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THE POTENTIAL OF OIL PALM FROND BIOCHAR IN PREVENTING LEACHABILITY

OF POTASSIUM FROM PEAT SOIL (ADSORPTION ISOTHERM STUDY)

NURUL AFIFI BT MAMAT


55101214130

A thesis submitted in partial fulfilment of the


Requirement for the award of the degree of
Diploma of Chemical Engineering Technology in Environment

Malaysian Institute of Chemical & Bioengineering Technology


University Kuala Lumpur

JANUARY 2016
ABSTRACT

The Potential of Oil Palm Frond (OPF) Biochar to prevent the Leachability of Potassium
(K) from Peat Soil (Adsorption Isotherm Study) was reported in this study. The amount of
K adsorbed was studied and analysed by Atomic Adsorption Spectroscopy (AAS). Then
the isotherm adsorption study was conducted to determine the adsorption capacity of
Potassium towards oil palm frond biochar. This isotherm study was tested by using
various parameters which were contact time, concentration, desorption study and pH.
From the result obtain, OPF biochar only took one hour to adsorb all the K, beyond than
that there was no detectable change. Besides, the Amount of K adsorbed was directly
perpendicular with the Concentration of Potassium (mg/g). The data were evaluated
using Langmuir isotherm. The Langmuir isotherm model determines the amount of the
maximum capacity of the potassium per unit weight of to form a complete monolayer on
the surface which is 6.78 mg/g. Desorption study was also evaluated to determine the
amount of K desorbed which showed the higher the initial concentration of K loaded in
the OPF Biochar, the higher the amount of metal ion recovered from the OPF Biochar.
The different of pH value also used to complete the isotherm study. By conducted pH 3,
5 and 7, it is proved that the highest amount of K adsorbed is at pH 3 (Acidic) compared
to pH 5 and 7 due to the weakening of electrostatic force of attraction between the
oppositely charged adsorbate and adsorbent. The OPF biochar has the potential to
prevent the leachability of potassium from the peat soil from the isotherm and desorption
study.

ii
ABSTRAK

The Potential of Oil Palm Frond (OPF) Biochar to prevent the Leachability of Potassium
(K) from Peat Soil (Adsorption Isotherm Study) was reported in this study. The amount of
K adsorbed was studied and analysed by Atomic Adsorption Spectroscopy (AAS). Then
the isotherm adsorption study was conducted to determine the adsorption capacity of
Potassium towards oil palm frond biochar. This isotherm study was tested by using
various parameters which were contact time, concentration, desorption study and pH.
From the result obtain, OPF biochar only took one hour to adsorb all the K, beyond than
that there was no detectable change. Besides, the Amount of K adsorbed was directly
perpendicular with the Concentration of Potassium (mg/g). The data were evaluated
using Langmuir isotherm. The Langmuir isotherm model determines the amount of the
maximum capacity of the potassium per unit weight of to form a complete monolayer on
the surface which is 6.78 mg/g. Desorption study was also evaluated to determine the
amount of K desorbed which showed the higher the initial concentration of K loaded in
the OPF Biochar, the higher the amount of metal ion recovered from the OPF Biochar.
The different of pH value also used to complete the isotherm study. By conducted pH 3,
5 and 7, it is proved that the highest amount of K adsorbed is at pH 3 (Acidic) compared
to pH 5 and 7 due to the weakening of electrostatic force of attraction between the
oppositely charged adsorbate and adsorbent. The OPF biochar has the potential to
prevent the leachability of potassium from the peat soil from the isotherm and desorption
study.

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APPROVAL PAGE

I have supervised and examined this report and verify that it meets the programmed and
Universitys requirements for the Diploma of Chemical Engineering Technology in
Environment.

Date: /------/------/ Signature: -------------------------------


Supervisor: KHAIRUL NADIAH
Official Stamp

iv
DECLARATION

I declare that this thesis entitled The Potential of Oil Palm Frond Biochar in Preventing
the Leachability of Potassium from Peat soil (Adsorption Isotherm Study) is the result of
my own research expects as cited in references. The thesis has not been accepted for
any degree and is not concurrently submitted in candidature of any other degree.

Date : Signature :
..

Name :

v
Special dedication to my beloved mother Rahimah binti Ismail and my father Mamat bin
Drahman that always inspire, love and stand beside me, my beloved siblings, my
supervisor, my friends especially the one who always help me and Technicians. For all
your love, support, care and believe in me. Thank you so much.

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ACKNOWLEGDEMENT

Firstly, I am grateful to ALLAH s.w.t. for this blessing and giving me the strength
and ability to completely finish this final year project successfully. I would like to take this
opportunity to express my sincere appreciation to my supervisor, Madam Khairul Nadiah
and my co-supervisor, Dr Amelia binti Md Som for her constant encouragement,
guidance, advise, monitoring and tolerance toward this project especially in writing this
report. From the help and guidance, I can finish this project and report successfully.
I also would like to thank the environment technicians of UniKL MICET, Encik Syukri
who helped me a lot by giving his guidance, advice and motivation during handling the
equipment of involved in this project. I also would like to thanks to all my friend for
helping me and for their support. Special deepest thanks also to my family who always
support me especially my mother that always giving me advices.

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TABLE OF CONTENTS

Tittle Page i

Abstract ii

Abstrak iii

Approval iv

Declaration v

Dedication vi

Acknowledgment vii

Table of Contents viii

List of Figure xi

List of Table xiii

CHAPTER 1: INTRODUCTION

1.1 Background study of biochar 1

1.2 Problem Statement 3

1.3 Objectives 3

CHAPTER 2: LITERATURE REVIEW

2.1 Overview of Biochar 4

2.1.1 Production of Biochar 5

2.1.2 The Advantages of Biochar to Environment 5

2.2 Oil Palm Frond Biochar 6

2.2.1 Advantages and Disadvantages of Oil Palm Frond Biochar 8

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2.3 Potassium (K) 8

2.3.1 Form of K in Soil 9

2.4 Overview of Peat Soil 10

2.5 Adsorption 11

2.5.1 Types of Adsorption Process 11

2.5.2 Factors Affecting Adsorption of Potassium 12

2.6 Adsorption Isotherm 14

2.6.1 Langmuir Isotherm 15

2.7 Theory and Mechanism of Atomic Adsorption Spectroscopy (AAS) 17

CHAPTER 3: METHODOLOGY

3.1 Process Flowchart 18

3.2 Feedstock Selection 19

3.2.1 Biochar Production 19

3.3 Preparation of Standard Curve by AAS 20

3.4 Potassium Isotherm Study and Analysis 21

3.4.1 Isotherm Study with variety of Contact Time 21

3.4.2 Isotherm Study with variety of Concentration 22

3.4.3 Desorption Study 24

3.4.4 Isotherm Study with Variety of pH 25

CHAPTER 4: RESULT AND DISCUSION

4.1 Introduction 27

4.2 Isotherm Study 27

4.2.1 Variety of Contact Time 27

4.2.2 Variety of Concentration 38

ix
4.2.3 Desorption Study 31

4.2.4 Variety of pH 32

CHAPTER 5: CONCLUSION

Conclusion 35

REFERENCES 36

x
LIST OF FIGURE

FIGURE NO. TITTLE PAGE

2.1 Form of K found in Soil 9

2.2 The Potassium Cycle 10

2.3 Langmuir Isotherm Graph 16

2.4 Schematic Diagram of AAS 17

3.1 Oil Palm Frond (OPF) Biochar 19

3.2 Prepared stem of OPF 19

3.3 a) Standard Solution of K Solution 20

b) AAS for Standard Curve 20

3.4 a) Sample with Biochar 22

b) Sample without Biochar 22

3.5 Water Bath Shaker 23

3.6 Filtration Process 23

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3.7 a) Dried Biochar 25

b) Rinse Process 25

3.8 a) 0.1M of NaOH and 0.1M of Nitric Acid 26

b) pH Meter Calibration 28

4.1 Contact time against Amount of K adsorbed Graph 28

4.2 Initial Concentration against Amount of K adsorbed Graph 29

4.3 Langmuir Isotherm Model 30

4.4 Bar Chart Initial Concentration against Amount K desorb 32

4.5 Bar Chart for pH Value against Amount of K adsorb 33

xii
LIST OF TABLE

TABLE NO. TITTLE PAGE

2.1 Main operating parameter pyrolysis 5

2.2 Advantages and Disadvantages of Oil Palm Frond Biochar 8

4.1 Relationship between RL and types of isotherm 31

xiii
CHAPTER 1

INTRODUCTION

1.1 Background study of biochar

Biochar is a charcoal that used for environmental purposes which can improve
soil physically or chemically and make it more suitable for plant growth. It is a fine-
grained and porous form of charcoal that also be used as a soil improver. It is created by
using a pyrolysis process, heating biomass in a low oxygen environment at elevated
temperatures between 300 C and 1000 C (Yoder, 2011).

In the production of biochar from biomass, approximately 50% of the carbon that
the plants absorbed as CO2 from the atmosphere is fixed into the charcoal (Gaunt &
Lehmann, 2008) .The carbon in charcoal is basically inert, showing a relative lack of
reactivity both chemically and biologically, and so it is strongly resistant to
decomposition. 400 million years old charcoal from wildfire has been found in sediment
layers. (James Samuel Clark, 1996)

Pyrolysis can be defined as a thermochemical decomposition of organic material


(Christine Wood, 2009). It involves irreversible change of chemical composition and
physical phase that occur simultaneously. The carbon content of the woody biomass
cannot combust without oxygen, so it is reduced by thermal decomposition to biochar
which is a form of charcoal. The carbon in biochar retains the porous cell structure of the
original feedstock material (J. & S, 2009).

Biochar has many advantages to agricultural. It can increases crop yields,


sometimes substantially if the soil is in poor condition. It helps to prevent fertilizer runoff

1
and leeching, allowing the use of less fertilizers and diminishing agricultural pollution to
the surrounding environment (Reddy, 2014). And it retains moisture, helping plants
through periods of drought more easily. Most importantly, it replenishes exhausted or
marginal soils with organic carbon and fosters the growth of soil microbes essential for
nutrient absorption, particularly mycorrhizal fungi (Kazmi, 2009).

In this study, oil palm frond (OPF) will be used as a feedstock to produce a
biochar. OPF are a by-product of the cultivation of oil palm trees. The rapid development
of the palm oil industry since the 1990s, notably in South-East Asia which are Malaysia
and Indonesia has caused an increasing output of fibrous wastes derived from the
harvesting of oil palm fruit bunches, from both pruning management practices and
replanting operations (Dahlan, 2000). Up to 100 kg/ha dry matter (DM) basis of OPF can
be produced daily (Ishida et al., 1997). OPF used to be burned but environmental
concerns led to banning the practice in the 1990s. Now they are usually left on the
ground to decompose and fertilize the soil (Lim et al., 2000). A considerable amount of
research, notably in Malaysia and Indonesia, has been carried out to demonstrate the
nutritional value and economic viability of OPF for ruminants in order to improve self-
sufficiency in dairy and meat production (Abu Hassan et al., 1996; Wan Zahari et al.,
2003). Oil palm fronds are a low-protein, high-fiber material that has been shown to be
palatable and to have a good feeding potential for many classes of herbivore livestock
(Mohamad, 2014).

The potential of OPF in Preventing Leachability of K+ from peat soil was


evaluated in this study through adsorption isotherm process. Adsorption is usually
described through isotherm that is the amount of adsorbate on the adsorbent as a
function of its pressure (gas) or concentration (liquid) at constant temperature. The
quantity adsorbed is always normalized by the mass of the adsorbent to allow
comparison of different materials. Currently, 15 different isotherm models were
developed but only one model is used in this study to to evaluate the adsorption
isotherms which is Langmuir isotherm. (Redlich & Peterson, 1959).

2
1.2 Problem Statement

This work is part of a larger study to identify the potential of OPF biochar in
preventing leachability of K+ from Peat Soil (Adsorption Isotherm Study). Numerous
studies have been conducted to optimize the use of fertilizer for oil palm grown on peat
soil. Peat soil has problem to retain potassium due to its porosity and its waterlogged
condition. OPF biochar has been shown to content high amount of potassium and it has
high adsorption rate for cations. It is therefore OPF biochar has the potential to reduce
the leachability of potassium from peat soil. Furthermore, palm frond is readily available
as raw material and has the great prospect to be converted into biochar, become source
of potassium and prevent the leachate.

1.2.1 Objectives

The objectives of this study are:


To determine the effect of contact time and pH on potassium adsorption capacity
onto biochar
To conduct Langmuir adsorption isotherm test on oil palm frond biochar in order
to determine adsorption capacity of potassium.
To study the desorption of potassium from biochar

3
CHAPTER 2

LITERATURE REVIEW

2.1 Overview of Biochar

Biochar is a type of charcoal produced by the conversion of biomass or


feedstock to a charred product under oxygen-limited condition in the reactor that known
as pyrolysis. Char is one of the most stable biologically produced carbon sources that
can add to soil says Dr Evelyn Krull from CSIRO Land and Water (Suzannah Lyons,
2009).

Biochar refers to carbon-rich materials (charcoal) produced by slow pyrolysis


process of biomass. Recently, biochar has been given much interest as soil
amendments to improve and maintain soil fertility and also its ability to increase soils
carbon sequestration (Downie. A and Joseph S, 2007). Carbon sequestration is a
natural or artificial process by which the carbon dioxide is removed from the atmosphere
and held in solid or liquid form. Biochar ability to sequester carbon in the soil depends on
its stable nature and therefore, it will provide long turnover time of biochar in soil. It is
one of the solutions for climate change. Biochar has the potential to be an immediate
solution to reducing the global impact of farming. The burning and natural decomposition
of trees and agricultural matter contributes a large amount of CO 2 that released to the
atmosphere. Biochar can store this carbon in the ground and reducing the greenhouse
effect.

4
2.1.1 Production of Biochar

Biochar can be produced by the pyrolysis process. Pyrolysis is defined as


the thermal decomposition of organic material through the application of heat without the
addition of extra air or oxygen. (Resource Recycling, 1995). At a temperature around
450C and under no addition of air, the hydrocarbon content of the waste reacts and
generates pyrolysis products, such as pyrolysis gas, pyrolysis coke, tar and biochar.
Basically, the pyrolysis process can be classified base on three operating conditions
which are slow pyrolysis, fast pyrolysis and flash pyrolysis. The biochar production will
increase through the slower rates pyrolysis while fast pyrolysis will formed mostly liquid
products. Generally, a low operating temperature and slow heating rate condition which
is slow pyrolysis is best choice for a high biochar yields. While, if the purpose is to
maximize the yield of bio-oils, a high temperature, short residence time and a high
heating rate is prefer (Demirbas, 2006). Table 1 below shows the main operating
parameters for different pyrolysis process.

Table 2.1: Basic operating parameters for pyrolysis processes. (Demirbas and Arin,
2002); and (Bolan et al. 2013)
Operating Slow pyrolysis Fast pyrolysis Flash pyrolysis
parameters
Pyrolysis 300-700 600-1000 800-1000
temperature (C)
Heating Rate 0.1-1 10-200 >1000
(C/Sec)
Particle Size (mm) 5-50 <1 <0.2

Solid Residence 300-550 0.5-10 <0.5


Time (Sec)

2.1.2 The Advantages of Biochar to Environment

Biochars physical and chemical properties have the ability to attract and hold
moisture, nutrients and agrochemical. (Verheijen et al, 2010). Recent research has

5
proven biochar enriched soils is able to reduce carbon dioxide and nitrous oxide
emission by 50-80% (Terrence Vaughn, 2012). Nitrous oxide is a significant greenhouse
gas, which are 310 times more potent than carbon dioxide. Researchers who have
tested the impact of bio-char on soil fertility say that much of the benefit may derive from
biochars vast surface area and complex pore structure, which is hospitable to the
bacteria and fungi that plants need to absorb nutrients from the soil. Steiner says, We
believe that the structure of charcoal provides a secure habitat for microbiota, which is
very important for crop production. Steiner and coauthors noted in the 2003 book
Amazonian Dark Earths that the charcoal-mediated enhancement of soil caused a 280
400% increase in plant uptake of nitrogen. Biochar complex pore structure can also
provide a secure habitat for microorganism and fungi. These fungi can form a symbiotic
relationship with plant root fibers and allows greater nutrient uptake by plants. There is
speculation that these fungi may play a part in terra pretas ability to regenerate itself.
Terra preta is the dark soil that owes the black color to its weathered charcoal content or
by adding the charcoal to the soil.

Biochar addition to soil also can enhance crops yield (Glaser et al., 2002). It
improves plant growth, food production and sustainability in areas with depleted soils,
limited organic resources, insufficient water and access to agrochemical fertilizers.
However, not all soils react to the same way with biochar but changes can be seen
within a year (Ref). Furthermore, biochar is able to enhance water and nutrient retention
by integrating into the soil structure. Biochar contain high surface area able to improve
water-holding capacity of soil. A study that is conducted by Tyron (1984) show the soil
water retention capacity increased about 18 % upon addition of 45% by volume of
biochar to sandy soil. Biochar can also help to prevent fertilizer runoff and leaching
(BIOCHAR info, 2009; Hamilton, 2007), reducing fertilizers uses and minimize
agricultural pollution to the surrounding environment.

2.2 Oil Palm Frond Biochar

The palm oil industry generates almost 94% of biomass in Malaysia, while other
agricultural and forestry by-products contribute the remaining of 6%. OPF are estimated
to be the highest available biomass amounting to 44.84 million tonnes in Malaysia

6
(Fauziah Sulaiman, 2012). OPF are a by-product of the cultivation of oil palm trees
(Elaeis guineensis Jacq.). The rapid development of the palm oil industry since the
1990s, notably in South-East Asia (Malaysia, Indonesia), has caused an increasing
output of fibrous wastes derived from the harvesting of oil palm fruit bunches, from both
pruning management practices and replanting operations (Dahlan, 2000). Up to 100
kg/ha (DM basis) of OPF can be produced daily (Ishida et al., 1997). Using an annual
production figure of 11 t DM/ha (Husin et al., 1986 cited by Lim et al., 2000) and a total
world harvest from 15 million ha in 2009 (FAO, 2011), it can be estimated that 164
million t DM of OPF are produced every year in the world.

OPF and oil palm trunks used to be burned but environmental concerns led to
banning the practice in the 1990s. Now they are usually left on the ground to decompose
and fertilize the soil (Lim et al., 2000). A considerable amount of research, notably in
Malaysia and Indonesia, has been carried out to demonstrate the nutritional value and
economic viability of OPF for ruminants in order to improve self-sufficiency in dairy and
meat production (Abu Hassan et al., 1996; Wan Zahari et al., 2003). OPF are a low-
protein, 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 (Dahlan et al., 2000; Dahlan et al., 1994). Whole OPF
(the petiole and leaflets) are usually chopped into lengths of about 2 cm and fed either
fresh, dried, pelleted or ensiled in combination with other ingredients as total mixed
rations. Many treatments have been proposed to increase its nutritional value (Abu
Hassan et al., 1996; Dahlan, 2000).

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2.2.1 Advantages and disadvantages of using Oil Palm Frond Biochar

Table 2.2 stated the advantages and disadvantages listed by Australia and New Zealand
Biochar Researches Network (2008)

Advantages Disadvantages

Neutralizes and maintain the pH of Soil Feedstock availability

Improves cation exchange capacity for Biochar handling


greater mineral delivery to plant roots.
Increases the water holding capacity of Biochar system deployment
the soil
Improves resistances to infestation by
fungus, nematodes and insects
Provides a rich source of carbon to build
hummus/organic matter and increase
productivity

2.3 Potassium

Potassium is an essential and major nutrient for crop production (Alfaro et al.,
2003; Zhang et al., 2011). Plants need potassium in large amount and it is referred as a
macronutrient (Black, 1957). Plants require K for photosynthesis, ATP production,
translocation of sugars, starch production in grains, nitrogen fixation in legumes, and
protein synthesis. In oil palm and other crops, K strengthens stalks and stems, thus
helping with disease and lodging. Plants take up potassium as K+ ions. The
concentration and availability of K in the soil is primarily controlled by inorganic
processes. Although K does not pose the potential environmental concerns that nitrogen
(N) and phosphorous (P) do, an understanding of K cycling and availability is important
for the management of profitable, long-term cropping systems because K exists in finite
amounts in the soil and can limit plant use of other nutrients. (Sparks D. L., 2000)

8
2.3.1 K in Soil

Potassium exists in the soil as dissolved K+ ions (solution K), exchangeable K,


non-exchangeable K, and mineral K (Figure 2.1). Plants can only directly absorb solution
K, yet solution K concentrations range from only 1 to 10 mg/L (ppm). Plant available K
includes solution K and exchangeable K. Solution K+ exists in equilibrium with the
exchangeable, nonexchangeable, and mineral phases of potassium (Figure 2.2). Unlike
N and P, K is not incorporated into the plant structure; therefore, K is not bound in
organic forms, but is quickly released back into the soil from crop residues and roots.
(Korb, Jones, & Jacobsen, 2002).

Exchangeable K is weakly sorbed to the surfaces of soil particles and can rapidly
replenish solution K. Nonexchangeable or fixed Kis held within clay layers by strong
bonds that make the nutrient inaccessible to plants. Mineral K is contained largely in un-
weathered primary minerals such as feldspars and micas. The processes governing the
availability of K are mineral weathering, clay fixation and release, sorption and
desorption, leaching, erosion, and plant uptake. K has been traditionally expressed as
potash, or K2O. (Korb, Jones, & Jacobsen, 2002).

Figure 2.1: K found in the soil (Hoeft et al., 2000)

9
Figure 2.2: The potassium cycle.

2.4 Overview of Peat Soil

Peat soil is an important ecosystem that provides a significant contribution to the


global climate stability. It fixes more carbon from the atmosphere and approximately
one-quarter of the carbon stored in land plants and soils. It consists of decomposed
plant fragments and in Malaysia, peat soils are considered as problematic soil with little
economic benefit, apart from it being used selectively for agricultural activity. The total
world coverage of peat soil is about thirty million hectares with Canada and Russia
having the largest distribution of peat (Zainorabiddin, 2010). More than sixty percent of
the worlds tropical peat lands are found in South-East Asia (Lette, 2006). Most notable
are the large peat land on the island of Borneo (belonging to Indonesia, Malaysia and
Brunei) and Sumatra (Indonesia). However, there are also significant occurrences in
other parts of Indonesia, Malaysia, Vietnam, Thailand and the Philippines. The main
contributory functions and benefits of peat soil are within the engineering disciplines of
hydrology, agriculture, social-economics, biodiversity habitats and carbon sequestration.
The western coastal lowlands of Malaysia (such as Kukup) are mangroves that
represent the initiation of peat soil formation.

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2.5 Adsorption

The word "adsorption" was coined in 1881 by German physicist (Heinrich Kayser,
1853-1940). Adsorption is the adhesion of atoms, ions, or molecules from a gas, liquid,
or dissolved solid to a surface. This process creates a film of the adsorbate on the
surface of the adsorbent. This process differs from absorption, in which a fluid (the
absorbate) is dissolved by or permeates a liquid or solid (the absorbent), respectively.
(Loebenstein & V., 1963).

Adsorption is the accumulation or enrichment of chemical substances onto a


surface or interface. The adsorbing phase is defined as the adsorbent, and the material
being adsorbed the adsorbate. The adsorbent is required to have an extremely large
surface area on which the adhesion of contaminants can occur. It can occur between
two phases, such as gas-liquid, gas-solid, liquid-liquid, or liquid-solid interface. In the
field of water treatment, adsorption 10 has been proven as an efficient removal process
for numerous types of pollutants, where ions or molecules are removed from liquids by
adsorption onto solid surfaces (Worch, 2012).

Solid surfaces are active and energetic sites, which are able to interact with
solutes due to their specific electronic and spatial properties. Since adsorption is a
surface based process, the surface area plays an important role in determining
adsorbents quality (Crittenden and Thomas, 1998). Adsorption process can be divided
into two types which is physical adsorption and chemical adsorption.

2.5.1 Type of Adsorption Process

Adsorption processes can be classified into two types which are physical
adsorption (van der Waals adsorption) or chemisorption (activated adsorption)
depending on the type of forces between the adsorbate and the adsorbent.

a) Physical Adsorption (Van Der Waals Adsorption)


Physical adsorption also known as physisorption, intermolecular attractions occur
between favorable energy sites (Pira, 2011)The adsorbate is attached to the surface by

11
weak van der Waals forces and therefore it is less strongly attached to the surface
compared to chemisorption. There is not any exchange of electrons in this process
(Cecen and Aktas, 2012). Physical adsorption occurs quickly and may be mono-
molecular (unimolecular) layer or monolayer, or 2, 3 or more layers thick (multi-
molecular). It begins as a monolayer then it becomes multi-layer, and if the pores are
close to the size of the molecules, more adsorption occurs until the pores are filled with
adsorbates. Accordingly, the maximum capacity of a porous adsorbent can be more
related to the pore volume rather than to the surface area.

b) Chemisorption
Chemisorption involves the formation of chemical bonds between the adsorbate
and adsorbent is a monolayer, often with a release of heat much larger than the heat of
condensation (Ref). Chemisorption from a gas generally takes place only at
temperatures greater than 200oC, and may be slow and irreversible. Since chemical
reactions happen more rapidly at higher temperatures, chemisorption is more
predominant at high temperatures compared to physical adsorption (Cecen and Aktas,
2012).

2.5.2 Factors Affecting Adsorption of Potassium

Adsorption is not a homogeneous process and there are many factor can affect the
efficiency of its process such as pH, temperature, surface area of adsorbent, particle
size of adsorbent, contact time or residence time and initial concentration.

a) pH
Many investigate has been done in studies about the effect of pH on the bio-
sorption of potassium onto different adsorbents. Coir-pith carbon activated chemically by
H2SO4 achieved the highest adsorption of potassium in the pH range of 6-10 (Kumar et
al., 2010). Varying results on the influence of pH on the adsorption process indicate its
complex nature. However, for the majority of other sorbents, most results infer that the
optimum pH is slightly acidic to around neutral (4 - 7) (Kumar et al., 2010).

12
b) Temperature
The connections between properties of the adsorbent and solute is also affected
the adsorption process of potassium. Thus, the effects of temperature are different for
different adsorbents and solutes. In general, numerous studies have shown that by
increasing the temperature of the solution to a specific range, the adsorption efficiency of
different adsorbents also increases. (Benyoucef and Amrani, 2011) attributed the higher
phosphorus adsorption capability with increasing temperature to the expansion of pore
size at higher temperatures. Moreover, Kumar et al. (2010) suggested that elevated
temperature leads to an increase in the rate of diffusion of potassium ions, which in turn
enhances the adsorption efficiency.

c) Surface area of adsorbent


Adsorbent is porous substances and have a high surface area that can adsorb
others substances called adsorbate onto its surface by intermolecular forces. Larger
sizes of adsorbent will have a greater adsorption capacity. Surface area measures how
much exposed area is there on solid material. Surface area of an adsorbent increasing
by breaking or grinding the solid material into smaller pieces.

d) Particle Size of Adsorbent


Internal diffusion and mass transfer limitation to the penetration of the adsorbate
inside the adsorbent can minimize by the smaller particles size. This can explain using
the higher rate of removal by adsorbent with smaller particle size due to availability of
more surface area on the adsorbent (Karthikeyan et. al., 2003).

d) Adsorbent Dosage
Many scientific studies indicated that potassium adsorption will increase when
adsorbent dose up to a specific level increasing, and then it retained constant. This can
be explained by adding more adsorbent to the solution so that more binding sites are
available for the sorption process. Hence, more potassium can be adsorbed (Kumar et
al., 2010).

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e) Contact Time
The design and economics of any adsorption system are mostly caused by the
kinetics process. The needed contact time varies between different adsorbents and
contaminants. The adsorption process will be more complete when the contact time is
hinger. This is because when contact time is higher, more molecules of contaminant can
adhere and accumulate to the surface of adsorbent. The adsorption process continues
until it reached an equilibrium states. Normally, the adsorption of potassium by most
adsorbents reached equilibrium in less than 1 hour (Yue et al., 2010).

f) Initial Concentration
Generally, the adsorption effectiveness decreases if there is a significant
increase in the initial concentration of potassium. It has been researched that the
increase in potassium uptake capacity when the initial concentration was raised from
100 mg/L to 300 mg/L (Xu et al. 2009)

2.6 Adsorption Isotherm

Adsorption is usually studied through graphs know as adsorption isotherm. The


adsorption isotherm indicates how the adsorbed molecules distribute between the liquid
phase and the solid phase when the adsorption process reaches an equilibrium state
(Nwabanne and Igbokwe 2008). The adsorption capacity and also the performance of
the activated carbon were usually predicted from equilibrium sorption isotherm (Kumal et
al., 2008). Adsorption isotherm is very useful in choosing the best carbon for adsorption
or purification need (Potgieter, 1991; Ochonogor and Ejikeme, 2005). It is the graph
between the amounts of adsorbate (x) adsorbed on the surface of adsorbent (m) and
pressure at constant temperature. Different adsorption isotherms have been Freundlich,
Langmuir and BET theory. Adsorption isotherm is useful in representing the capacity of
an activated carbon for adsorbing organics from a biochar. The more effective certain
activated carbons were shown by steeper isotherm produced (Weber, 2005).

Several models describe the process of adsorption. Although many theories of


adsorption have been put forward to explain the phenomena of adsorption (Ansari and
Mohammad-Khan, 2009; Potgieter, 1991; Amuda and Ibrahim, 2006) the isotherms of

14
Freundlich and Langmuir is the most well-known isotherm that used in adsorption to
understand the extent and degree of favorability of adsorption. (Ding, 2008).

2.6.1 Langmuir Adsorption Isotherm

In 1916, Irving Langmuir published a new model isotherm for adsorption, which
retained his name. It is a semi-empirical isotherm derived from a proposed kinetic
mechanism. This isotherm was based on different assumptions one of which is that
dynamic equilibrium exists between adsorbed gaseous molecules and the free gaseous
molecules.

Below are the characteristics of Langmuir model (Armenante, 2010) and figure
2.3 illustrate the Langmuir isotherm graph:

a) Adsorption is a reversible process

b) Adsorbed layer is made up from a single layer of molecules

c) The adsorbed molecules do not move on the surface of the adsorbent. However, they
can lose back to the solution.

d) The enthalpy of adsorption is the same for all molecules independently of how many
have been adsorbed.

15
Figure 2.3: Graph of Langmuir Isotherm (Armenante, 2010)

The linear form of Langmuir isotherm equation is given as:


1 1
=( ) + ( )

Where:
Qe = Amount of solute adsorbed on the bio-sorbent at equilibrium
Ce =Residual concentration of solute remaining in solution after adsorption is completed.
Q0 = Maximum amount of the solute per unit weight of to form a complete monolayer on
the surface (mg / g).
b = constant related to the affinity of the binding sites (L/m)

16
2.7 Theory and Mechanism of Atomic Adsorption Spectroscopy (AAS)

Atomic absorption spectroscopy (AAS) is a spectra analytical procedure for the


quantitative determination of chemical elements using the absorption of optical radiation
(light) by free atoms in the gaseous state. In analytical chemistry the technique is used
for determining the concentration of a particular element (the analyte) in a sample to be
analyzed. AAS can be used to determine over 70 different elements in solution or
directly in solid samples used in pharmacology, biophysics and toxicology research.
When a small amount of a solution of a metal ion is placed in the flame of a Bunsen
burner, the flame turns a color that is characteristic of the metal ion. A sodium solution
gives a yellow color, a potassium solution results in a violet color, a copper solution
gives a green color. As implied previously, only a very small number of the atoms in the
flame are actually present in an excited state at any given instant. Thus there is a large
percentage of atoms that are in the ground state and available to be excited by some
other means, such as a beam of light from a light source. AA takes advantage of this fact
and uses a light beam to excite these ground state atoms in the flame. Thus AA is very
much like molecular absorption spectrophotometry in that light absorption (by these
ground state atoms) is measured and related to concentration. The major differences lie
in instrument design, especially with respect to the light source, the "sample container,"
and the placement of the monochromator.

Figure 2.4: Schematic diagram of AAS (A.Erxleben, 2009)

17
CHAPTER 3

METHODOLOGY

3.1 Introduction

The overall experiments conducted during this study is illustrated in the flow chart

Flowchart 3.1: Overall process of the project

18
3.2 Feedstock selection

The sample used in this project is biochar from stems of oil palm frond which
already produced by previous students.

Figure 3.1: Oil Palm Frond (OPF)

3.2.1 Biochar Production (Fares, 2015)

Fresh oil palm frond was collected in selected location then was cut into 3 cm x 3
cm dimension as in Figure 3.4 before put in oven at 40 0 C to reduce moisture content
as low as possible or dry the frond under sun for 3 days or until the frond was dried.

Figure 3.2: Prepared Stem of Oil Palm Frond

19
After that the dried frond were arrange in single layer and wrapped with two layer
of aluminum foil to prevent presence of oxygen during pyrolysis process. The pyrolysis
process were conducted in a muffle furnace with temperature 345 0 C for 45 minutes.
The temperature of 345 0 C and 45 minutes retention time was choosen based on
recent research that this temperature and retention time produce the lowest pH value
and minimum hydrophobicity (Fahmi,2015) .

3.3 Preparation of standard curve of potassium by Atomic Adsorption


Spectroscopy

Solutions for standard curve were prepared by diluting Potassium standard


solution (1000 mg/L) using 100mL volumetric flask based on formula (M1V1=M2V2). As
in Figure 3.3(a) and analysed by using AAS in Figure 3.3(b)

(a) (b)

Figure 3.3: (a) Diluting standard solution (b) AAS for standard curve

3.4 Potassium Isotherm Study and analysis of potassium

The samples were studied by using several methods as stated in 3.4.1 to3.4.4 below:

20
3.4.1 Isotherm study with variety of contact time

50 ppm of potassium solution was prepared from KOH. The solution was poured
into six test tubes and added with 0.1 g of biochar. Another six test tubes were also
prepared as blank (without biochar). All test tubes then put in the water bath shaker with
constant temperature 25 C. Every hour, one of test tube with biochar and one without
biochar were taken out from the shaker, filtered and analyze by using AAS. This was
repeated for six hours.

3.4.2 Adsorption isotherm study with variety of concentration

The potassium solution was prepared from the potassium hydroxide (KOH) for 0.1, 0.5,
1.0, 2.0, 5.0, 10, 50, 100, 150 ppm by using 100mL volumetric flask and then transferred
the solution into three test tubes as triplicate samples and added with 0.1 g biochar for
each. Another three test tubes were prepared without adding biochar as blank. Control
was done by adding 0.1 g biochar into three test tubes that contained 10mL of deionized
water. As showed in Figure 3.4 (a) and (b)

a) b)

Figure 3.4: (a) Sample with Biochar (b) Sample without biochar

All the test tube were sealed with plastic wrap and put in the water bath shaker
with temperature 25C for 24 hours as in Figure 3.5

21
Figure 3.5: Water Bath Shaker

After 24 hours, the samples then filtered by using filter paper and keep the
biochar. The filtered samples were analyzed their concentration of potassium by AAS.

Figure 3.6: Filtration process

22
3.4.3 Desorption Study

The biochar in the filter paper was filtered and put in the oven at the temperature
of 105C for 24 hours. After 24 hours, the biochar on the filter paper were rinse with 10
ml distilled water. The collected filtrate used for test potassium adsorbed. These have
been shown at figure 3.7 (a) and (b) below.

(a) (b)

Figure 3.7: (a) Dried Biochar (b) Rinsing process

3.4.4 Adsorption isotherm with variety of pH

500 ppm of Potassium solution was prepared in volumetric flask. The solution
then divided into three beakers by adjusting to difference pH which were pH 3, 5 and 7
with 0.1M sodium hydroxide and 0.1M nitric acid using dropper. The pH value was
checked by using pH meter. Before used pH meter, it must be calibrate with buffer 4 and
buffer 7 to make sure the reading of pH accurate. Then, distribute the solution in each
beaker to six different test tubes for 10mL each. Three test tubes were added with 0.1g
biochar and other rest as blanks. Brought all the test tubes and put in water bath shaker
with constant temperature 25C for 24 hours. After that filter the solution using filter

23
paper and measured the adsorption of potassium by AAS. This has shown at figure 3.8
(a) and (b) below.

(a) (b)
Figure 3.8: (a) 0.1M of Sodium Hydroxide and 0.1M Nitric Acid (b) Standardising pH
meter

24
CHAPTER 4

RESULT AND DISCUSSION

4.1 Introduction

This chapter shows all the result recorded for this study. Potassium (K)
adsorption isotherm was carried out to determine the maximum amount of K able to be
adsorbed by oil palm frond (OPF) biochar. The amount of K adsorbed was determined
by using Atomic Absorption Spectroscopy and the data was fitted into Langmuir
Isotherm Model

4.2 K Isotherm Study

K adsorption isotherm study studies onto biochar was conducted with variable
parameters as reported below.

4.2.1 Adsorption isotherm study with various contact time

This research started with analysis between contact time (hour) and the amount
of K adsorbed. The experiment was conducted for 6 hours with 50 mg/L of K in the initial
samples. Samples were taken every hour and analyzed for K remaining in the solution.
Adsorption of K by OPF biochar only took only one hour to adsorb all the K, beyond that
there was no detectable change (Figure 4.1).

25
This deduced that maximum amount of K was fully adsorbed by the biochar by
an hour. After one hour, there was no longer adsorption of K because the K already fully
adsorb by the biochar.

2
1.8
Amount Adsorbed, mg/g

1.6
1.4
1.2
1
0.8
0.6
0.4
0.2
0
0 1 2 3 4 5 6 7
Contact Time (Hour)

Figure 4.1: Graph for contact time (hour) against amount of K adsorbed (ppm)

Contact time is one of the most effective factors in batch adsorption process.
Adsorption rate initially increased rapidly, and the optimal removal efficiency was
reached within about 60min. Further increase in contact time did not show significant
change in equilibrium concentration that is, the adsorption phase reached equilibrium.
These results indicated that so far as adsorption kinetics is concerned 24 hours is
enough time to reach a satisfactory equilibrium condition. Our findings agree with the
results of Du et al. (2004) who have reported 24 hour times for achieving steady state
condition in biochar.

4.2.2 Adsorption isotherm study with variety of concentration

26
After completion of contact time experiment against the amount of potassium
adsorbed, the research then proceeds with the effect of initial concentration to the
adsorption of K. The effect of the initial concentration of K adsorbed onto OPF biochar
was studied at different initial concentrations ranging from 0.1 to 200 ppm. The sample
was equilibrated on a horizontal shaker for 24 hours. Then the solution was filtered with
Whatman filter paper and analyze for K by atomic adsorption spectroscopy. Sorbed K
was calculated as the difference between equilibrium solution K concentration and initial
K concentration of solution based on below formula:

Blank (without biochar) (sample with biochar - Control) = Amount Adsorbed

Theoretically, the amount of K to adsorb must increase with increasing initial


concentration. This indicates saturation of the active sites on the biochar. The increase
adsorption of K and reduction in availability of adsorbed K in biochar may be due high
base concentration in biochar which can provide larger quantities of positive charge to
surface and free divalent base cations. (Sui et al, 2012). The adsorption isotherm of K
was shown in Figure 4.2. The amount K adsorbed (ppm) directly proportional to the
increasing of initial concentration of K (ppm). This revealed that the adsorption sites
remain unsaturated during the adsorption reaction whereas the number of sites available
for K adsorption by increasing the initial concentration. (Mitra & Prakash, 1956)

27
30

25
Amount K adsorbed, mg/g

20

15

10

0
0 5 10 15 20 25
Initial Concentration, K, ppm

Figure 4.2: Graph for Initial Concentration K (mg/L) against Amount K adsorbed (mg/g)

Adsorption is usually described through adsorption isotherms, that is, functions


which connect the amount of adsorbate on the adsorbent at constant temperature.
Distribution of K between the liquid phase and the solid phase can be described by
several isotherm models such as Langmuir. The Langmuir isotherm assumes monolayer
adsorption onto a surface containing a finite number of adsorption sites of uniform
strategies with no transmigration of adsorbate in the plane surface. Once a site is filled,
no further sorption can take place at that site. This indicates that the surface reaches a
saturation point where the maximum adsorption of the surface will be achieved. (Angelo
Lucia, 2013). The isotherm is represented by

1 1
=( ) + ( )

The linear plot of specific adsorption (Ce/qe) against the equilibrium


concentration (Ce) (Figure 4.3). shows that the adsorption obeys the Langmuir model.

28
0.12
y = 0.0069x + 0.0017
0.1
R = 0.9798

0.08
Ce/qe

0.06

0.04

0.02

0
0 2 4 6 8 10 12 14 16
Ce

Figure 4.3: Langmuir Isotherm Model

From above equation and graph the amount of maximum capacity of the
potassium per unit weight of to form a complete monolayer on the surface (mg/g) can be
determine which is 6.78 mg/g . As shown from R2 value, the adsorption data fitted to
Langmuir equation. This is because the fit value for correlation coefficient is 1. So based
on the result, the R2 value of Langmuir isotherm is fit because the correlation coefficient
is 0.9798 which approximate to 1. The essential characteristics of the Langmuir
isotherms can be expressed in terms of a dimensionless constant separation factor or
equilibrium parameter, RL which is defined as:

RL=1/ (1+b Co)

Where b is the Langmuir constant and Co is the initial concentration of K. The RL value
indicates the shape of isotherm as shown in table 4.3.1. An isotherm is favorable, if its
fixation capacity grows rapidly with concentration in equilibrium in liquid phase, convex
form. The maximum for a highly favorable isotherm is irreversible adsorption, where the
amount adsorbed does not depend on the decrease in concentration, down to very low

29
values, unlike unfavorable isotherms, which have a low adsorption capacity at low
concentrations in equilibrium, concave forms.

The RL values between 0 and 1 indicate favorable adsorption. The RL were found
to be 0.9101 to 0.0051 for the initial concentrations of 0.1-200 mg/L K, indicating that the
adsorption of K by biochar was favorable.

Table 4.1: Relationship between RL and the type of isotherm (Manoj Kumar, 2013)
Relationship between RL and the type of isotherm

RL Type of Isotherm

RL > 1 Unfavorable

RL = 1 Linear

0 < RL < 1 Favorable

RL = 0 Irreversible

4.2.3 Desorption study

Desorption studies help in the elucidating the mechanism of metal ion removal
and recovery from metal-loaded adsorbent and also for the regeneration and recycling of
spent adsorbents, which in turn may reduce operational cost and protect the
environment. In order to assess the OPF biochar ability to release the K adsorbed,
desorption was evaluated at varying initial concentration of potassium.

30
Figure 4.4: Bar Chart for an initial concentration mg/g against amount of K desorb mg/g

Figure 4.4 showed that the higher the initial concentration of K loaded in the OPF
Biochar, the higher the amounts of K ion are. The rate of desorption increased with
increasing hydrogen ion or hydroxonium ion concentration. Although complete
desorption were not achieved, it is clear from the results that the amount of K desorb
was depends to the amount of K adsorbed. The data also indicates that desorption is a
time dependent variable. It may be possible to obtain 100% desorption if the initial
concentration is extended.

4.2.4 Adsorption isotherm study with variety of pH.

The pH of a solution is an important parameter in the adsorption process. During


this study, results revealed that the adsorption of K was strongly dependent on the pH of
the solution. The effect of pH on adsorption of K onto biochar was studied at pH 3, 5, 7
and the maximum adsorption capacity of biochar was found to be at pH 3. K precipitated

31
because of the high concentration of OH ions in the adsorption medium and so
adsorption experiments at pH 5 and 7 could not be performed. (Mitra & Prakash, 1956)

16

Amount of K adsorbed mg/g 14


12
10
8
6
4
2
0
3 5 7
pH value

Figure 4.5: Bar Chart pH value against Amount of K adsorbed (ppm)

Increasing pH value from 3.0 to 5.0 was observed to diminish K adsorption


capacity by OPF. The pH 7 showed the highest variability base on their standard
deviation. There was no reason for the character of adsorption to be uniform. At pH 5,
there was no adsorption occurs might be involve chemisorption in some system that
indicated by a shift of K in the OPF biochar and also because at pH 5 there was no
electrostatic attraction so adsorption of K was zero. Besides, more probably at pH 5, K
preferred to be solutions rather than adsorb the biochar and its tend to the leachability of
K. Further study need to be done to determine the reason behind reduced leaching in pH
5.

32
CHAPTER 5

CONCLUSION

This study were to determine the effect of contact time and pH on potassium
adsorption capacity onto biochar and to conduct Langmuir adsorption isotherm test on
OPF biochar in order to determine maximum adsorption capacity of potassium. It also to
study desorption of potassium from biochar by the peat soil. The result obtained from the
isotherm study of different initial concentration then was plotted to Langmuir isotherm
model. It deduced that the Langmuir Model is fitted with isotherm study because the
value of R2 is approximate to 1 which the correlation coefficient is 0.9798. This model
then determined the maximum capacity of K to form a complete monolayer on the
surface (mg/g) which is 6.78 mg/g. Desorption of potassium also has been studied
through bar chart that showed the higher the initial concentration of K loaded in the OPF
Biochar, the higher the amount of metal ion recovered from the OPF Biochar. Although
complete desorption were not achieved, it is clear from the results that the amount of K
desorb was depends to the initial K concentration. Besides, the bar chart has been done
to display the relationship between pH value and amount of K adsorbed. It showed the
maximum adsorption capacity of biochar was found to be at pH 3 compared to pH 5 and
pH 7 due to the weakening of electrostatic force of attraction between the oppositely
charged adsorbate and adsorbent. At pH 5no adsorption occurs might be K preffered to
be solution rather than adsorb the biochar which cause the leachability of K. Overall,
these study conclude that oil palm frond biochar has the potential to prevent the
leachability of potassium from peat soil except for pH further study need to be done to
find the reason behind the K leachability.

33
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