkali catalysts like KOH and NaOH are the most common used.
These economical catalysts can expedite to lowered the reaction times and increase its mobility and ease of
storage [4]. It has been reported that the reaction rate of homogeneous base-catalyzed has 4000 times faster than
homogeneous acid-catalyzed[4]. However, homogeneous base-catalyzed transesterification is very sensitive to
the presence of free fatty acids (FFA) in the oil, which can cause to the development of undesired soap.
Production of soap can lower the reaction yield and facilitates the formation of emulsions and can cause the
downstream separation process become difficult [4].
In order to avoid saponification occur, the reactant for the alkali-catalyzed transesterification must be
anhydrous [5]. Anhydrous is indicated to the term that substances are bare from water, for example, salts lacking
their water of crystallization. The yield of the resulting esters can be lowered by the formation of soap and
causing difficulties in separation and purification process.

Heterogeneous
Heterogeneous catalyst is the alternative method that suitable to replace the usage of alkali or acid
homogeneous catalyst in a biodiesel [6]. A heterogeneous catalyst can be easily removed from the formed
biodiesel. The examples of the heterogeneous catalyst that can be used are basic solid catalyst, acidic solid
catalyst, acid-base solid catalyst and enzymatic catalyst [7].

Figure 1: Design consideration of the catalyst properties for the transesterification process [8].

Activated Carbon
Activated carbons are known as porous materials that have a wide surface area and have great adsorption
capacity. Activated carbons are acknowledged as an effective substance in removing pollutants such as gases,
dyes, pesticides and heavy metal. ACs is used to detoxify, purify, filter, discolor or adjust the concentration of
many liquid and gaseous materials and deodorize [9].These utilizations are of main concern in many kind of
industrial sectors such as chemical, food, mining, pharmaceutical, oil and in treatment of drinking water [10].
There has been a unified consensus that activated carbon is greatly effective as a catalyst support in liquid
and vapour phase reactions. The attributes of said material contributed upper hand advantage for it to be used as
catalyst support in transesterification reaction. Activated carbon possesses great surface area, permitting catalyst
to scatter over it effectively. The bones of activated carbon are completely inert, providing no interference with
the process of transesterification itself. However, reaction could be improved by lowering the ash content of
carbon. Activated carbon could also be utilized in reaction of which the conditions are high (temperature and

Corresponding Author: Mirdza Farouk Murhan Mukhoyiddin, Faculty of Chemical Engineering, Universiti
Teknologi MARA (Terengganu), 23200 Bukit Besi, Terengganu, Malaysia, E-mail:
[email protected]
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pressure). This is due to the fact that surface property of activated carbon does not change at high temperature
and pressure [8].
A long time ago, during Ancient Egyptians ACs have been uses for cleaning oil and medicinal purposes.
However, in Ancient India it use for the filter of drinking water. In 19th century, charcoals from wood and bone
have been used for decolourization and purification of cane sugar in the large scale. Until today it has been used
in industries. The AC has variation purpose for variation type of industry such as filtering air and gases,
wastewater treatment, removal of liquid phase contaminants, including organic pollutants, heavy metal ions,
organics dyes and as catalyst support [11].

Oil Palm Kernel Shell (OPKS)

Oil palm kernel shell is the unwanted product of the extracting emollient from oil palm tree by pulverizing
the palm nut in the palm oil mills. Oil palm tree known as Elaeis guineensis (in the scientific known) mainly
found in East Africa [12]. Being the second largest country that produces palm oil, Malaysia is also liable for
creating a large amount of palm oil wastes. From this problem, many researchers initiate many ways to overcome
this problem. As the result, OPKS have been use in many industries region such as root based material, granular
strainer material for treatment of water and floor roofing [12].

Figure 2: Oil palm kernel shell

Potassium hydroxide
In the recent study, KOH are most used heterogeneous catalyst in the biodiesel production [13]. KOH are
been supported by AC to increase catalyst performance. For example, the catalytic activities of Na/NaOH
/Aluminium and K/KOH/Aluminium toward the process of esterification were improvised by the presence of
strong, basic site in the catalyst that is resulted by the ionization of potassium or sodium based [8].

Effect of Calcination Temperature

Temperature of the calcinations process plays an important role in determining the percentage yield of FAME
production. In achieving the high catalytic performance it is vital to optimize the calcination of temperature in
the preparation of the catalyst [8]. In can be proven from the studied by Xie and Huang (2006), the catalyst
calcined at 500°C- 600°C like KI/Al2O3 and KNO3/Al2O3 showed better performance in the transesterification
of vegetable oil. As the temperature of calcination process increases, the surface area of the particles decreases
but the size of the pore and the pore volume the catalysts are increases [14].

Thermo Gravimetric Analysis (TGA)

TGA is commonly used to determine selected properties of materials that exhibit either mass loss or gain by
reason of the decomposition, oxidation, or loss of volatiles (such as moisture). The importance of the mass loss
study is it can evaluate the thermal stability of a material. In a desired temperature range, there will be no
observed mass change if a species is thermally stable. Mass loss that corresponds to little or no slope in the TGA
trace could be neglected. Besides that, TGA also gives the upper use temperature of a material. The material will
be degrading if it exceeds the temperature.

METHODOLOGY
Raw Materials and Chemical
In this experiment, the raw material used to produce activated carbon is oil palm kernel shell. Oil palm kernel
shell is collected from Jerangau Palm Oil Factory. For the production of catalyst, distilled water and potassium
hydroxide solution are used.

Corresponding Author: Mirdza Farouk Murhan Mukhoyiddin, Faculty of Chemical Engineering, Universiti
Teknologi MARA (Terengganu), 23200 Bukit Besi, Terengganu, Malaysia, E-mail:
[email protected]
3
Preparation of Activated Carbon
OPKS has been wash by using distilled water several times to remove impurities and dirt that present. Then,
it was dry by using sunlight dry to remove the moisture content that present in the OPKS. After that, the OPKS is
undergoes further drying using oven for 3 hours at 200℃. This is done to make sure all the moisture content in
OPKS was removed to prevent it from rotten due to present of bacteria. Later, the dried OPKS is burned in the
furnace for 3 hours at 500℃ to produce activated carbon. This process is known as carbonization process.
Activated carbons are produced. Then, the activated carbon is grinded by using mortar or blender in order to turn
it into smaller size. Finally, it was sieved with the size between 45µm to 1000µm.

Wet Impregnation Process

The mass of AC needed is weighted by using the electronic balance. Next, the volume of KOH solution
needed is measured using burette. Then, the powder AC and the KOH solution are mixed in the beaker. After
that, the mixture is heated on hot plate at 150°C for several hours until the solution is evaporated and dried. The
dried reaction mixture is placed in the oven at 120°C for 2 hours to ensure all the moisture in the mixture is
removed. The dried mixture is calcinated for 3 hours at 550°C by using furnace.

Thermo Gravimetric Analysis (TGA)

All sample of the catalyst produce is analyzed by using thermo gravimetric analysis (TGA). TGA is one of
the techniques uses examining the decomposition of solid. Its principal uses include measurement of a material's
thermal stability and composition. TGA provides significant measurement of mass change in materials together
with transition and thermal degradation. TGA records change in mass from dehydration, decomposition, and
oxidation of a sample with time and temperature.

RESULT AND DISCUSSION

The study intended to characterize the catalyst produced in term of weight percent change as function of
temperature by using Thermo Gravimetric Analysis (TGA). The Thermo gravimetric Analysis (TGA) was
performed at 400°C of the target temperature and at a constant temperature ramping rate which between
temperatures 0°C - 1000°C/min. The purpose doing this analysis is to study the decomposition behavior of
powdered K/OPKS catalysts. Measurements are used to determine the composition and to predict their thermal
stability at temperature at 1000°C.
The Thermal Gravimetric Analysis (TGA) curves displayed generally two stages of degradation. The first
stage represented the dehydration process of the samples which is indicative of moisture. During this stage, water
and moisture components are removed. The losses of moisture content had occurred at average temperature
below 200°C for all of the samples. For the second stage, it exhibits the decomposition of potassium in the metal
carbon. During this stage, the chemical bonds between OPKS and potassium are begun to break and the lightest
volatile compounds were released [15]. It was observed that the decomposition of K had occurred at average
temperature below 600°C of all samples. The difference between the first stage and the second stage is that the
temperature degradation is higher in the second stage compared to the first stage due to the higher energy is
required to break the bond of the potassium. The remaining material was considered as residue. This happened
because by the chemical reaction that takes place when using high temperature in the reaction.
At temperature range of 90°C-200°C, the dehydration process occur. In this process, water and the other
moisture that exist in the catalyst are completely removed. Water, oil and fat will turn into carbon during the
calcination process. On the other hand, the decomposition of K happens at temperature 500°C to 700°C. During
this process, metal (potassium) that presences in the catalyst start to vaporized. The boiling point for potassium is
at 759°C. After the temperature reached above 759°C, potassium will complete vaporized. The upper limit of
temperature that the catalyst can withstand is around 800°C. Therefore, the metal carbon still exists and survives
around temperature range of 0-800°C. At the higher temperature, the metal will completely turn into residue. All
the activated carbon and metal turn into ashes after undergo the high temperature process.
Figure 3 show the graph of TG and DSC for the for the sample catalyst of 10 wt% of 1M KOH at calcination
temperature of 450 °C. TG is representing thermal gravimetric (red line) and DSC is representing differential
scanning calorimeter (blue line). At the first stage of degradation which is hydration process occurs, it shown that
the gradient of the graph is steeper compared to other stage. The percentage of water loss from 0°C to 150°C is
about 10%. The gradient of the graph decreases after several degree of temperature. At the second stage of
degradation which is the decomposition of K occurs. At this stage, K is started to vaporize. The losses of K start
to occur from 500°C until 759 °C. The entire graphs show the same patterns.
Corresponding Author: Mirdza Farouk Murhan Mukhoyiddin, Faculty of Chemical Engineering, Universiti
Teknologi MARA (Terengganu), 23200 Bukit Besi, Terengganu, Malaysia, E-mail:
[email protected]
4
 Figure 3: 10wt% of 1M KOH 450 °C (TG, DSC)

Figure 4: 20wt% of 1M KOH 450 °C (TG, DSC)

CONCLUSION AND RECOMMENDATIONS

The objective of this experiment are to the synthesize the heterogeneous catalyst of potassium/ oil palm
kernel shell at different ratio of the weight percent of loading active metal and oil palm kernel shell and also To
characterize the catalyst produced in terms of weight percent change as function of temperature by using
Thermal Gravimetric Analysis (TGA). All the catalysts was successful synthesize. The heterogeneous catalyst
was prepared with different ratio of weight percent of the active metal loading and different calcination
temperature. The potential of different types of catalyst produced to give the best characteristics of catalyst was
varied. The characteristic of the catalyst is determined from this study using TGA. The thermal stability of the
catalysts produced is being study from the result of TGA.
From the result, the upper limit of the temperature that all of the catalysts of K/OPKS produced can withstand
around 800°C means while the transesterification temperature of biodiesel production is only about 60°C-70°C,
which is still within the temperature at which K is still exist within the catalyst. Therefore, all the catalysts
produced are thermally stable and has the potential to be used in the production of biodiesel.

Corresponding Author: Mirdza Farouk Murhan Mukhoyiddin, Faculty of Chemical Engineering, Universiti
Teknologi MARA (Terengganu), 23200 Bukit Besi, Terengganu, Malaysia, E-mail:
[email protected]
5
 The production of heterogeneous catalyst from oil palm kernel shell (OPKS) is totally cost effective. This is
because OPKS is one of the environmentally friendly alternative sources to prepare activated carbon and it can
be used to sustain the environment by synthesizing catalyst.
There are several recommendation for further research that can be used such as use another different raw
material of the activated carbon such as oil palm frond (OPF), empty fruit bunch (EFB), olive husk, coffee
endocarp, plum kernels and many more, used other type of alkali such as sodium hydroxide as solution that will
be used in the impregnation method so it can compare the effectiveness of the catalyst produce, used the different
calcination temperature for the activated carbon, used the different time of calcination to produce the catalyst so
that the effect of calcination time can be study and follow the optimum temperature and time in any process
involve in the production of catalysts to get the highest efficiency.

ACKNOWLEDGEMENT

The authors would like to thank Ms Norkamruzita Saadon for her guidance and assistance in getting this
paper published.

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Corresponding Author: Mirdza Farouk Murhan Mukhoyiddin, Faculty of Chemical Engineering, Universiti
Teknologi MARA (Terengganu), 23200 Bukit Besi, Terengganu, Malaysia, E-mail:
[email protected]
6