FINAL YEAR PROJECT 2: DISSERTATION

REMOVAL OF ZINC USING AGRICULTURAL WASTES BY COLUMN

ADSORPTION METHOD

PREPARED BY:
ELISHA LEE SU ERN
15111

SUPERVISOR:
AP. DR. SHAMSUL RAHMAN MOHAMED KUTTY

Dissertation submitted in partial fulfilment of the requirements for the

Bachelor of Engineering (Hons)
(Civil Engineering)

MAY 2014

Universiti Teknologi PETRONAS

Bandar Seri Iskandar
31750 Tronoh
Perak Darul Ridzuan

1
 CERTIFICATION OF APPROVAL

REMOVAL OF ZINC USING AGRICULTURAL WASTES BY COLUMN

ADSORPTION METHOD

by

Elisha Lee Su Ern

15111

A project dissertation submitted to the

Civil Engineering Programme
Universiti Teknologi PETRONAS
in partial fulfillment of the requirement for the
BACHELOR OF ENGINEERING (Hons)
(CIVIL)

Approved by,

_____________________
(Dr. Shamsul Rahman)

UNIVERSITI TEKNOLOGI PETRONAS

TRONOH, PERAK
May 2014

2
 CERTIFICATION OF ORIGINALITY

This is to certify that I am responsible for the work submitted in this project, that the
original work is my own except as specified in the references and acknowledgements,
and that the original work contained herein have not been undertaken or done by
unspecified sources or persons.

__________________
(ELISHA LEE SU ERN)

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 ACKNOWLEDGEMENT

I would like to express my gratitude to all those who gave me assistance and support to
in completing this thesis.

First and foremost, I would like to express my heartfelt gratitude to my supervisor, AP.
Dr. Shamsul Rahman Mohamed Kutty, for his continuous support of my final year
project study and research. His immerse knowledge, stimulating suggestion and
unending patience has been crucial throughout the duration of this project.

Besides that, I would like to thank Mr. Henry and Miss Leong for their time, continuous
support and insightful comments in ensuring the success of this project. I also extend my
thanks to the lab technicians, Mr. Zaaba and Mr. Khairul, for their invaluable assistance
throughout the project duration.

Last but not least, I would like to thank my family for the unending love and
encouragement in helping me finish this research project.

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 ABSTRACT

The adsorption of Zinc ions in a fixed bed column using rice husk ash, Ageratum
Conyzoides ash, sugarcane bagasse ash and RSA was investigated. Adams-Bohart model
and Yoon-Nelson kinetic models were used to analyze the column performance. The rate
constant for Adams-Bohart model decreases with increase in bed depth. Adsorption
capacity for the adsorption of Zinc obtained from Adams-Bohart model ranged from
484.8 mg/L to 1653.4 mg/L for sugarcane bagasse, 1057.8 mg/L to 2550.2 mg/L for rice
husk ash, 727.2 mg/L to 1830.3 mg/L for Ageratum Conyzoides and 375.3 mg/L to
1308.0 mg/L for RSA. The maximum adsorption capacity increases with increase in bed
depth. For Yoon-Nelson model, the rate constant decreases with increase in bed depth.
The time required for 50% breakthrough obtained from Yoon-Nelson model ranged
from 39.89 mins to 882.76 mins for sugarcane bagasse, 41.49 mins to 954.30 mins for
rice husk ash, 38.38 mins to 916.55 mins for Ageratum Conyzoides, and 31.09 mins to
733.28 mins for RSA. The time required for 50% breakthrough increases with increase
in bed depth. The kinetic data fitted well to both models with R2 values generally above
0.9.

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 TABLE OF CONTENTS

ACKNOWLEDGEMENT ............................................................................................................. 4
ABSTRACT................................................................................................................................... 5
LIST OF TABLES ......................................................................................................................... 8
CHAPTER 1 ................................................................................................................................ 10
INTRODUCTION ....................................................................................................................... 10
1.1 Background of Study ......................................................................................................... 10
1.2 Problem Statement ............................................................................................................. 11
1.3 Objectives .......................................................................................................................... 14
1.4 Scope of Study ................................................................................................................... 14
CHAPTER 2 ................................................................................................................................ 15
LITERATURE REVIEW ............................................................................................................ 15
2.1 Adsorbate ........................................................................................................................... 15
2.1.1 Zinc Chloride .............................................................................................................. 15
2.2 Adsorbents ......................................................................................................................... 16
2.2.1 Rice Husk Ash ............................................................................................................ 16
2.2.2 Sugarcane Bagasse Ash .............................................................................................. 17
2.2.3 Ageratum Conyzoides Ash .......................................................................................... 18
2.2.4 RSA ............................................................................................................................. 19
2.3 Adsorption.......................................................................................................................... 20
2.3.1 Fixed Bed Column Adsorption ................................................................................... 21
2.3.2 Estimation of Breakthrough Curve ............................................................................. 22
CHAPTER 3 ................................................................................................................................ 23
METHODOLOGY ...................................................................................................................... 23
3.1 Project Flow Chart ............................................................................................................. 23
3.2 Experiment Methodology .................................................................................................. 23
3.2.1 Adsorbate Preparation ................................................................................................. 23
3.2.2 Adsorbents Preparation ............................................................................................... 24
3.2.3 Column Studies ........................................................................................................... 24
CHAPTER 4 ................................................................................................................................ 26
RESULTS AND DISCUSSION .................................................................................................. 26

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 5.1 Absorbent Characteristics .................................................................................................. 26
5.2 Breakthrough curves .......................................................................................................... 27
5.3 Modeling of breakthrough curves ...................................................................................... 32
5.3.1 Adams-Bohart Model .................................................................................................. 32
5.3.2 Yoon-Nelson Model .................................................................................................... 35
CHAPTER 5 ................................................................................................................................ 38
CONCLUSION ............................................................................................................................ 38
REFERENCES ............................................................................................................................ 39
APPENDICES ............................................................................................................................. 42

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LIST OF TABLES
Table 1.1 Malaysia’s Effluent Discharge Limits 10

Table 1.2 Maximum Contaminant Levels and Health Risks Associated 11

Table 1.3 Comparison of Heavy Removal Technologies 11

Table 5.1 Throughput volume to exhaustion and breakthrough 29

Table 5.2 Adams-Bohart constant and correlations at different bed 32

depths

Table 5.3 Yoon-Nelson constant and correlations at different bed 35

depths

LIST OF FIGURES

Figure 2.1 Rice husk sample 15

Figure 2.2 Sugarcane bagasse sample 16

Figure 2.3 Ageratum Conyzoides sample 17

Figure 3.1 Schematic Diagram of Column 23

Figure 3.2 Experimental Setup 23

Figure 5.1 Electron micrograph of Aegratum Conyzoides leaves ash 24

Figure 5.2 Electron micrograph of rice husk ash 24

Figure 5.3 Electron micrograph of sugarcane bagasse ash 25

Figure 5.4 Breakthrough curves expressed as Ct/C0 versus t 26

for 3 cm bed depth

Figure 5.5 Breakthrough curves expressed as Ct/C0 versus t 26

for 10 cm bed depth

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Figure 5.6 Breakthrough curves expressed as Ct/C0 versus t 27
for 15 cm bed depth

Figure 5.7 Breakthrough curves expressed as Ct/C0 versus V 28

for 3 cm bed depth

Figure 5.8 Breakthrough curves expressed as Ct/C0 versus V 28

for 10 cm bed depth

Figure 5.9 Breakthrough curves expressed as Ct/C0 versus V 29

for 15 cm bed depth

Figure 5.10 Adams-Bohart model for sugarcane bagasse ash 31

Figure 5.11 Adams-Bohart model for rice husk ash 31

Figure 5.12 Adams-Bohart model for Ageraturum Conyzoides ash 31

Figure 5.13 Adams-Bohart model for RSA 31

Figure 5.14 Yoon-Nelson model for sugarcane bagasse ash 34

Figure 5.15 Yoon-Nelson model for rice husk ash 34

Figure 5.16 Yoon-Nelson model for Ageraturum Conyzoides ash 34

Figure 5.17 Yoon-Nelson model for RSA 34

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 CHAPTER 1
INTRODUCTION

1.1 Background of Study

The adsorption method for heavy metal removal has been popular ever since its
introduction into the wastewater treatment industry due to its simplicity, sludge-free
operation and the availability of various adsorbents (Sugashini & Begum, 2012). Up till
recently, the conventional adsorbent used was activated carbon, but despite its prolific
use has remained costly due to the processes it is required to undergo to achieve higher
removal capacity. These high operation costs will be pose a problem to many smaller
scale companies looking to meet their discharge limits

Due to this, research has intensified over the years looking for low cost
alternatives with high metal binding properties as adsorbents. Low cost adsorbents are
defined as those materials that are abundant in nature, a form of by product or waste
material, and require little or no processing. In this project, the removal capacity of rice
husk ash, sugarcane bagasse ash, Ageratum Conyzoides ash, and a mixture of all three
materials, termed RSA, in removing Zinc, Zn ions is investigated using fixed bed
column adsorption method.

Rice husk is one of the most popular low cost agro based adsorbent because of its
high availability. In Malaysia, over 2 million tons of rice is produced yearly and about
20% of that is wasted in the form of rice husk (Giaccio, Sensale, & Zerbino, 2007).
Sugarcane baggase is an equally available waste product which is evident in its
utilization as a biofuel in North America. Besides that, Ageratum Conyzoides, better
known as ‘goat weed’ is known to be found in abundance in tropical and sub-tropical
climates (Chandrakala, 2013).

The utilization of these biosorbents based on recent publications is further

elaborated in this paper and their removal efficiency compared.

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1.2 Problem Statement
Heavy metals are defined as metals whose density exceeds 5 g/cm3. Heavy
metals are essential to the human body in minute amounts but poses significant health
hazards in higher concentrations. The existence of stringent laws regarding the discharge
limits of heavy metals is due to its ability to remain in a system and accumulate over
time. Table 1.1 shows the discharge limits according to Malaysia's Environmental Law,
ENVIRONMENTAL QUALITY ACT, 1974, the Malaysia Environmental Quality
(Sewage and Industrial Effluents) Regulations, 1979, 1999, 2000. Zinc has a density of
7.14 g/cm3 and is therefore categorized as a heavy metal and is known to cause ‘metal
fume fever’ with severity increasing as toxic level increases. Table 1.2 shows the
various health risks associated with zinc poisoning.

Among the various methods of wastewater treatment available, activated carbon

adsorption has gained increasing popularity due to its simplicity, sludge-free operation
and the availability of various adsorbents (Sugashini et al., 2012). However, despite its
prolific use, activated carbon proves to be still a costly option because of its lack of
availability. Table 1.3 summarizes the advantages and disadvantages of current heavy
metal removal methods. Therefore, extensive research has been made to identify low
cost alternatives as adsorbents.

This project addresses the issue of availability of conventional activated carbon

adsorbents and investigates the removal efficiencies of three agro based adsorbents
namely rice husk ash, sugarcane bagasse ash and Ageratum Conyzoides ash.

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Table 1.1: Malaysia’s Effluent Discharge Limits ([Link]
[Link]/resources/discharge-standards/[Link])

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Table 1.2: Maximum Contaminant Levels and Health Risks Associated (Babel &
Kurniawan, 2003)

Table 1.3: Comparison of Heavy Removal Technologies (Farooq et al., 2010)

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1.3 Objectives
The aim of this project is to study the removal efficiency of Zinc, Zn ions using rice
husk ash, sugarcane bagasse ash, Ageratum Conyzoides ash, and the mixture of all three
adsorbents by adsorption method.

The effect of varying bed depths on the adsorption process is also investigated by
increasing adsorbent mass under constant flow rate.

1.4 Scope of Study

The experiment is conducted using Zinc Chloride solution as the adsorbate, which is
fed to columns with different adsorbents. The experiment will cover:

1. Rice husk ash, Sugarcane bagasse ash, Ageratum Conyzoides ash and a
mixture of all three materials, termed RSA.

2. Bed depths of 3 cm, 10 cm and 15 cm.

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 CHAPTER 2
LITERATURE REVIEW

2.1 Adsorbate
2.1.1 Zinc Chloride
Zinc has a density of 7.14 g/cm3 and is therefore categorized as a heavy metal
and is known to cause ‘metal fume fever’ with severity increasing as toxic level
increases. One of the methods in removing heavy metals that has grown in popularity
over the years is the adsorption method (Sugashini et al., 2012). This is due to its
simplicity, sludge free operation and the availability of various adsorbents. Numerous
researches have been conducted using different adsorbents in investigating Zn ions
removal.

A study conducted on Zn(II) removal by Rocha et al. (2008) using rice straw as a
biosorbent portrayed excellent efficiency in metallic ions removal from its aqueous
solution. The study also investigated the effects of temperature and pH on the adsorption
process using batch adsorption method.

Similar studies were conducted on Zn(II) removal by Meunier et al. (2003) and
Saeed et al. (2005) using cocoa shells and papaya wood respectively found removal
efficiencies to be more than 50% for both adsorbents. Both experiments were testing
several metal ions and encouraging results were obtained for all cases. Cocoa shell and
papaya wood registered Zn ions removal efficiencies of 64% and 67% respectively.

In 2000, an experiment investigating both modified and unmodified fruit residue

(FR) in removing toxic heavy metals was documented (Senthilkumar et al., 2000). The
author found phosphated-FR (P-FR) to be slightly more effective than untreated FR in
removing Zn ions at lower pH levels. P-FR tested with initial adsorbate pH of 4.0 was
found to be most effective clocking a maximum value of 88%.

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2.2 Adsorbents
2.2.1 Rice Husk Ash
Among the various agro based adsorbents, rice husk is one of the most readily
available, with Malaysia producing approximately 2.2 million tons of rice in 2007 (Food
and Agriculture Organization, 2008). Out of that figure, 20% is wasted in the form of
rice husk (Giaccio, Sensale, & Zerbino, 2007). In recent years, numerous innovations
have been seen using both modified and unmodified rice husk ash. These can be
credited to its chemical stability and high mechanical strength, thus increasing its
adsorbing potential (Ahmaruzzaman & Gupta, 2011).

In 2011, the usage of alternative low cost adsorbents in Lead, Pb removal was
investigated (Surchi, 2011). Rice husk was among the several materials tested with all of
them exhibiting high adsorption capacity of more than 80% removal efficiency. The
effects of contact time were investigated by running the experiments for different
durations of 10 to 300 minutes in separate runs. The experiment also observed a general
trend of decreasing removal efficiency with increasing Pb ion concentration.

A similar research was conducted a year later with modified chitosan carbonized
rice husk in the removal of Chromium, Cr(VI) ions (Sugashini & Begum, 2012). It also
reported similar results with a maximum removal of 99.8% under optimum conditions.
The experiment was conducted using both batch and fixed bed column adsorption
methods. From the batch studies conducted, Cr(VI) ions percentage removal was found
to be maximum at pH 2. This value was then used as a constant in investigating effect of
flow rate and bed height.

16
 Figure 2.1: Rice husk sample

2.2.2 Sugarcane Bagasse Ash

Sugarcane bagasse is a waste material that originates from sugarcane stalks. It
appears in the form a fibrous material that contains typically 40 to 50% moisture which
is detrimental to its current use as a biofuel. However, with suitable processing,
sugarcane bagasse has proved to be a valuable innovation in various fields. A good
example can be seen in studies conducted on the utilization of sugarcane bagasse as a
biosorbent in metallic pollutants removal (Joseph et al., 2009). This article highlighted
its uses as both a biofuel and the potential of improving its characteristics for its
implementation in the adsorption process.

A research done by Universiti Teknologi MARA in 2006 identified the potential

of sugarcane bagasse as a low cost adsorbent in the removal of Cadmium, Cd ions
(Ibrahim, Hanafiah, & Yahya, 2006). The study was conducted using batch experiments
and shown dependency on agitation rate, pH and contact time and the results fitted the
Langmuir isotherm model. However, it was found to be less efficient in the removal of
Zinc, Zn ions with maximum value obtained at a mere 30% (Kishor, Vilas, Nilesh, &
Motiraya, 2012). The author’s preparation methods include drying the adsorbents at
100oC and sieving the grinded residue to a range of 1.5 mm to 1.8 mm. The experiment
concluded by identifying the limitations of its activation methods in preparing sugarcane
bagasse for adsorption of Zn ions.

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 Figure 2.2: Sugarcane bagasse sample

2.2.3 Ageratum Conyzoides Ash

More commonly known as ‘goat weed’, Ageratum Conyzoides is found in
abundance in tropical and sub-tropical climates. It is traditionally known for its
medicinal properties but such uses were limited due to its toxicity. As research
progresses with technology, its alternative application is currently being explored in the
adsorption process.

Due to it being comparatively new, there is a lack in literature regarding its

adsorption properties and capacities. However, an in-depth study conducted by
Chandrakala, G. (2013) using batch experiments found the maximum removal capacity
of Ageratum Conyzoides leaf powder under optimum conditions were close to 90% for
both Lead, Pb and Chromium, Cr ions. The study was conducted under varying
parameters investigating the effects of agitation time, biosorbent size, biosorbent dosage,
pH of aqueous solution, and the initial concentration of Cr in aqueous solution. A similar
study conducted in 2012 with Ageratum Conyzoides leaf powder as a biosorbent in Iron,
Fe(III) ions removal, concluded that it is a promising material with encouraging results
portraying high removal capacity (Chandrakala et al., 2012). The study also highlighted
the optimum conditions required for biosorption of Fe(III) from wastewater.

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 Figure 2.3: Ageratum Conyzoides sample

2.2.4 RSA
RSA is a mixture of rice husk ash, sugarcane bagasse ash and Ageratum
Conyzoides leaf ash (1:1:1 ratio by mass). With a growing demand for cheap and readily
available adsorbents, more and more innovation can be seen in the wastewater treatment
industry. The method of mixing different adsorbent to obtain a specific performance is
not entirely new and has seen a few researches exploring this possibility.

A study conducted by Singh et al. (2008) investigated the removal efficiency of

Arsenic, As(III) from its aqueous solution using a homogenous mixture of china clay
and fly ash has concurred that is dependent on the various operating parameters such as
concentration, temperature and pH. The experiment was conducted using batch
experiments and found that the homogenous mixture showed favorable results under
suitable conditions.

Aziz et al. (2005) conducted a similar research in investigating the possibility of

mixture a number of carbons with limestone in removing heavy metals (Ni, Cd, Pb, Zn)
from its aqueous solution. The author investigated charcoal, coconut shell carbon and a
mixture of these carbons with limestone. The results obtained showed an increase in
heavy metals removal efficiency where limestone was present.

Positive results from previous researches have opened up possibilities in mixing

various biosorbents with conventional activated carbon or other materials. If proved

19
feasible, this can be seen as a move to overcome issues of limited availability and
substantially reduce costs where activated carbon is involved, without sacrificing
adsorbent efficiency. Apart from that, a mixture of biosorbents may also complement
each other in target treatment of various heavy metals in wastewater.

2.3 Adsorption
Adsorption is defined as a process where the atoms of the adsorbate form a layer
on the surface of the adsorbent. This differs from the absorption process where
absorption involves the entire volume of the materials involved. Sugashini and Begum
(2012) affirmed the efficiency of the adsorption method at lower concentration levels
due to its simplicity, sludge-free operation and availability of various adsorbents.
Adsorbents used are required to be thermally stable and able to resist abrasion with
small pore diameters resulting in a larger surface area for higher adsorption capacity.
Although activated carbon has been widely utilized in adsorption processes throughout
the region, it continues to pose a significant cost due to its lack of availability. In view of
this issue, research has intensified over the years, focusing on various low cost waste
products as alternative adsorbents to replace conventional activated carbon (Babel &
Kurniawan, 2002). Under lower concentration, various agro based waste has exhibited
efficient removal capacity while substantially reducing costs.

The rate of separation between the components is affected by 2 main factors

which are adsorbent activity and solvent polarity. To encourage good separation, the
factors have to be inversely proportional to each other. A high adsorbent activity with
low solvent polarity will yield better results and vice versa (Faizal & Kutty, n.d.). Faizal
and Kutty (n.d.) also highlighted the limitations of batch adsorption in larger scale
processes. In this project, the fixed bed column adsorption method will be adopted to
investigate the efficiency of 3 different agro based waste product in relation to different
bed depths. In this process, industrial wastewater will be simulated in the form of Zinc
Chloride solution as the adsorbate. It will be contacted with the adsorbents until
saturation. A graph denoting effluent over influent ratio (Ct/C₀) with time (t) will be
plotted in the form of an S-shape breakthrough curve. The breakthrough point and

20
exhaustion point are between the ranges of 5 to 10% and 90 to 95% respectively (Faizal
& Kutty, n.d.).

2.3.1 Fixed Bed Column Adsorption

This process typically involves a packed bed of adsorbents in a fabricated
column of predetermined dimensions. The absorbate usually in the form of aqueous
solutions is contacted with the adsorbents until saturation occurs. A graph denoting
effluent over influent ratio (Ct/C0) with time (t) will be plotted in the form of an S-shape
breakthrough curve. The process is affected by various factors such as influent flow rate
and adsorbent bed depths.

A study conducted in 2012, investigated the adsorption of Pb(II) and Cu(II) in a

fixed bed column using activated carbon prepared from nipa palm nut. The author
utilized Thomas model and Yoon and Nelson kinetic model in analyzing the column
performance. For Yoon and Nelson model, the rate constant increased when flow rate,
initial ion concentration and bed height is increased. Conversely, the time required for
50% breakthrough decreased with increase in flow rate, bed height and initial ion
concentration.

A similar experiment was conducted using fixed bed columns to investigate

aqueous phenol removal with activated carbon prepared from sugarcane bagasse
(Karunarathne et al., 2013). However, analysis of the column performance was done
using Langmuir and Freundlich equilibrium isotherms. There are various parameters to
consider when evaluating performance such as solution initial concentration, flow rate,
and amount and particle size of adsorbents. The study concluded that an increase in
adsorbent dose increases the adsorbent capacity of the bed.

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 2.3.2 Estimation of Breakthrough Curve
a) Adams–Bohart Model
The Adams–Bohart adsorption model was applied to the experimental data for
description of the initial part of the breakthrough curve (Kumar et al., 2012). This
Adams–Bohart model was developed by Adams and Bohart (1920) for the
adsorption of chlorine on charcoal (Bohart et al., 1920) which focused on
characteristic parameters, such as maximum adsorption capacity (N0) and kinetic
constant (kAB). The linearized form of Adams–Bohart model is presented in the
equation below:

C  k N Z
ln  t   k AB C t  AB 
 C  F

Where;
kAB is the kinetic constant (L/[Link]), F is the linear flow rate (mL/min), Z is the bed
depth of the column (cm), N0 is the saturation concentration or the maximum sorption
capacity (mg/L) and t is the time (min)

b) Yoon–Nelson Model
A simple theoretical model developed by Yoon–Nelson was applied to investigate
the breakthrough behavior of zinc on the various adsorbents tested. Thus, the values
of kYN (a rate constant) and τ (time required for 50% breakthrough) could be obtained
using non-linear regressive analysis from Yoon–Nelson equation as presented in
equation below:

Ct
ln[ ]  KYN t  KYN
Co  Ct

Where;
KYN is the rate velocity constant (L/min), τ is time required for 50% adsorbate
breakthrough (min), and t is time (min)

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 CHAPTER 3
METHODOLOGY

3.1 Project Flow Chart

• Preliminary research on existing studies on the topic from journals and

books
Literature
Review • Understand the concept of adsorption and wastewater treatment

• Design an experiment to compare the efficiency of rice husk, sugarcane

bagasse and Ageratum Conyzoides
Experiment • Prepare the equipment and materials needed prior to the experiment

• Conduct the experiment and collect the data

Data • Analyse the data and prepare discussion
collection

• Conclude the experiment

Conclusion • Prepare the final report

3.2 Experiment Methodology

3.2.1 Adsorbate Preparation
Wastewater will be simulated in the form of Zinc Chloride, ZnCl2 solution. A
stock solution of 0.1 M is prepared by dissolving 13.62 g of ZnCl2 in 1000 ml of distilled
water. The stock solution is then diluted to the desired concentration of 20.0 mg/L with
distilled water. Metallic ions concentration is measured using a spectrophotometer.

23
 3.2.2 Adsorbents Preparation
The Ageratum Conyzoides plants were collected from Tronoh, Perak and the
leaves separated. The leaves are washed with distilled water and dried extensively at
80oC for 24 hours before undergoing incineration in a floor standing Carbolite Furnace
at 800oC for 1 hour. The subsequent ash is sieved into size range of 75 μm to 150 μm
and stored in air tight bags until required.

Both sugarcane bagasse and rice husk will be obtained from a local production
mill and will undergo the same preparation procedures for a more precise comparison.

3.2.3 Column Studies

A fixed bed column experiment was carried out using simulated wastewater in
the form of aqueous ZnCl2 solution. The adsorbents were packed in a clear pipe column
of 4.6 cm internal diameter and 40 cm height at varying bed depths of 3 cm, 10 cm and
15 cm. The ZnCl2 solution was pumped into the columns via peristaltic pumps at a
constant flow rate of 8 mL/min. The column was allowed to run until saturation occurs
with effluent Zn concentration readings taken every 5 minutes via a spectrophotometer.
Adsorbent sizes were kept constant between 75 μm to 150 μm. The experiment was
conducted under constant laboratory temperature of 25oC. Pressure in the column was
maintained at atmospheric pressure by leaving the top of the column open. A graph
denoting effluent over influent ratio (Ct/C0) with time (t) will be plotted in the form of an
S-shape breakthrough curve. Results will be fitted to Adams – Bohart model and Yoon –
Nelson model. Figure 3.1 shows the schematic diagram of the column. Figure 3.2 shows
the actual columns under preparation.

24
Figure 3.1: Schematic Diagram of Column

Figure 3.2: Experimental Setup

25
 CHAPTER 4
RESULTS AND DISCUSSION

5.1 Absorbent Characteristics

The figures below show the morphologies of the adsorbents under SEM analysis.
It can be observed that the materials exhibit a similar trend which is generally porous
and fibrous in nature. An uneven and heterogeneous surface area can be seen in the
structure of the Ageratum Conyzoides ash particles in Figure 5.1. Figure 5.2, however,
shows a smoother and larger surface area in the rice husk ash particles formed after
incineration at 800oC. The sugarcane bagasse ash consists of particles with different
shapes and sizes. Both coarse and porous particles are observed which concur with
morphology results obtained by Paya et al. (2002) and Batra et al. (2008).

Figure 5.1: Electron micrograph of Age- Figure 5.2: Electron micrograph of

ratum Conyzoides leaves ash rice husk ash
(Chandrakala, G., 2013) (Faizal & Kutty, n.d.)

26
 Figure5.3: Electron micrograph of sugarcane
Bagasse (Torres, J., 2014)

5.2 Breakthrough curves

A breakthrough curve is a plot of relative concentration versus time, where
relative concentration is defined as Ct/C0 with Ct as the concentration at a time, t, and C0
as the initial concentration. The breakthrough point is the time taken for the
concentration to reach its allowable value which is usually 5 to 10% of the initial value.
The time when the bed is fully saturated is known as the exhaustion point which occurs
when the concentration of the effluent is 90 to 95% of its initial concentration.

Figure 5.4 below shows the measured breakthrough curves for adsorption of Zinc,
Zn onto rice husk ash, sugarcane bagasse ash, Ageratum Conyzoides ash and RSA. A 20
mg/L Zinc Chloride, ZnCl2 solution was passed through the columns with bed depth
3cm at constant flow rate of 8 mL/min. It can be observed that the breakthrough time
varied with different adsorbents with rice husk ash having the longest breakthrough time.
The exhaustion points for all three materials are similar but RSA is seen to have slightly
reduced adsorption capacity with shorter breakthrough and exhaustion time. Rice husk
ash higher adsorption capacity can be attributed to its larger surface area and higher
silica content (Faizal & Kutty, n.d.).

27
 1
0.9
0.8
0.7
Ct/C0 0.6
0.5
0.4
0.3
0.2
0.1
0
20 40 60 80 100
Time, t (min)

Sugarcane Bagasse Ash Rice Husk Ash

Ageratum Conyzoides Ash RSA

Figure 5.4: Breakthrough curves for 3 cm bed depth expressed as Ct/C0 versus time, t
with different adsorbents (initial zinc concentration 20 mg/L, initial pH 5.0, flow rate 8
mL/min and temperature 25 ±1°C)

1
0.9
0.8
0.7
0.6
Ct/C0

0.5
0.4
0.3
0.2
0.1
0
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16
Time, t (hr)

Sugarcane Bagasse Ash Rice Husk Ash

Ageratum Conyzoides Ash RSA

Figure 5.5: Breakthrough curves for 10 cm bed depth expressed as Ct/C0 versus time, t
with different adsorbents (initial zinc concentration 20 mg/L, initial pH 5.0, flow rate 8
mL/min and temperature 25 ±1°C)

28
 The breakthrough curves in Figure 5.5 shows similar results for bed depth of 10
cm with similar breakthrough and exhaustion points for all three materials except RSA
which has slightly reduced performance due to the mixture.

1
0.9
0.8
0.7
0.6
Ct/C0

0.5
0.4
0.3
0.2
0.1
0
2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38
Time, t (hr)

Sugarcane Bagasse Ash Rice Husk Ash

Ageratum Conyzoides Ash RSA

Figure 5.6: Breakthrough curves for 15 cm bed depth expressed as Ct/C0 versus time, t
with different adsorbents (initial zinc concentration 20 mg/L, initial pH 5.0, flow rate 8
mL/min and temperature 25 ±1°C)

However, when the bed depth is increased to 15cm as shown in Figure 5.6, the
column containing rice husk ash sample is seen to pull forward in terms of exhaustion
point which is due to its higher adsorption capacity while RSA remains the least
performing column.

The breakthrough curves can also be represented in the form of Ct/C0 against
volume of water treated, V (mL) to determine the throughput volume required for
breakthrough and exhaustion. Figure 5.5 below shows the relationship between the
concentration ratios with volume of water treated (mL) for the different adsorbents. The
data clearly depicts the characteristic “S” shaped curve in ideal adsorption systems. The
throughput volume to breakthrough and exhaustion point for each adsorbent is tabulated
in Table 5.1 below.

29
 1
exhaustion point
0.9
0.8
0.7
0.6
Ct/C0

0.5
0.4
0.3
0.2
0.1 breakthrough point
0
80 160 240 320 400 480 560 640 720 800
Volume of water treated, V (mL)

Sugarcane Bagasse Ash Rice Husk Ash

Ageratum Conyzoides Ash RSA

Figure 5.7: Breakthrough curves for 3 cm bed depth expressed as Ct/C0 versus volume of
water treated, V (mL) with different adsorbents (initial zinc concentration 20 mg/L,
initial pH 5.0, flow rate 8 mL/min and temperature 25 ±1°C)

1
exhaustion point
0.9
0.8
0.7
0.6
Ct/C0

0.5
0.4
0.3
0.2
breakthrough point
0.1
0
0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 5.5 6 6.5 7 7.5 8
Volume of water treated, V (L)

Sugarcane Bagasse Ash Rice Husk Ash

Ageratum Conyzoides Ash RSA

Figure 5.8: Breakthrough curves for 10 cm bed depth expressed as Ct/C0 versus volume
of water treated, V (mL) with different adsorbents (initial zinc concentration 20 mg/L,
initial pH 5.0, flow rate 8 mL/min and temperature 25 ±1°C)

30
 1
0.9 exhaustion point
0.8
0.7
0.6
Ct/C0

0.5
0.4
0.3
0.2
breakthrough point
0.1
0
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19
Volume of water treated, V (L)

Sugarcane Bagasse Ash Rice Husk Ash

Ageratum Conyzoides Ash RSA

Figure 5.9: Breakthrough curves for 15 cm bed depth expressed as Ct/C0 versus volume
of water treated, V (mL) with different adsorbents (initial zinc concentration 20 mg/L,
initial pH 5.0, flow rate 8 mL/min and temperature 25 ±1°C)

Adsorbent Bed depth Throughput volume Throughput volume

(cm) to breakthrough, VB to exhaustion, VE
(mL) (mL)
3 160 580
Rice husk ash 10 2000 6750
15 4000 17000
Ageratum 3 100 560
Conyzoides ash 10 1750 7000
15 4500 14000
Sugarcane bagasse 3 120 660
ash 10 2000 6250
15 3500 13000
3 40 480
RSA 10 1000 6000
15 2500 12000

Table 5.1: Throughput volume to exhaustion and breakthrough for different type of
adsorbent and at different bed depths

31
 A general trend of increase in breakthrough and exhaustion point can be seen as
bed depth increases. This is due to an increase in binding sites as higher bed depth
increases the surface area available for adsorption. From the table 5.1, rice husk ash is
seen to generally have the longest breakthrough and exhaustion point, followed by
Ageratum Conyzoides, sugarcane bagasse and RSA.

5.3 Modeling of breakthrough curves

In this project, two models were used to describe fixed-bed column behavior and
to scale it up for industrial applications, namely Adams-Bohart and Yoon-Nelson
models. These models were applied to the experimental data to analyze performance
using fix bed column method.

5.3.1 Adams-Bohart Model

Adams–Bohart model was applied to the experimental data for description of the
initial part of the breakthrough curve. This model mainly focused on estimation of
characteristic parameters, such as maximum adsorption capacity (N0) and kinetic
constant (KAB). The linearized equation for Adams-Bohart model is:

C  k N Z
ln  t   k AB C t  AB 
 C  F

Where;
KAB is the kinetic constant (L/[Link]), F is the linear flow rate (mL/min), Z is the bed
depth of the column (cm), N0 is the saturation concentration or the maximum sorption
capacity (mg/L) and t is the time (min)

32
 0 0
5 10 15 20 25 30 35 40 5 10 15 20 25 30 35 40
-2
-2
-4
-4
-6

-6 -8

3 cm 10 cm 15 cm 3 cm 10 cm 15 cm

Figure 5.10: Adams-Bohart model for Figure 5.11: Adams-Bohart model for
sugarcane bagasse ash rice husk ash

0 0
5 10 15 20 25 30 35 40 5 10 15 20 25 30 35 40
-0.5
-1
-1
-2 -1.5
-2
-3
-2.5
R² = 0.9907
-4 -3

3 cm 10 cm 15 cm 3 cm 10 cm 15 cm

Figure 5.12: Adams-Bohart model for Figure 5.13: Adams-Bohart model for RSA
Ageratum Conyzoides ash

33
 The values of N0 and KAB for the breakthrough can be determined from the slope
and intercept respectively. Results are tabulated in Table 5.2 below:

Adsorbent Z KAB N0 R2
(cm) (L/[Link] x (mg/L)
10-2)
Sugarcane 3 2.4 484.8 0.9735
bagasse ash 10 2.0 923.4 0.9655
15 1.7 1653.4 0.9856
3 1.1 1057.8 0.9283
Rice husk ash 10 1.0 1704.9 0.9503
15 0.8 2550.2 0.9407
Ageratum 3 1.6 727.2 0.8948
Conyzoides ash 10 1.5 1278.6 0.9441
15 1.4 1830.3 0.9918
3 3.1 375.3 0.9849
RSA 10 2.9 901.8 0.9807
15 2.8 1308.0 0.9907

Table 5.2: Adams-Bohart constant and correlations at different bed depths for sugarcane
bagasse ash, rice husk ash, Ageratum Conyzoides ash and RSA

The Adams-Bohart adsorption model was applied to the experimental data for
the description of the initial part of the breakthrough curve. From Table 5.2, rice husk
ash is found to have the highest maximum adsorption capacity, N0 of 2550.2 mg/L at 15
cm bed depth. This is followed by Ageratum Conyzoides at 1830.3 mg/L, sugarcane
bagasse at 1653.4 mg/L and RSA at 1308.0 mg/L. It can also be seen from the table that
when bed depth increases, values of KAB reduces and N0 increases respectively. This is
due to an increase in surface area for binding during the adsorption process. The Adams-
Bohart model provides an accurate prediction of the breakthrough curve with most R2
values between 0.9 and 0.99.

34
 5.3.2 Yoon-Nelson Model
This model is applied to investigate the breakthrough behavior of Zn onto the
various different adsorbents tested. Thus, this model is focusing on the values of KYN (a
rate constant) and τ (time required for 50% breakthrough) which can be obtained using
non-linear regressive analysis from Yoon–Nelson equation as presented in below
equation:

Ct
ln[ ]  KYN t  KYN
Co  Ct

Where;
KYN is the rate velocity constant (L/min), τ is time required for 50% adsorbate
breakthrough (min), and t is time (min)

35
 2 0
5 10 15 20 25 30 35 40
0 -2
5 10 15 20 25 30 35 40
-2 -4
-4 -6
-6 -8
-8 -10

3 cm 10 cm 15 cm 3 cm 10 cm 15 cm

Figure 5.14: Yoon-Nelson model for Figure 5.15: Yoon-Nelson model for
sugarcane bagasse ash rice husk ash

1 1
0 0
5 10 15 20 25 30 35 40 5 10 15 20 25 30 35 40
-1
-1
-2
-2
-3
-4 -3

-5 -4

3 cm 10 cm 15 cm 3 cm 10 cm 15 cm

Figure 5.16: Yoon-Nelson model for Figure 5.17: Yoon-Nelson model for RSA
Ageratum Conyzoides ash

36
The values of KYN and τ for the breakthrough can be determined from the slope and
intercept respectively. Results are tabulated in Table 5.3 below:

Adsorbent Z KYN τ R2
(cm) (min-1) (min)
Sugarcane 3 0.0152 39.89 0.9856
bagasse ash 10 0.0133 432.45 0.9938
15 0.0110 882.76 0.9822
3 0.0188 41.49 0.9532
Rice husk ash 10 0.0176 488.02 0.9565
15 0.0155 954.30 0.9970
Ageratum 3 0.0142 38.38 0.9291
Conyzoides ash 10 0.0128 515.67 0.9839
15 0.0115 916.55 0.9956
3 0.0121 31.09 0.9850
RSA 10 0.0104 387.90 0.9957
15 0.0087 733.28 0.9968

Table 5.3: Yoon-Nelson constant and correlations at different bed depths for sugarcane
bagasse ash, rice husk ash, Ageratum Conyzoides ash and RSA
The Yoon-Nelson model confirms the data obtained from Table 5.2 with rice
husk having the longest 50% breakthrough time, τ at 15 cm bed depth, 954.30 mins.
Similarly, this is followed by Ageratum Conyzoides at 916.55 mins, sugarcane bagasse
at 882.76 mins and finally RSA at 733.28 mins. The experimental data fits well with the
Yoon-Nelson model with adsorbents having R2 values within ideal range of 0.93 to 0.99.
Comparing the values of R2 and breakthrough curves, both the Adams-Bohart and Yoon-
Nelson models can be used to describe the behavior of the adsorption of Zn in a fixed-
bed column.

37
 CHAPTER 5
CONCLUSION

The adsorptive removal of Zinc(II) from aqueous solution in a fixed bed column
using rice husk ash, sugarcane bagasse ash, Ageratum Conyzoides ash and RSA has been
investigated. Adams-Bohart and Yoon-Nelson kinetic models were used to describe the
column adsorption kinetics. The experimental data fitted the kinetic models. The rate
constants, adsorption capacity and time for 50% adsorbate breakthrough were dependent
on bed depth. The experimental breakthrough curve compared satisfactorily with the
breakthrough profile calculated by both models. The determined column parameters can
be scaled up for the design of fixed bed columns

38
 REFERENCES

1. Sugashini, S., & Meera, K.M. (2012). Column adsorption studies for the removal of
cr(vi) ions by ethylamine modified chitosan carbonized rice husk composite beads
with modelling and optimization. Journal of Chemistry, 2013(460971), 11.
2. Chandrakala, G. (2013). Studies on biosorption of chromium and lead using
ageratum conyzoides leaf powder and anacardium occidentale testa powder.
(Doctoral dissertation).
3. Food and Agriculture Organization for the UN. (2008, January 18). Rice market
monitor, vol. X, Issue 3. Retrieved from http:// [Link]/giews/english/
countryupdates/ 0607e/[Link]
4. Giaccio, G., de Sensale, G. R., & Zerbino, R. (2007). Failure mechanism of normal
and high-strength concrete with rice-husk ash. Cement and Concrete
Composites, 29(7), 566-574.
5. Ahmaruzzaman, M., & Gupta, V. K. (2011). Rice husk and its ash as low-cost
adsorbents in water and wastewater treatment. Manuscript submitted for publication,
Department of Chemistry, National Institute of Technology Silchar, Silchar-788010,
Assan,.
6. Surchi, K. M. S. (2011). Agricultural waste as low cost adsorbents for pb removal:
Kinetics, equilibrium and thermodynamics. International Journal of Chemistry, 3(3),
103-112.
7. Joseph, O., Rouez, M., Métivier-Pignon, H., Bayard, R., Emmanuel, E., & Gourdon,
R. (2009). Adsorption of heavy metals on to sugar cane bagasse: Improvement of
adsorption capacities due to anaerobic degradation of the biosorbent. Environmental
Technology, 30(13), 1371-1379. doi: 10.1080/09593330903139520
8. Ibrahim, S. C., Hanafiah, M. A. K. M., & Yahya, M. Z. A. (2006). Removal of
cadmium from aqueous solutions by adsorption onto sugarcane bagasse. American-
Eurasian Journal of Agricultural & Environmental Science, 3(1), 179-184.
9. Kishor, P. P., Vilas, S. P., Nilesh, P., & Motiraya, V. (2012). Adsorption of copper
(Cu2 ) & zinc (Zn2 ) metal ion from waste water by using soybean hulls and
sugarcane bagasse as adsorbent. International Journal of Scientific Research and
Reviews, 1(2), 13-23.
39
10. Chandrakala, G., Abhishek, B., Kumar, C. V. S., Meera, I., Naidu, S. V., &
Narasimha, R. M. (2012). Ageratum conyzoides leaf powder for decontamination of
iron (iii): Removal, adsorbent characterization and equilibrium modeling. Journal of
Environmental Research And Development,7(1A), 257-266.
11. Babel, S., & Kurniawan, T. A. (2002). Low-cost adsorbents for heavy metals uptake
from contaminated water: A review. Journal of Hazardous Materials, (B97), 219-
243.
12. Faizal, A. M., & Kutty, S. R. M. (n.d.). Removal of oil from water using microwave
incinerated rice husk ash (mirha) by using column adsorption method. Unpublished
manuscript, Civil Engineering Department, Universiti Teknologi PETRONAS, Perak,
Malaysia.
13. Kumar A. et al. (2012). Properties and Industrial Applications of Rice husk: A
review. International Journal of Emerging Technology and Advanced Engineering,
ISSN 2250-2459, Volume 2, Issue 10.
14. [Link], E.Q. Adams (1920), “Some aspects of the behavior of charcoal with
respect to chlorine,” J .Am Chem Soc, Vol.42, pp.523–44.
15. Y.H. Yoon and J.H. Nelson. (1984). “Application of gas adsorption kinetics. Part 1.
A theoretical model for respirator cartridge service time,” J. Am. Ind. Hyg. Assoc.,
Vol.45, pp.509-516.
16. Senthilkumaar, S., Bharathi, S., Nithyanandhi, D., & Subburam, V. (2000).
Biosorption of toxic heavy metals from aqueous solutions. Bioresource
Technology, 75(2), 163-165.
17. Meunier, N., Laroulandie, J., & Blais, J.F. (2003). Cocoa shells for heavy metal
removal from acidic solutions. Bioresource Technology, 90(3), 255-263.
18. Saeed, A., Akhter, M.W., & Iqbal, M. (2005). Removal and recovery of heavy
metals from aqueous solution using papaya wood as a new biosorbent. Separation
and Purification Technology, 45(1), 25-31.
19. Karunarathne, H.D.S.S., & Amarasinghe, B.M.W.P.K. (2013). Fixed bed adsorption
column studies for the removal of aqueous phenol from activated carbon prepared
from sugarcane bagasse. Energy Procedia, 34, 83-90.

40
20. Farooq, U., Kozinski, J.A., Khan, M.A., & Athar, M. (2010). Biosorption of heavy
metal ions using wheat based biosorbents – A review of the recent literature.
Bioresource Techonology, 101, 5043-5053.

41
 APPENDICES

1) Raw data for 3 cm bed depth

Sugarcane Ageratum
Bagasse Rice Conyzoides
Ash Husk Ash Ash RSA
0 0 0 0
0 0 0 3.2
1 0 2 4.4
20 1.8 0.6 3.4 6
3 1.8 6 7
5.8 3.8 7.8 8.2
9 5.8 8.6 10.2
40 10.2 7.4 9.6 13
13 10 12 15.6
13.4 15 13 16.8
15.6 15.8 14.4 18.4
60 16.8 18 16 19
17 18.4 17.6 19.6
18 18.8 19.2 20
18.6 19.4 19.4 20
80 18.8 19.6 19.8 20
19.4 20 20 20
19.8 20 20 20
20 20 20 20
100 20 20 20 20

42
2) Raw data for 10 cm bed depth

Sugarcane Ageratum
Bagasse Rice Conyzoides
Ash Husk Ash Ash RSA
0 0 0 0
1 0 0 0 0
0 0 0 1.8
2 0 0 1 3
0.2 0.6 1.8 3.8
3 0.8 1.6 2.6 4.6
2.6 2.4 3.4 5.8
4 3.2 3 4.8 6.4
4 3.6 5.4 7
5 4.6 4.6 5.8 8
6 5.6 6.6 8.4
6 6.8 6 7 9.2
7.4 6.6 7.8 10.2
7 8 7.8 8.4 11
9.6 8.8 8.8 12
8 11 10 9.6 12.4
13.4 11.6 10.6 13.2
9 14.2 12.6 11.2 14.2
15 13.4 12.4 15.4
10 16.8 14.6 13.6 16.4
17.8 15.8 14.4 17
11 18 16.8 15 18.2
18.4 17.2 16 18.8
12 18.8 17.8 17.2 19.2
19.2 18.4 17.8 19.8
13 19.6 18.6 18.4 20
19.8 19 18.8 20
14 20 19.4 19.2 20
20 19.8 19.6 20
15 20 20 19.8 20
20 20 20 20
16 20 20 20 20
20 20 20 20

43
3) Raw data for 15 cm bed depth

Sugarcane Ageratum
Bagasse Rice Conyzoides
Ash Husk Ash Ash RSA
0 0 0 0
2 0 0 0 0
0 0 0 0.6
4 0.4 0 0.2 1.8
1.2 0.8 0.6 3
6 2.2 1.2 1 4.4
2.8 2 1.8 5.4
8 3.4 3 2.4 6.8
4.4 3.6 3 7.6
10 5.2 4.4 4 8.8
6.4 4.6 4.8 9.4
12 7 5.2 5.6 10
7.8 7 6.6 10.6
14 9 7.6 7.4 11.6
9.8 8.4 8.4 12.8
16 10.2 8.8 9.6 13.8
10.8 9.8 10.6 15
18 12.4 10.6 11.2 16
13.8 11.4 12.4 16.6
20 14.4 12.2 13.6 17.2
15.4 12.8 14.4 17.8
22 16.6 13.6 15 18.4
17.6 14.6 16 18.8
24 18.2 15 17.2 19.2
18.6 15.8 17.8 19.8
26 19 16 18.4 20
19.4 16.6 18.8 20
28 19.8 17 19.2 20
20 17.4 19.6 20
30 20 17.6 19.8 20
20 18 20 20
32 20 18.4 20 20
20 18.6 20 20
34 20 19 20 20
20 19.4 20 20
36 20 19.8 20 20
20 20 20 20
38 20 20 20 20
20 20 20 20

44
45