CHAPTER 2

LITERATURE REVIEW

2.0 Introduction
This chapter discusses an overview about agricultural waste based catalyst as the main
topic. The subtopic contains of biodiesel, heterogeneous catalyst, and catalyst support.
All the reviewed topic related with previous studies which are relevant to this study.
2.1 Biodiesel
Biodiesel is a non-petroleum based diesel fuel which consists of the mono alkyl esters
of long chain fatty acids derived from renewable lipid sources. Biodiesel is typically
produced through the reaction of a vegetable oil or animal fat with methanol in the
presence of a catalyst to yield glycerin and biodiesel (chemically called methylesters).
(John, 2006)

Nowadays, the method of producing biodisel have been known quiet a while.
However, there has been interest significant in the production of biodisel. Biodiesel, a
methyl ester, is an alternative to diesel that is made from a triglyceride (like vegetable
oil) and either ethanol or methanol. The oil used in the process can come from many
sources including soybeans, corn, canola, and used frying oil. Because it comes from
renewable resource, it is referred to as a biofuel (John, 2006). The process involves
taking the oil, a triglyceride, combining it with an alcohol, to form biodiesel, which is
either an ethyl ester or a methyl ester.

2.1.2 Transestrification

In the transesterification of different types of oils, triglycerides react with an alcohol,

generally methanol or ethanol, to produce esters and glycerin. To make it possible, a
catalyst is added to the reaction
The reaction is shown below:
Figure 2.1 Transesterification of Oil and methanol to produce FAME(Sharif, 2010)

Marchetti et. al (2007) mention that the overall process is normally a sequence
of three consecutive steps, which are reversible reactions. In the first step, from
triglycerides diglyceride is obtained, from diglyceride monoglyceride is produced and
in the last step, from monoglycerides glycerin is obtained. In all these reactions esters
are produced. The stecheometric relation between alcohol and the oil is 3:1. However,
an excess of alcohol is usually more appropriate to improve the reaction towards the
desired product.

2.2 Heterogeneous catalyst

Catalysts mainly belong to the categories of homogeneous or heterogeneous.
Homogeneous catalysts act in the same phase as the reaction mixture, whereas
heterogeneous catalysts act in a different phase from the reaction mixture. Being in a
different phase, heterogeneous catalysts have the advantage of easy separation and

reuse. The widely used alkaline catalysts NaOH and KOH are easily soluble in
methanol, forming sodium and potassium methoxide and augmenting the reaction to
completion.
The major drawback of heterogeneous catalysts in general lies their
preparation and reaction conditions which is energy intensive which will escalate their
production cost and their leaching aspect. For a catalyst to be truly heterogeneous in
nature, it should not leach into the reaction medium and should be reused. In addition,
the catalyst should have high selectivity for the desired product formation and should
give high yield and conversion to biodiesel. The combustion characteristics of the fuel
are independent of the catalyst used for transesterification.
However, the characteristics of the fuel depend on the feedstock used in
synthesis of biodiesel. The solid catalysts can be categorized as solid base and solid
acid catalyst. Di Serio et al. have discussed the mechanism of various heterogeneous
catalysts. Heterogeneous catalysts (acid and base) have been classified as Brnsted or
Lewis catalysts. A catalyst may possess one or both of the sites and the relative
importance of these two sites is not known so far. The mechanism of reaction for
heterogeneous catalysts is similar to that of homogeneous catalysts.

2.2.1 Acid Catalyst

This way of production is the second conventional way of making the biodiesel. The
idea is to use the triglycerides with alcohol and instead of a base to use an acid. The
most commonly used is sulfuric acid (J.M. Marchetti, 2007) and some authors prefer
sulfonic acid (J.M. Marchetti, 2007). This type of catalyst gives very high yield in
esters but the reaction is very slow, requiring almost always more than one day to
finish. Freedman and Pryde (2001) get the desirable product with 1 mol% of sulfuric
acid with a molar ratio of 30:1 at 65C and they get 99% of conversion in 50 h, while

the butanolysis will need 117C and the ethanolysis 78C but the times should be 3
and 18 h, respectively. As in the alkali reaction, if an excess of alcohol is used in the
experiment then better conversion of triglycerides is obtained, but recovering glycerol
becomes more difficult and that is why optimal relation between alcohol and raw
material has should be determined experimentally considering each process as a new
problem.
The possible operation condition is, usually, molar ratio 30:1. The type of
alcohol, as well as the oils, is the same as the one that can be used in alkali catalyst
reaction. The amount of catalyst supposed to be added to the reactor varies from 0.5 to
1 mol%. The typical value is 1%, but some authors have used 3.5 mol% (J.M.
Marchetti, 2007). The temperature range varies from 55 to 80C. The acid
transesterification is a great way to make biodiesel if the sample has relatively high
free fatty acid content. In general, a 1 mol% of sulfuric acid is a good amount for a
final conversion of 99% in a time around 50 h. A kinetics modeling for soybean oil
has been made by Freedman (J.M. Marchetti, 2007)

2.2.2 Alkali Catalyst

For a basic catalyst, either sodium hydroxide (NaOH) or potassium hydroxide (KOH)
should be used with methanol or ethanol as well as any kind of oils, refine, crude or
frying. In this process it is better to produce the Alcoxy before the reaction to obtain a
better global efficiency. The alcoholoil molar ratio that should be used varies from
N=1:16:1. However N=6:1 is the most used ratio giving an important conversion for
the alkali catalyst without using a great amount of alcohol. The types of alcohol are
usually methanol and ethanol. The last one has fewer safety problems because it is
less toxic. The oils used could come from any vegetable, e.g., corn, canola, peanut,

sunflower, soybean, olive, palm, palm kernel. The amount of catalyst that should be
added to the reactor varies from 0.5% to 1% w/w (Barnwal and Sharma,2005) and
more preferred advice are any values between 0.005% and 0.35% w/w (Hanna, 1999)
should be used.
The last but not least important variable is the reaction temperature. The
standard value for the reaction to take place is 60C, but depending on the type of
catalyst different temperatures will give different degrees of conversion, and for that
reason the temperature range should be from 25 to 120C (Barnwal and
Sharma,2005). The reason there is a great interest in the alkali process is it is more
efficient and less corrosive than the acid process, making it a preferred catalyst to be
used in industries. In this study case, the heterogeneous catalyst as a NaOH supported
on agricultural waste that has been chosen to be studied and the effectiveness of the
catalyst will be tested in transesterification.
2.3 Catalyst Support
Catalyst support is the material, usually a solid with a high surface area, to which a
catalyst is affixed (Johnny J,2002). The reactivity of heterogeneous catalysts and
nanomaterial-based catalysts occurs at the surface atoms. Consequently great effort is
made to maximize the surface area of a catalyst by distributing it over the support.
The support may be inert or participate in the catalytic reactions. Typical supports
include various kinds of carbon, alumina, and silica (Zaera, 2006).
In multiphase catalysts, the active catalytic material is often present as the
minor component dispersed upon a support sometimes called a carrier. The support
may be catalytically inert but it may contribute to the overall catalytic activity. Most
catalytic processes are heterogeneous in nature, and often rely on the use of transition
metal particles dispersed on high surface area supports. Finally, several promising
new research directions related to the future development of heterogeneous metal
catalysis are highlighted, in particular those associated with the designing and
characterization of novel catalytic materials, the surface science of catalysis, high
throughput catalyst testing, improved selectivities, and green chemistry (Zhen Ma,
2006).
2.3.1 Palm kernel shell

Palm kernel shell are a hard endocarp of palm kernel fruit that surround palm kernel
seed of oil palm tree (abiola, 2006). Oil palm tree native of west africa also known as
Elaeis guineensis and nowadays widely spread throughout the tropic. In palm oil
industry, the crash shell without nut is referring to palm kernel shell.
The palm kernel shell are obtain after threshing or crushing the palm kernel
into crushed pieces (Yusuf, 2010). At crude palm oil process, after the cyclone
separation process, mesocarp fibre and oil palm nut will be separated. The oil palm
nut will be drying to remove moisture at nut drying process and then cracking at nut
cracking process. Kernel will be separated for kernel oil process and the nut shell will
place in the waste section (Hoong, 2009).
Otherwise, palm kernel shell can be considered as pellet form because of it
nature form, due to its high grade solid, low ash and low sulphur content, palm kernel
shell has been used as a burner for power plant. One of the most favorable used of
palm kernel shell is to process become charcoal. Furthermore, the burned palm kernel
shell charcoal has other economy value too. Palm kernel shell charcoal has also been
used as activated carbon for water purification, promote organic farming, and also and
active agent for soil improvement (Hoong, 2009).

2.3.2 Activated Carbon

Activated Carbon (AC) also called activated charcoal, activated coal, or carbo
activatus, is a form of carbon processed to be riddled with small, low-volume pores
that increase the surface area available for adsorption or chemical reactions. Activated
carbon has been clarified in different method of definition from authors this will
provide basis understanding of activated carbon as solid carbon material (Ain,2007).
Based on T. Deithorn and F. Mazzoni (2013) the carbon-based material is
changed over to activated carbon by thermal decomposition deterioration in a furnace
utilizing a controlled atmosphere and heat. The resultant product has an amazingly

have large surface area per unit volume, and a system of submicroscopic pores where
adsorption happens. The dividers of the pores give the surface layer particles crucial
for adsorption. AC can be prepared from a large number of raw materials, especially
agro-industrial by-products like palm kernel shells by one of the following process
which is physical reactivation and chemical activation (Zafirah, 2010).
2.3.3

Factors Affecting Activated Carbon Production

2.3.3.1 Raw material

Most organic materials rich in carbon that do not fuse upon carbonization can be
used as raw material for the manufacture of activated carbon. The selection of raw
material for preparation of porous carbon, several factors are taken into consideration.
There are a severel factor that affect AC production which is high carbon content, low
in inorganic content, high density and sufficient volatile content, the stability of
supply in the countries, potential extent of activation, inexpensive material, and low
degradation upon storage.

Low content in organic materials is important to produce activated carbon with

low ash content, but relatively high volatile content is also needed for the control of
the manufacturing process. Raw materials such as palm kernel shell are very popular
for many types of activated carbon, because their relatively high density, hardness and
volatile content are ideal for production of hard granular activated carbon (Guo and
Lua, 2001)
2.3.3.2 Temperature
Temperature, particularly the final activation temperature, affects the characteristic of
the activated carbon produced. Generally, for commercial activated carbon usually
conducted at temperature above 800C in a mixture of steam and CO 2 (Ain, 2007) .
Recently, the researches have been working out on optimizing the final activation

temperature to economize the cost of production and time. Activation temperature

significantly affects the production yield of activated carbon and also the surface area
of activated carbon (Zafirah 2010).
The optimum temperatures have been reported to be between 400C to 500C by
most the earlier researchers irrespective of the time of activation and impregnation
ratio for different raw material. The increasing of activation temperature reduces the
yield of the activated carbon continuously (Zafirah, 2010). According to Guo and Lua
(2001), this is expected since an increasing amount of volatiles is released at
increasing temperature from 500C to 900C. The decreasing trend in yield is
paralleled by the increasing activation temperature due to the activation reaction.
These phenomena are also manifested in the decreasing volatile content and
increasing fixed carbon for increasing activation temperature. Previously, it is
suggested that the percentage of volatile matter decreased with an increased of
carbonization temperature and the variation of this parameter was maximum between
200C and 800C due to rapid carbonization occurring in this region. It is also
unsuitable to prepare activated carbon when carbonization temperature was more than
800C since the successive decreased in volatile matter is minimal above this range
(Guo and Lua, 2001)

2.3.3.3 Activation time

Besides activation temperature, the activation time also affects the carbonization
process and properties of activated carbon. From previous study, the activation times
normally used were from 1 hour to 3 hour for palm shell (Ibrahim T, 2010). As the
time increased, the percentage of yield decreased gradually and the surface area also
increased.