ABSTRACT

Catalyst is very important part in every reaction nowadays especially in

manufacturing industry as the catalyst can help to speed up reaction by promoting less
activation energy to reach transition state of reaction. There are many types of catalyst
that can be used in a chemical process such as homogenous catalyst and
heterogenous catalyst. It is recently discover that is supported catalyst which promising
higher yield of production than unsupported catalyst. Therefore, this study was
conducted to synthesize the heterogeneous catalyst of Potassium (K), Sodium (Na),
and Magnesium (Mg) on activated carbon made based on Oil Palm Kernel Shell
(OPKS) at a different ratio of weight percent of loading active metal and oil palm kernel
shell and to analyze the characterizations of thermal stability of the catalysts by using
TGA and FTIR as the catalyst supported by activated carbon has to go through
calcination process where the heat at high temperature will be introduced. The catalyst
(K, Na and Mg) was used widely in industry of biodiesel production. Activated carbon
which made up based on OPKS has high accessibility as the OPKS one of the waste
can be found as abundant of waste in palm oil industry. Due to the catalyst properties,
heat supply in calcination process can cause damage to catalyst if the catalyst not
achieved thermal stability. Hence, in order to achieve thermal stability different ratio of
sample is introduced in impregnation process. The sample was tested on
Thermogravimetric Analysis (TGA) and Fourier transform Infrared Spectroscopy (FTIR)
to check the thermal stability and the content of catalyst on the activated carbon. The
result achieved from the analysis to determine the ideal mass of catalyst that can
achieve thermal stability under the calcination process and the potential of the catalyst
can be tested in the production of biodiesel.
 CHAPTER 1

1.1 Background of work

Thermal stability is defined as the stability of water body and its resistance of
mixing it is ability to remain unchanged at micro-structural level. The thermal stability
that will be studied is applied on catalyst that are supported by activated carbon
because we wanted to recognize the heat resistance capacity of the catalyst which can
be used in producing biodiesel through transesterification process. The catalyst that we
studied is the heterogeneous catalyst instead of homogeneous catalyst due to some
lacking reasons. Heterogeneous catalyst have more advantages than homogeneous
catalyst, the solid catalyst can easily was be improved and reprocessed (Vasudevan &
Briggs.,2008; Lee dw, Park ym & Lee ky., 2009).

Heterogeneous catalysts are environmentally benign, non-corrosive, easy to

separate from the liquid products, higher activity and have longer catalyst life time.
Besides, heterogeneous catalysts are known for their activity, stability, economic
benefits, ease of recovery and resistance to poisoning (Baskar & Aiswarya., 2016).
Heterogeneous catalyst is the alternative method that is appropriate to replace the
usage of alkali or acid homogeneous catalyst in a biodiesel production (Baroutian,
Aroua., Raman& Sulaiman.,2010). Besides, heterogeneous base-catalyst is preferable
in the transesterification process for biodiesel production (Bilgin,Gülüm,Koyuncuoglu.,
Nac, & Cakmak.,2015). However, in a transesterification reaction, heterogeneous
catalyst rate of reaction is lower than a homogeneous system due to the diffusion
limitations in three phases. Hence, one of the ways to overcome this mass transfer
problem is to use structured promoters like activated carbon which can provide more
specific surface area and pores for active species, where they can hold metal and will
react with a larger triglyceride molecules (Evangelista, Gondim, Souza & Araujo,.2016).
 Activated carbon acts as a catalyst support is needed to provide extremely
porous, large surface area and thermal stability thus enhancing adsorption or chemical
reactions. Metal loading that will be used are potassium, sodium and magnesium.A
study shown by Konwar, Boro & Deka ( 2014) Carbon-based catalyst are easily
prepared by functionalizing with acids or bases but its main use is in the form of a
catalyst support for active catalysts like KOH, MGO and NaOH due to its surface oxides
and unique properties like its heat resistance, stability in both acidic and basic media,
and the possibility of easy recovery of precious metals supported on it. There are
various biomass sources that can be used as activated carbon, like oil palm frond (OPF)
and oil palm kernel shell (OPKS).

1.2 Objectives

The objectives of this experiment are:

1. To analyse the effect of different type of metal loading on thermal stability

of carbon supported catalyst.
To determine the effect of different weight ratios of activated carbon and
loading metal on thermal stability of the catalyst by using analysis of TGA
and FTIR.

1.3 Scopes of work

The scopes of this project emphasize the specific methodology applied in
each objective identified earlier.
1. Oil palm kernel shells (OPKS) collected from FELCRA Berhad factory.
2. Use oil palm kernel shells (OPKS) as activated carbon and types of
the heterogenous catalyst such as magnesium supported by activated
carbon, sodium supported by activated carbon and potassium
supported by activated carbon to be prepared using wet impregnation
process.
3. Fatty acid methyl ester (FAME) is produced using the
transesterification process with the presence of the heterogenous
catalyst.
 CHAPTER 2

LITERATURE REVIEW

2.1 Thermal Stability

Thermal stability is the ability of a water body and its resistance to mix to be stabilized. This
required a number of energy needed to change the water body at a uniform water density.
Thermal stability was founded by Schmidt in 1928. Most of the matters in the world has thermal
stability. Thermal stability can also be applied on catalyst (D.L Trimm, 1991).

2.2 Homogenous and Heterogenous Catalyst

Homogenous catalyst is widely used in industries because it is simple to use, requires less time
for completion and only needs mild operating conditions for the reaction to take place but the
disadvantages in using homogenous catalyst it is easily consumed along the process thus
generating large amount of wastewater. More research has been done to overcome this
problem. When using homogenous acid catalyst the reaction requires more reaction time and
alcohol compared to base catalyst. Heterogeneous catalyst which can be derived from biomass
is effective because of its large surface area and pores. It can easily be separated and reused,
can be used for both simultaneous esterification and transesterification process, non-corrosive
and has higher selectivity in case of alkaline catalyst but the disadvantages in using
heterogeneous catalyst is it tends to form three phases with oil and alcohol thus creating
limitation in mass transfer (Baskar & Aiswarya,. 2016). This problem can be overcome when
catalyst support is used because it helps provide more specific area and pore for active species
which can act with large triglyceride molecules. Hence, heterogeneous catalysts have
commercially gained its significance over homogeneous catalyst.

2.3 Heterogenous Pottasium Catalyst

Catalyst with high basicity and surface area can increases the yield of Fatty Acid Methyl
Ester (FAME). Addition of K2O to the CaO-ZnO catalyst produces a catalyst with this
characteristic. This study has been found that potassium hydroxide (KOH) was the most used
heterogeneous catalyst in the production of biodiesel (Araujo et al., 2013). Moreover, another
study conducted by Evangelista, et al (2016) found that Potassium Oxides is an ideal solid
based catalyst in 3 economical points of view. In recent study, potassium is taken into account
in producing Alumina-supported potassium oxides catalyst for the transesterification of
vegetable oil to biodiesel. By using various potassium compounds such as KOH, KNO3, KI, KF,
and K2CO3 are combined with alumina the best catalyst. Lastly can be determined conclude
the best catalyst based from the data and result that obtained. KF/Al2O3 has been proven as
the most economical and efficient catalyst.

2.4 Heterogenous Sodium Catalyst

According to Manríquez-Ramírez et al.(2013), a study on the advances in the transesterification

of triglycerides to biodiesel using MgO–NaOH, MgO–KOH and MgO–CeO2 as solid basic
catalysts found that sodium and potassium have a strong basic strength. Besides, another study
carried by Cazetta et al., (2011) the catalytic activities of Na/NaOH /Aluminium and
K/KOH/Aluminium toward the process of esterification was improved with the presence of a
strong, basic site in the catalyst, that resulted in the ionization of potassium or sodium based
catalyst. The researchers reported that the greater the basic strength, the greater the
conversion, then concluded that sodium are suitable for application at industrial level for
biodiesel production.

2.5 Oil palm kernel shell activated carbon

Oil palm kernel shell activated carbon has high amount of porosity (Chong et al., 2001).Usually,
oil palm kernel shell is a waste product in the of industry; hence, it is easy to obtain at high
quantity and at low cost. Oil palm kernel shell has been studies for wide usage in industry
nowadays such as for alternative fuel due to its abundance (Mohammad, 2005). Carbon-based
catalyst are easily prepared by functionalizing with acids or bases but its main use is in the form
of a catalyst support for active catalysts due to its surface oxides and unique properties like its
heat resistance, stability in both acidic and basic media, and the possibility of easy recovery of
precious metals supported on it. A study by Konwar et al.(2014), under optimized conditions it
was observed that a conversion higher than 90% was possible and the catalyst could be reused
for 5 times with slight loss in activity over various carbon based catalysts. Biomass source could
also be used as a potential raw material for the synthesis of environmentally benign catalysts.
OPKS have been used in many industries as a root based material, granular strainer material
for treatment of water and floor roofing (Alengaram et al., 2013). Activated carbons are
acknowledged as an effective substance in removing pollutants such as gases, dyes, pesticides
and heavy metal and they are used to detoxify, purify, filter, discolor or adjust the concentration
of many liquid and gaseous materials and deodorize (Crini et al., 2006).
2.6 Parameters

Some ties have been conducted by Bilgin et al.(2015) state among the important parameters
that have to be taken into account are the catalyst concentration, reaction temperature, reaction
time and ratio of alcohol to oil. One of the disadvantages of biodiesel is its high viscosity thus we
need to find suitable parameters to produce biodiesel with low viscosity. Different type of
catalysts gives out different result example is the different in mass ratio referred to the different
amount of mass catalyst to the amount of activated carbon. Different mass is to determine ideal
mass of catalyst to be applied on activated carbon as the supported catalyst to be introduced to
heat for thermal stability in calcinations process. An ideal mass of catalyst can be the most
effective because there is less number of damaged catalysts during calcination. The amount of
mass catalyst to the amount of activated carbon decided as ratio catalyst to activated carbon in
our study are 1:1, 1:3 and 1:4.

2.7 Calcination Temperature

The right calcination temperature also plays a very important role to produce catalyst that can
produce high yield of biodiesel. In this experiment we use 700 degree Celsius calcinations
temperature. From the study by Xie and Huang (2006), the catalyst, like KI/Al2O3 and
KNO3/Al2O3, was calcined at 500°C- 600°C, proven to be better in the transesterification
performance of vegetable oil. As the temperature of the calcination process increases, the size
of the pore and the pore volume the catalysts increases but the surface area of the particles
decreases. The temperature of calcination process indeed the most important parameter to
make the catalyst. This is proven by Narandalai Byamba-Ochir, after physical mixing or
impregnation, the mixture was preheated at 450 °C for 2 hours in a tubular furnace to remove
moisture and volatile contaminants under Nitrogen atmosphere. This support the statement that
the higher the temperature used the more effective the catalyst is.

2.8 Thermo Gravimetric Analysis (TGA) and Fourier Transform Infrared spectroscopy (FTIR)

From study by Shan et al. (2016), TGA is Thermo gravimetric analysis or thermal gravimetric
analysis. TGA is one of the techniques used to analyze the decomposition of a mass. It can
detect changes in physical and chemical properties of materials composition and also determine
its material thermal stability. TGA can detect changes in 4 mass forms and record it, either the
mass loss or gain due to 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 no observed mass change if the species is thermally stable.
Meanwhile, Fourier Transform Infrared Spectroscopy (FTIR) and Mass Spectrometry were used
in tandem to investigate the surface chemistry and reactivity of the different catalyst systems.