CHAPTER 2

LITERATURE REVIEW

2.1 Introduction to palm oil

2.1.1 History of palm oil
Elaeis guineensis also known as palm oil originated in the tropical rain forest
region of West Africa. The main belt runs through the southern latitudes of
Cameroon, Cte dIvoire, Ghana, Liberia, Nigeria, Sierra Leone, Togo and into the
equatorial region of Angola and the Congo. The production of edible palm oil has
been practiced in Africa for thousands of years, and the oil produced, highly colored
and flavored, is an essential ingredient in much of the traditional West African
cuisine. The traditional process is simple, but tedious and inefficient. The
development of oil palm as a plantation crop started in the South East Asia; the first
introduction of the African oil palm was four seedlings from Mauritius and
Amsterdam that were planted in the Botanic Gardens in Bogor in 1848.
European merchants trading with West Africa occasionally purchased palm oil
for use in Europe, but as the oil was bulky and cheap, palm oil remained rare outside
West Africa. In the Asante Confederacy, state-owned slaves built large plantations of
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oil palm trees, while in the neighboring Kingdom of Dahomey, King Ghezo passed a
law in 1856 forbidding his subjects from cutting down oil palms.
Palm oil became a highly sought-after commodity by British traders, for use as
an industrial lubricant for the machines of Britains Industrial Revolution. By 1870,
palm oil constituted the primary export of some West Africa countries such as Ghana,
and Nigeria, although this was overtaken by coca in the 1880s.
Oil palm was introduced to Java by the Dutch in 1848 and Malaysia (then the
British colony of Malaya) in 1910 by Scotsman William Sime and English banker
Henry Darby. The first few plantations were established and operated by British
plantation owners, such as Sime Darby and Boustead. The large plantation companies
remained listed in London until the Malaysian government engineered the
Malaysianisation policy throughout the 1960s and 1970s (Zainal Zakariah, 2010).
The first commercial oil palm plantation was established in Sumatra,
Indonesia by M. Adrien Hallet, a Belgian agronomist with interests in the Belgian
Congo (Zaire). The development of the industry in Malaysia is attributed to
Frenchman, Henri Fauconnier and his association with Hallet. In 1911, Fauconnier
visited Hallets oil palm development in Sumatra and had purchased some oil palm
seeds and these were planted at his Rantau Panjang Estate in Selangor. He returned to
Sumatra the following year to obtain seeds that he had selected together Hallet from
Tanjong Morawa Kiri Estate for further planting. With seedlings obtained from the
1911 and 1912 importation, Fauconnier established the first commercial oil palm
planting at Tennamaram Estate, to replace an unsuccessful planting of coffee bushes
(Teoh.C.T. 2002)
Oil palm tree will start bearing fruits after 30 months of field planting and will
continue to be productive for the next 20 to 30 years; thus ensuring a consistent
supply of oils. Each ripe bunch is commonly known as Fresh Fruit Bunch (FFB). In
Malaysia, the oil palm trees planted are mainly the tenera variety, a hybrid between
the dura and pisifera. The tenera variety yields about 4 to 5 tons of crude palm oil
(CPO) per hectare per year and about 1 tons of palm kernels.

2.1.2 The oil palm Biomass

Figure 2. 1: Distribution of oil palm biomass (http://www.bioenergyconsult.com/bioenergysoutheast-asia/, 2014)

The palm oil industry generates large quantity of wastes whose disposal is a
challenging task. Oil palm biomass (OPB) is an agricultural by-product left in the
field during the replanting, pruning and milling processes of oil palm. OPB is
classified as lignocellulosic residues that typically contain 50% cellulose, 25%
hemicellulose and 25% lignin in their cell wall. As shown in Figure 2.1, the biomass
from oil palm comprises of:
a) Palm fiber from pericarp of palm fruits
b) Palm shell from oil palm nuts
c) Fiber from empty fruit bunch
d) Fiber from oil palm tree trunks and leaves
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About 70 million tons of oil palm biomass was produced annually which
comprises only small fraction of oil from the total biomass produced in the plantation.
The remaining biomass is an immense amount of lignocellulosic materials in the form
of fronds, trunks and empty fruit bunch. Oil palm biomass waste can create
substantial environmental and major disposal problems when simply left on the
plantation fields. The fundamental principle of waste managements is to minimize and
recycle the waste, recover the energy and finally dispose the waste. Presently, EFB
mainly used as mulch, but the economic are marginal due to the high transport cost. It
is seldom burnt as fuel, as the shell and fruit fibers are sufficient for oil palm mills.
In the palm oil mill, fresh fruit bunches are sterilized after which the oil fruits
can be removed from the branches. The empty fruit bunches are left as residues, and
the fruits are pressed in oil mills. The palm oil fruits are then pressed, and the kernel
is separated from the press cake (mesocarp fibers). The palm kernels are then crushed
and the kernels then transported and pressed in separate mills. In a typical palm oil
plantations, almost 70% of the fresh fruit bunches are turned into wastes in the form
of empty fruit bunches, fibers and shells, as well a liquid effluent. These by-products
can be converted to value-added products or energy to generate additional profit for
the palm oil industry (Salman Zafar, 2014).
In a typical Palm Oil mill, empty fruit bunches are abundantly available as
fibrous material of purely biological origin. EFB contains neither chemical nor
mineral additives, and depending on proper handling operations at the mill, it is free
from foreign elements such as gravel, nails, wood residues, waste etc. However, it is
saturated with water due to the biological growth combined with the steam
sterilization at the mill. Since the moisture content in EFB is around 67%, preprocessing is necessary before EFB can be considered as a good fuel. In contrast to
shells and fibers, empty fruit bunches are usually burnt causing air pollution or
returned to the plantations as mulch. Empty fruit bunches can be conveniently
collected and are available for exploitation in all Palm Oil mills. Since shells and
fibers are easy-to-handle, high quality fuels compared to EFB, it will be advantageous
to utilize EFB for on-site energy demand while making shells and fibers available for
off-site utilization which may bring more revenues as compared to burning on-site.
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The oil palm fronds are a by-product of the cultivation of oil palm trees. The
rapid development of the palm oil industry has caused an increasing output of fibrous
wastes derived from the harvesting of oil palm fruit bunches, both from pruning
management practices and from the replanting operations. Oil palm fronds are a lowprotein, high-fiber material that has been shown to be palatable and to have a good
feeding potential for many classes of herbivore livestock, including cattle, buffaloes,
sheep, goats, deers and rabbits. Whole oil palm fronds (the petiole and leaflets) are
usually chopped into lengths of about 2 cm and fed fresh, dried, pelleted or ensiled in
combination with other ingredients as total mixed ration. Leaving oil palm fronds to
rot between the rows of palm trees can help soil conservation and erosion control. Oil
palm fronds contain more than 55 % water and tend to become moldy during storage.
When fresh, they should be collected and used readily within two days after
harvesting or pruning. For longer storage, it is necessary to dry or ensile it.
Oil palm tree normally passed their economic age, on an average after 25
years, and due to replanting. Oil palm trunk (OPT) is a solid waste obtained in large
quantities after the felling of oil palm trees and is available year round. The oil palm
trunks have high water and moisture content make it unsuitable to be made as fuel and
furniture. OPT consists of vascular bundle and parenchyma. From the structural point
of view, OPT ultimately becomes a hazardous material to farmers and have no
economic value. Because OPT consists of lignocellulosic materials, its cellulosic
material is utilized I the production of panel products such as particle board, medium
density board and cement board. In order to control the OPT wastes; it is essential to
consider its alternative utilization inside buildings as lightweight construction material
Mohammad Jawaid et, Al., 2013).
Palm kernel shells (or PKS) are the shell fractions left after the nut has been
removed after crushing in the Palm Oil mill. Kernel shells are a fibrous material and
can be easily handled in bulk directly from the product line to the end use. Large and
small shell fractions are mixed with dust-like fractions and small fibers. Moisture
content in kernel shells is low compared to other biomass residues with different
sources suggesting values between 11% and 13%. Palm kernel shells contain residues
of Palm Oil, which accounts for its slightly higher heating value than average
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lignocelluloses Biomass. Compared to other residues from the industry, it is a good

quality Biomass fuel with uniform size distribution, easy handling, easy crushing, and
limited biological activity due to low moisture content. Press fiber and shell generated
by the Palm Oil mills are traditionally used as solid fuels for steam boilers. The steam
generated is used to run turbines for electricity production. These two solid fuels
alone are able to generate more than enough energy to meet the energy demands of a
Palm Oil mill (Salman Zafar, 2014).
Palm Oil processing also gives rise to highly polluting waste-water, known as
Palm Oil Mill Effluent, which is often discarded in disposal ponds, resulting in the
leaching of contaminants that pollute the groundwater and soil, and in the release of
methane gas into the atmosphere. POME could be used for biogas production through
anaerobic digestion. At many Palm-oil mills this process is already in place to meet
water quality standards for industrial effluent. The gas, however, is flared off. In a
conventional Palm Oil mill, 600-700 kg of POME is generated for every ton of
processed FFB. Anaerobic digestion is widely adopted in the industry as a primary
treatment for POME. Liquid effluents from palm oil mills can be anaerobically
converted into biogas which in turn can be used to generate power through gas
turbines or gas-fired engines.

2.1.3 The characteristics of oil palm biomass

The chemical composition of biomass is very different from others such as
coal oil. The presence of large amount of oxygen in plant carbohydrate polymers
means a pyrolytic chemistry differs sharply from these other fossil fuels. Plant
biomass is essentially a composite material constructed from oxygen-containing
organic polymers. The major structural chemical component with high molar masses
is carbohydrate polymers and oligomers and lignin. Minor low molar mass extraneous
material mostly organic extractives and inorganic minerals are also present in
biomass. The major constituents consist of cellulose (a polymer glucosan),
hemicellulose (also called polyose), lignin extractives, and inorganic minerals. The

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high silica content causes difficulties in cutting and chipping of the biomass into
desired shapes and sizes.
The composition of the lignocellulosic material varies between the species and
affects the properties of the lignocellulosic material. The cell walls of all plants
contain fibers of cellulose, an organic material known to chemical as a linear
polysaccharide of glucose. The cellulose represents 40 45% of the dry weight of
wood. Hemicellulose consists of various sugars other than glucose that encloses the
cellulose fibers and represents 20 35% of dry weight of wood. Lignin is complex
amorphous non-sugar polymer with high molecular mas that gives strength to the
wood fiber. It accounts 15 30% of the dry weight of wood. Typical lignin,
hemicellulose and cellulose composition for some type of plant is shown in figure 2.2
The fiber length of both OPT and OPF is an intermediate between hardwood and
softwood, this characteristics is affected by high fines (parenchyma) content:
parenchyma contents in trunk and frond are about 50% and 30% respectively, while
as 5% only in EFB.

Figure 2. 2: Typical lignin, hemicellulose, and cellulose composition for some type of
plant biomass (H.Berg, 2013)

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Figure 2. 3: The Proximate and ultimate analysis of biomass waste composition

(H.Berg, 2013)
The biomass feed stocks composition analyzed in term of volatile content,
fixed carbon, ash, and moisture is called the proximate analysis, whereas an analysis
of the volume percentage of carbon, oxygen, nitrogen, and sulfur compound is called
the ultimate analysis. Figure 2.3 shows the proximate analysis and ultimate analysis
according to the type of biomass feedstock. The type of hardwood and soft word will
was focused on.
Table 2.1: Oil palm biomass chemical composition (% dry weight) (Khalil et al,
2012)
Oil palm trunk

Oil palm frond

Empty fruit bunch

Cellulose

29 37

40 50

43 65

Hemicellulose

12 17

34 38

17 33

Holocellulose

42 45

80 83

68 86

Lignin

18 23

20 21

13 37

Xylose

15 18

26 29

29 33

Glucose

30 32

62 67

60 66

Ash

23

23

16

Table 2.1 shows the composition of constituents in different type of oil palm
biomass; oil palm trunk, oil palm frond and empty fruit bunch. It can be seen that EFB

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has the highest cellulose content whereas OPF has higher hemicellulose and lignin
content.

2.2 Oil palm biomass as energy resources

Since palm oil has a high fossil energy balance, it is a key source of raw material for
biodiesel production. Palm oil can be characterized as vegetable oil cannot be used
directly in diesel engines because of the problem associated with it of the using pure
vegetable oils as fuels in diesel engines. The most detrimental properties of these oils
are their high viscosity, low volatility, poor atomization and auto oxidation. Palm oil
is mostly used in the manufacture of food products; however, palm oil is now starting
to be used as an ingredient in bio-diesel and as a fuel for electricity generation.
Table 2.2: Oil palm biomass collected in Malaysia in 2005 and their energy potential
(Bazmi, A. A. et. Al, 2011)
Biomass

Quantity available

Calorific value

Potential

component

(million tons)

(kJ / kg)

generation (Mton)

18 838

7.65

Empty

fruit 18.00

energy

bunches
Shell

5.92

20 108

2.84

Fiber

9.60

19 068

4.37

Palm kernel

2.11

18 900

0.95

Fronds and trunks

21..10

Total

55.73

-0

15.81

Based on table 2.2, EFB has the highest potential energy generation with the
value of 7.65 Million tons. Frond and trunk contributed to highest amount of collected
material over a year.
For todays technologies, after refining and processing processes, palm oil
wastes were sent to the palm oil mills to be burned to provide heat for the electricity
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generation. The generated electricity then will be used back to support the power and
electricity usage throughout the palm oil processing plant. Further development and
research was made to discover other methods which can be used to utilize the
potential of palm oil as renewable energy to the maximum. Palm oil has been
discovered to be potential biofuels resources when blended with diesel oil. Palm oil
blended biodiesel has emerged as an alternative fuel for an internal combustion engine
satisfying certain criteria, such as requiring minimum engine modification, offering
uncompromised engine life and not being hazardous to human health and the
environment during production, transportation, storage and utilization. Direct use of
crude palm oil has been shown feasible in the Elsbett engine. However, a problem of
clogging of the filter by impurities is observed, which can be eliminated by using
processed liquid palm oil directly or in blends with petroleum diesel to overcome this
problems (Nagi J., Ahmed S. K., Nagi F., 2008).

2.3 Thermal decomposition of oil palm biomass

Decomposition is a type of chemical reaction and it may be defined as the
reaction in which a single compound splits into two or more simple substances under
suitable conditions. Thermal decomposition is a chemical reaction where a single
substance breaks into two or more simple substances when heated. The reaction is
usually endothermic because heat is required to break the bonds present in the
substance. Thermal analysis is a group of analysis in which a physical property of a
substance and/or its reaction products is measured as a function of temperature whilst
the substance is subjected to a controlled temperature program. Heat is flow into a
substance induces many physical and chemical changes which can help to identify
and characterize a sample. In practice, thermal analysis gives properties like enthalpy,
thermal capacity, mass changes and the coefficient of heat expansion. Solid state
chemistry uses thermal analysis for studying reactions in the solid state, thermal
degradation reactions, phase transitions, and phase diagrams.

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2.3.1 Pyrolysis technology

Pyrolysis is the thermal conversion or the destruction or degradation of
organics in biomass materials in the absence of oxygen. Pyrolysis is commonly
referred to as lower temperature thermal processes producing liquids as the primary
product. It is normally conducted at moderate temperature (400 - 600C) over a short
period of retention time. It products comprise of liquids (water, oil/ tars), solids
(charcoal) and gases (methane, hydrogen, carbon monoxide and carbon dioxide). The
efficiency of pyrolysis and the amount of solid, liquid, and gaseous fractions formed
largely depend on the process parameters such as pretreatment condition, temperature,
retention time and type of reactors. Pyrolysis is the first step in combustion and
gasification processes, it is known as a technology for producing charcoal and
chemicals for thousands of years before.
Bio-oil is a term used for liquid fuel product of biomass pyrolysis. The color
varies from light brownish yellow to dark brown for various fractions during
condensation phases with pungent-smoky odor and acidic pH. Bio-oils are complex
mixtures of chemical compounds that are obtained from the decomposition of
cellulose, hemicellulose, and lignin along with other organic entities. The single most
abundant compound in any bio-oils would be water (up to 40% w/w) which is crucial
in determining the energetic value as well as physiochemical properties such as pH,
viscosity and phase separation. Bio-oils can also contain some fine solid particles
(aerosols). The fuel characteristics of bio-oils are in principle due to hundreds of
organic compounds that belong to sugars, organic acids, alcohols, aldehydes, ketones,
phenols, esters, ethers, furans, nitrogen, and sulfur compounds, and multifunctional
compounds.

2.3.2 The mechanism of thermal decomposition of oil palm biomass.

Biomass decomposition has been reported from previous studies happened in
two steps; first is the volatilization of the main biomass constituents and production of
char residue at low temperature, the second step includes the decomposition of lignin
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and the combustion of the charcoal generated in the early stage. The decomposition of
carbonaceous matter during pyrolysis is very complicated and depends on heat
transfer by convection, conduction and radiation. Important parameters that determine
the quality and yield of pyrolysis products are heating rate, final temperature, holding
time at the final temperature and the nature and physical properties of raw materials.

2.3.3 Pre-treatment of Oil Palm Biomass by Torrefaction

Torrefaction can be defined as a mild pyrolysis process, which involves
heating of the feedstock at moderate temperatures under an inert atmosphere.
Referring to figure 2.5, the total torrefaction process consists of drying, torrefaction
and cooling. Three time temperature phases are recognized in torrefaction window.
The reaction time of torrefaction is defined as the sum of heating time from 200C to
desired temperature plus reaction time/ holding time at desired torrefaction
temperature and the duration of torrefaction stage is around 30 minutes. After
torrefaction, the last stage is cooling the biomass from 200C to ambient temperature.

Figure 2.4: Heating stages of drying biomass during a typical torrefaction batch
process. Explanation: Ttor: Torrefaction temperature. th: heating time to drying. tdry:
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drying time, th.int: intermediate heating time to torrefaction, ttor: reation time/ holding
time at desired torrefaction temperature, ttor.h: heating time from 200C to desired
temperature, ttor.c: cooling time from Ttor to 200C, tc: cooling time to ambient (Luo X.
2011).
During torrefaction of lignocellulosic biomass, mainly hemicellulose are
decomposed, where as cellulose and lignin may be partly decomposed at relatively
higher temperature within temperature range for biomass torrefaction. Figure 2.5
shows the decomposition regimes of lignocellulosic component of biomass was. The
scarlet color region is where the carbonisation and extensive devolatilization occur.
The orange color region is where limited devolatilization and carbonization while as
the yellow color region where the depolymerization commences.
Similar to pyrolysis, the chemical structure of plant biomass is changed during
the torrefaction. Biomass torrefaction results in products found in three phases: solid,
liquid, and gas. The solid is the main product of biomass torrefaction and also called
torrefied biomass which has very low moisture contents and high caloric values. By
cooling the exhaust gas from biomass torrefaction, liquid of yellowish colour is
obtained from condensable gases. Non-condensable gases leave the process in the gas
phase, which include carbon monoxide, carbon dioxide and little amount of methane.
Torrefaction also cause energy densification of biomass fuel. Typically, 70% of the
feed mass is retained after torrefaction as solid products or also known as torrefied
biomass which contained 90% of initial energy. The other 30% of the feed mass is
converted to the gas products, but the energy contains only 10% of the initial energy.

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Figure 2.5: Temperature distribution of decomposition of biomass component (Luo

X., 2011)
In torrefaction, typically only 70% of the feed mass was retained after
torrefaction as solid product which contained 90% of initial energy. The rest

of

30% of the feed mass is converted to the gas products, but the energy contained only
10% of the initial energy. Torrefaction made the biomass more coal-like substances; it
becomes darker in color, more brittle in structure and requires much less energy for
size reduction and pelletizing. The final moisture content of the product is very low
and torrefied biomass is hydrophobic.

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2.4 Thermogravimetric analysis

TGA is an analytical technique used to determine a materials thermal stability
and its fraction of volatile components by monitoring the weight change that occurs as
a specimen is heated. The measurement is normally carried out in air or in an inert
atmosphere, such as Helium or Argon, and the weight is recorded as a function of
increasing temperature. Sometimes, the measurement is performed in a lean oxygen
atmosphere (1 to 5% O2 in N2 or He) to slow down oxidation. The instrument used in
this study is the TGA/DSC. It can measure the weight change and heat flow
simultaneously.

2.4.1 TGA operating principle

TGA measures the changes in weight in relation to changes in temperature
subjected to a controlled temperature programmed. The temperature programed is
most often a linear increase in temperature, but, isothermal studies can also be carried
out, when the changes in sample mass with time are followed. It can be used to
examine the gasification processes and kinetic process happened in the sample. A
derivative weight loss curve can be used to tell the point at which weight loss is most
apparent. The measured weight loss curve gives information on

Changes in sample composition

Thermal stability

Kinetic parameters for chemical reaction in the sample

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Figure 2. 6: Example of thermogram obtained from TGA

The weight loss curve, also known as thermogram is a graph of mass versus
temperature. It sometimes was give as % of original mass. Figure 2.7 shows the
example of graph obtained from the analysis. Tangent is draw at the curve to find the
onset and the offset point. However, due to the gradual initiation of transition
(sometimes up to 100oC) it may be difficult to determine Tonset precisely. The weight
loss due to carbon oxidation is often superimposed on the weight increase due to
catalyst oxidation at low temperatures. In some cases this leads to an upward swing of
the TGA curve prior to the bulk of the weight loss, which makes the definition of
Tonset even more difficult and ambiguous.

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