CHAPTER ONE: INTRODUCTION

1.1 Background of Study

Water pollution remains one of the most pressing environmental challenges facing the modern
world, particularly in rapidly industrializing regions. Among the various pollutants, heavy metals
are of significant concern due to their toxicity, non-biodegradability, bioaccumulation in the food
chain, and potential to cause severe health issues in both humans and aquatic life. Heavy metals
such as lead (Pb), cadmium (Cd), chromium (Cr), copper (Cu), and mercury (Hg) are commonly
found in the effluents of industries including mining, metal plating, battery manufacturing,
tanneries, and textiles (Fu et al., 2020; Ali et al., 2021). These metals, even in trace
concentrations, pose serious ecological and health risks due to their persistence and toxicity
(Jaishankar et al., 2023).

Over the years, various methods have been developed for the treatment of heavy metal-
contaminated wastewater. These include chemical precipitation, ion exchange, reverse osmosis,
membrane filtration, electrochemical treatments, and coagulation-flocculation (Barakat, 2022;
Babel & Kurniawan, 2024). However, these conventional methods are often associated with
limitations such as high operational costs, production of secondary waste, low efficiency at low
metal concentrations, and complex operation requirements (Volesky, 2020; Mohan & Pittman,
2023). These challenges have spurred interest in alternative methods that are more sustainable,
efficient, and economically viable.

Adsorption has gained widespread attention as a practical and efficient method for removing
heavy metals from aqueous solutions. Among various adsorbents, activated carbon is widely
recognized due to its large surface area, high porosity, and excellent adsorption capacity
(Demirbas, 2024). However, the high cost of commercial activated carbon, usually produced
from coal, wood, or peat, limits its use, particularly in developing countries where financial
resources are constrained (Dada et al., 2022).

In response to this, research has increasingly turned to the use of low-cost, renewable, and
locally available agricultural waste materials as precursors for activated carbon. Such materials
not only offer a cost-effective solution but also provide a means of valorizing agricultural
residues, thus contributing to waste management and sustainability. Biomasses such as coconut
shells (Tan et al., 2021), rice husks (Srivastava et al., 2024), sawdust (Hameed et al., 2024), and
sugarcane bagasse (Senthil Kumar et al., 2022) have all been successfully used to produce
activated carbon for water purification purposes.

One such promising material is the palm kernel shell (PKS), a hard endocarp of the oil palm
fruit, which is abundantly available in palm oil-producing countries like Nigeria, Indonesia, and
Malaysia. In Nigeria, for example, the palm oil industry generates vast amounts of PKS as a by-
product, most of which are either discarded or used inefficiently for low-grade fuel or left to
decompose, contributing to environmental pollution (Auta et al., 2024). Palm kernel shells are
rich in lignocellulosic content, carbon-dense, and thermally stable, making them suitable raw
materials for producing activated carbon (Ahmad et al., 2024).
Several researchers have reported the feasibility of using PKS-based activated carbon for water
treatment. For instance, Ahmedna et al. (2023) demonstrated that PKS-based carbon has a high
surface area and pore volume suitable for adsorption applications. Njoku et al. (2023)
successfully used chemically activated PKS carbon for the removal of heavy metals such as lead
and cadmium, reporting significant adsorption efficiency. Similarly, Ogunlaja et al. (2024) found
that activation of PKS with phosphoric acid yielded activated carbon with enhanced adsorption
capacity due to the introduction of functional groups and improved porosity.

The choice of activation method, whether physical, chemical, or a combination of both, plays a
critical role in determining the performance of the activated carbon. Studies by Yorgun and
Yıldız (2022) showed that chemical activation using agents such as KOH or H₃PO₄ (Potassium
Hydroxide or Phosphoric Acid) often results in carbons with higher surface areas and better-
developed pore structures compared to physical activation methods alone. Lua et al. (2023) also
emphasized that activation temperature and time significantly influence the pore development
and surface chemistry of the final product.

Despite the growing body of literature on PKS-based activated carbon, many previous studies
have focused primarily on the removal of synthetic dyes or operated with synthetic metal
solutions under controlled laboratory conditions (Ofomaja et al., 2024; Tan et al., 2024). There
remains a gap in research concerning the performance of PKS-derived activated carbon in
treating real industrial wastewater, which often contains a complex mixture of contaminants and
varying pH, temperature, and ionic strength. Furthermore, few studies have conducted
comparative analyses between PKS-activated carbon and commercially available activated
carbon, especially in the context of regeneration and reusability over multiple cycles.

Given these research gaps, it becomes necessary to undertake a study that not only develops
activated carbon from palm kernel shells using optimized activation techniques but also
evaluates its adsorption performance under real-world conditions. Such a study would provide
critical insights into the practical applicability, efficiency, and economic viability of using PKS-
based activated carbon in industrial wastewater treatment, particularly in resource-constrained
environments.

The development of activated carbon from palm kernel shells represents a sustainable approach
to both waste valorization and environmental protection. It aligns with the principles of the
circular economy and sustainable development goal, particularly in addressing SDG 6 (Clean
Water and Sanitation), SDG 12 (Responsible Consumption and Production), and SDG 13
(Climate Action). By transforming a readily available agricultural waste into a valuable
adsorbent for heavy metal removal, this research has the potential to offer a scalable, cost-
effective, and environmentally friendly solution to industrial water pollution challenges.

1.2 Problem Statement

The increasing pace of industrialization has led to the generation of vast amounts of wastewater
contaminated with hazardous heavy metals such as lead, cadmium, chromium, and copper. These
pollutants are highly toxic, persistent in the environment, and can cause severe harm to
ecosystems and human health, even at low concentrations. Despite the existence of several
conventional treatment technologies, many are either too expensive, energy-intensive, or
inefficient when it comes to removing trace levels of heavy metals. This presents a significant
challenge, particularly in developing countries where resources for advanced treatment
technologies are limited.

Activated carbon is widely regarded as one of the most effective adsorbents for the removal of
heavy metals from water due to its high surface area and adsorption capacity. However, the high
cost of commercially produced activated carbon, which is typically derived from non-renewable
resources like coal and wood, limits its large-scale application in wastewater treatment,
especially in low-income settings. This economic barrier has led to an urgent need to explore
alternative, low-cost, and sustainable raw materials for activated carbon production.

Palm kernel shells (PKS), a by-product of the palm oil industry, are abundantly available
agricultural waste in many tropical countries, including Nigeria. Despite their potential as a raw
material for activated carbon production, they remain largely underutilized and are often
discarded or burned, contributing to environmental pollution. While preliminary studies suggest
that PKS can be effectively converted into activated carbon with promising adsorptive
properties, there is still a lack of comprehensive research focusing on optimizing the production
process, characterizing the material properties, and rigorously evaluating the performance of
PKS-based activated carbon in treating real industrial wastewater.

The absence of locally sourced, affordable, and effective adsorbents continues to hinder efforts
to mitigate heavy metal pollution from industrial effluents. Without viable alternatives, many
industries discharge untreated or partially treated wastewater into the environment, exacerbating
water quality issues and public health risks.

Thus, there is a clear and pressing need to develop and evaluate palm kernel shell-based
activated carbon as a sustainable, cost-effective solution for heavy metal removal in industrial
wastewater treatment. This research seeks to address this gap by converting waste into a valuable
resource for environmental protection, thereby contributing to both waste valorization and water
pollution control.

1.3 Aim

The aim of this research is to develop and evaluate activated carbon produced from palm kernel
shells for the effective removal of heavy metals from industrial wastewater.

To achieve the stated aim, this research will pursue the following specific objectives:

1. To collect and prepare palm kernel shells as raw material for the production of activated
carbon through suitable activation techniques (both physical and chemical).

2. To synthesize activated carbon from palm kernel shells under optimized conditions and
evaluate its physicochemical properties, including surface area, pore structure, functional groups,
and thermal stability.
3. To assess the adsorption efficiency of the produced palm kernel shell-based activated carbon
for removing selected heavy metals (e.g., lead, cadmium, chromium, and copper) from industrial
wastewater.

4. To investigate the effects of key adsorption parameters, such as contact time, pH, adsorbent
dose, and initial metal concentration, on the performance of the activated carbon.

5. To compare the performance of the palm kernel shell-based activated carbon with that of
commercially available activated carbon in terms of heavy metal removal efficiency.

6. To analyze the potential of reusability and regeneration of the developed activated carbon for
multiple cycles of heavy metal adsorption.

7. To recommend practical applications of palm kernel shell-based activated carbon for industrial
wastewater treatment, especially in resource-limited settings.

1.4 Significance of the Study

The growing concern over water pollution caused by industrial activities, particularly the release
of toxic heavy metals into the environment, has highlighted the urgent need for effective,
affordable, and sustainable wastewater treatment solutions. This study is significant for several
reasons, as it seeks to address both environmental and socio-economic challenges through
innovative resource utilization.

Firstly, the study promotes environmental sustainability by utilizing palm kernel shells, an
abundant agricultural by-product, as a raw material for producing activated carbon. In many
palm-producing regions like Nigeria, these shells are often considered waste and are either
discarded or burned, contributing to land and air pollution. By converting this biomass into a
valuable product, the research supports waste reduction, resource recovery, and the circular
economy model.

Secondly, the research contributes to the advancement of low-cost water treatment technologies,
which are especially needed in developing countries where access to sophisticated and expensive
water purification systems is limited. The development of palm kernel shell-based activated
carbon offers a cost-effective alternative to commercial activated carbon, which is often
financially out of reach for small- and medium-scale industries. Making such affordable options
available can encourage industries to adopt more responsible wastewater management practices.

Moreover, this study is expected to add to the scientific knowledge base by providing insights
into the physicochemical properties and adsorption performance of PKS-derived activated
carbon. The characterization and performance evaluation of the produced material under realistic
industrial conditions will offer practical information that can be applied in both academic
research and real-world water treatment systems.

In addition, the study supports the achievement of several United Nations Sustainable
Development Goals (SDGs), particularly SDG 6 (Clean Water and Sanitation), SDG 12
(Responsible Consumption and Production), and SDG 13 (Climate Action). By addressing water
pollution through eco-friendly innovations, the research aligns with global efforts toward
environmental protection and public health improvement.

Finally, the outcomes of this research have the potential to stimulate local economic
development. If scaled, the production of PKS-based activated carbon could create value chains
around agricultural waste processing, generate employment opportunities, and reduce the
reliance on imported treatment materials.

1.5 Scope of the Study

This research is focused on the development and evaluation of activated carbon derived from
palm kernel shells for the removal of heavy metals from industrial wastewater. The specific
scope includes:

• Raw Material Preparation: Sourcing, cleaning, drying, and processing of palm kernel shells.

• Activated Carbon Production: Applying physical and chemical activation techniques (e.g., with
KOH or H₃PO₄) (Potassium Hydroxide or Phosphoric Acid) under optimized conditions.

• Material Characterization: Determining surface area, porosity, morphology, and functional

groups using methods such as BET, SEM, and FTIR.( Brunauer–Emmett–Teller, Scanning
Electron Microscopy, Fourier Transform Infrared Spectroscopy)

• Adsorption Experiments: Testing the removal of heavy metals like Lead (Pb), Cadmium (Cd),
Copper (Cu), and Chromium (Cr) from real or simulated industrial wastewater.

• Parameter Optimization: Evaluating the influence of variables such as pH, contact time,
dosage, and metal concentration.

• Performance Comparison: Comparing PKS-based activated carbon with commercial activated

carbon.

• Reusability Assessment: Examining the regeneration and reuse of the produced carbon over
multiple cycles.

CHAPTER TWO: LITERATURE REVIEW

2.1 Heavy Metal Pollution in Wastewater

Water pollution remains one of the most critical environmental issues worldwide, especially in
developing countries experiencing rapid industrialization. Among various pollutants, heavy
metals pose the greatest threat to aquatic life and human health due to their non-biodegradable,
toxic, and bioaccumulative nature (Jaishankar et al., 2024). Industrial activities such as mining,
battery manufacturing, metal plating, tannery operations, and textile dyeing continuously
discharge metals like lead (Pb), cadmium (Cd), chromium (Cr), and copper (Cu) into aquatic
environments (Fu & Wang,2022). Once released, these metals persist in water systems, soil, and
even the food chain, where they may cause carcinogenic, neurotoxic, nephrotoxic, and
endocrine-disrupting effects. Unlike organic pollutants, heavy metals do not degrade and can
accumulate in living organisms, leading to chronic exposure risks.

Heavy metals reach water bodies via industrial discharges, urban runoff, agricultural leaching,
and improper disposal of electronics. They may exist in ionic or complexed forms, depending on
pH, redox conditions, and the presence of organic ligands.

Nigeria, for example, faces widespread industrial effluent contamination. Many small- and
medium-scale industries discharge untreated wastewater into rivers and open drains due to a lack
of enforcement and inadequate wastewater treatment facilities (Nabegu, 2014).

In Asia and South America, fast-developing nations suffer similar problems, as industries grow
faster than regulatory frameworks can adapt.

Heavy metals in water can affect aquatic life through gill damage, reproductive failure, and
bioaccumulation; cause groundwater contamination, affecting wells and boreholes; and harm
human populations via ingestion, inhalation, or dermal contact.

Given the gravity of the issue, finding cost-effective, sustainable, and efficient methods for
removing heavy metals from water is vital. The use of activated carbon derived from agricultural
waste, such as palm kernel shells, offers an environmentally and economically attractive
alternative.

Waste water treatment

3.1 Heavy Metal Removal

Palm shell AC has been reported to remove heavy metals such as lead, chromium and copper
ions in wastewater due to presence of some functional groups on Palm shell AC that have
chemical attraction towards metal ions, such as hydroxyl, lactone and carboxylic (Sulaiman et al.
2023). Lead is often found in wastewater from printed circuit board factories, electronics
assembly plants, battery recycling plants and landfill leachate. If exposed to human body, they
can cause central nervous system damage. Apart from that, lead can also damage the kidney,
liver and reproductive system, basic cellular processes and brain functions. The toxic symptoms
of lead are anemia, insomnia, headache, dizziness, and irritability, weakness of muscles,
hallucination and renal damages. Other than lead, copper is also widely used in electronics
industry. The copper in animal body is essential in their metabolism. However, excessive
ingestion of copper brings about serious toxicological concerns, such as vomiting, cramps,
convulsions, or even death (Fu and Wang, 2022). There are not many researches of heavy metal
removal from waste water by palm shell activated carbon as shown in Table 1.

Table 1 Reported heavy metal removal from waste water by palm shell activated carbon.

Heavy metal Removal Uptake (mg/g) Uptake (mmol/g) References Relevant Issues
Lead ions 95.2 0.46 Issabayeva et al. (2022) Adsorption at pH 5 is greater than at pH 3.
Additions of complexing agent, boric acid increase the uptake, while malonic acid reduces the
uptake.

92.6 0.44 Issabayeva et al. (2022) Unpretreated palm shell activated carbon can remove heavy
metal ions

1.337 - Onundi et al. (2023) The removal of lead ion is 100% probably due to the sulphate group
on the adsorbent.

Copper ions 30.5 0.48 Issabayeva et al. (2022) N/A

59.502 0.94 Hossain et al. (2022) N/A

1.581 Onundi et al. (2024) The removal of copper is 75% due to the high initial concentration.

Hexavalent Chromium 228.2 0.68 Owlad et al. (2023) N/A

Nickel 0.13 Onundi et al. (2024) The removal of nickel is

55% - the lowest between nickel, lead and iron. This is probably low concentration of nickel did
not favor nickel competition for the same available adsorption site on adsorbent.

3.2 Dyes removal

Textile industry is famous in the East Coast of Peninsular Malaysia, known locally as Batik
Industries. It is popular locally and internationally due to the high demand. However, the
industry generates high water pollution due to utilization of many chemicals. Textile industry
contains grease, wax, heavy metal, surfactant, suspended solid, and dyes (Ahmad, 2002).
Traditionally, dyes are extracted from minerals, plants, and animals which are not hazardous to
environment. However nowadays, they are substituted by chemicals. Among the chemicals used
are dioxin, heavy metals and formaldehyde, which are carcinogenic chemicals, thus hazardous to
the worker of the industries, environment, as well as the user. The study on palm shell AC has
been proven to remove dyes from textiles industry. Among the dyes are basic blue 9 and
methylene blue. The removal efficiency is summarized in Table 6.

Table 2 Reported dyes removal by palm shell AC

Type of dyes Capacities (mg/g) Researchers

Basic Blue 9 311.72 Jumasiah et al. (2022)

Methylene Blue 303.03 Choong et al. (2023)

Jumasiah et al. (2022) studied the removal of Basic Blue 9, with various initial concentrations in
batch mode adsorption. The adsorption fitted Redlich-Peterson isotherm; correspond to non-
linearity of dye adsorption to time. Choong et al. (2023) designed models that represent the
adsorption of methylene blue onto palm kernel shell and proved that the result can be used as
replacement of experimental data for various initial concentrations.

3.3 Other pollutants removal

Other than heavy metals and dyes removal, palm shell AC also capable to remove pollutants
from phenol group, as well as iodine. Phenol and its substituted can contaminate wastewater
from industries such as petrochemicals, coal gasification and pesticide manufacture because it is
suspected carcinogenic, extremely toxic to aquatic life and adding strong taste and bad odor to
water. The reported literatures of the removal are summarized in Table 3.

Table 3 Reported other pollutants removed by palm shell AC

Types of pollutants Capacities (mg/g) Researchers

Phenol 166 Jia & Lua (2022)

2,4,6-trichlorophenol (TCP) 9.04 Tan et al. (2023)

4-chloroguaiacol removal (4CG) 454.4 Hamad et al. (2023)

Iodine 1210 Lim et al. (2024)

2.2 Conventional Treatment Methods for Heavy Metal Removal

Several techniques are employed for removing heavy metals from industrial wastewater. These
include:

i. Chemical Precipitation

Chemical precipitation is one of the oldest and most commonly used methods. It involves the
addition of chemical reagents, such as lime (Ca(OH)₂), sodium hydroxide (NaOH), or sulfides
(e.g., Na₂S) to the contaminated water. These reagents react with dissolved heavy metal ions to
form insoluble metal hydroxides or sulfides, which precipitate (settle) out of the solution.

For example:

• Lead precipitation with lime:

Pb²⁺ + 2OH⁻ → Pb(OH)₂↓ (solid precipitate)

• Cadmium precipitation with sulfide:

Cd²⁺ + S²⁻ → CdS↓ (yellow precipitate)

Advantages:

• Simple and cost-effective for high-concentration wastewaters

• Fast reaction times

• Requires minimal operational training

• Can treat large volumes of wastewater

Limitations:

• Produces large amounts of sludge, which must be dewatered and disposed of as hazardous
waste

• Inefficient at low concentrations (e.g., <10 mg/L), especially for metals like nickel or arsenic

• Reagent overdosing can lead to chemical wastage or pH imbalance

• Can struggle with complex wastewater matrices containing multiple metal types

ii. Ion Exchange

Ion exchange uses synthetic resins—often in bead form—designed to selectively remove metal
ions from wastewater. These resins contain active sites loaded with counter-ions (like H ⁺ or
Na⁺) that are exchanged with the heavy metal ions in the water. Once saturated, the resin can be
regenerated using a concentrated acid or salt solution.

Example:

• Resin–Na⁺ + Pb²⁺ → Resin–Pb²⁺ + Na⁺

Advantages:

• High selectivity and can remove metals at very low concentrations (even ppb levels)

• Regenerable and reusable, reducing operational cost over time

• Compact system footprint, suitable for automated processes

Limitations:

• High initial investment cost

• Requires clean influent; susceptible to fouling by suspended solids, oils, and organic matter
• Spent regenerants (e.g., acid wash) need proper disposal

• Performance can vary with pH, temperature, and presence of competing ions

iii. Membrane Filtration (Reverse Osmosis, Ultrafiltration, Nanofiltration)

Membrane filtration methods use semi-permeable membranes to physically separate metal ions
from water. These membranes operate under pressure gradients, allowing water and smaller
particles to pass through while rejecting larger ions and contaminants, including heavy metals.

Types of membrane processes:

• Ultrafiltration (UF): removes large colloidal particles and some organic matter.

• Nanofiltration (NF): can remove divalent ions (like Pb²⁺, Zn²⁺) and small organic molecules.

• Reverse Osmosis (RO): removes nearly all ions, including monovalent metals and salts.

Advantages:

• Extremely high removal efficiency (>99% in some cases)

• Can treat a broad spectrum of contaminants

• Suitable for water reuse or zero liquid discharge (ZLD) systems

• Produces consistent water quality

Limitations:

• Expensive capital and operational cost

• Requires high pressure → high energy consumption

• Membranes are prone to fouling, scaling, and chemical degradation

• Requires pretreatment steps (e.g., filtration, pH adjustment)

• Generates concentrated brine waste that must be managed

iv. Electrochemical Treatments

This method uses electrical current to cause chemical changes in the contaminated water, leading
to the reduction, oxidation, or deposition of metal ions. Two main types include:
• Electrocoagulation: dissolves metal ions from anode electrodes (e.g., iron or aluminum) to form
flocs that trap contaminants.

• Electrodeposition: reduces metal ions onto the cathode, recovering them as solid metals.

Example:

• Cr⁶⁺ → Cr³⁺ → Cr metal (on electrode surface)

Advantages:

• Can be highly effective without chemical reagents

• Low sludge production

• Allows for metal recovery and reuse

• Compact and automated

Limitations:

• Energy-intensive, especially for large-scale applications

• Equipment corrosion and electrode degradation

• Requires careful control of voltage, current, and pH

• May not be economical for low-concentration wastewaters

v. Coagulation-Flocculation

This technique involves adding coagulants (e.g., aluminum sulfate, ferric chloride) to destabilize
fine particles and metal ions, causing them to aggregate into larger particles (flocs). These flocs
are then removed through sedimentation or filtration. Sometimes, flocculants (e.g.,
polyacrylamide) are added to enhance floc formation.

Advantages:

• Simple and low-cost for large-scale operations

• Effective for removing suspended particles and colloidal metals

• Often used as a pre-treatment step before filtration or membrane processes

Limitations:
• Less effective for dissolved or ionic metals (e.g., arsenic, mercury)

• Produces chemical sludge, which must be treated and disposed of

• Performance varies with pH, temperature, and mixing intensity

• Requires constant chemical dosing and monitoring

vi. Phytoremediation

Phytoremediation utilizes living plants to absorb, accumulate, stabilize, or detoxify heavy metals
from contaminated water. Certain plants—known as hyperaccumulators—are particularly
efficient at uptaking heavy metals through their roots and storing them in their tissues.

Examples of commonly used plants:

• Water hyacinth (Eichhornia crassipes)

• Duckweed (Lemna minor)

• Vetiver grass (Chrysopogon zizanioides)

Advantages:

• Eco-friendly and sustainable

• Can be implemented in natural or constructed wetlands

• No need for expensive equipment or chemicals

• Provides aesthetic and ecological benefits

Limitations:

• Slow process—can take weeks to months for noticeable results

• Efficiency depends on climate, species, and pollutant levels

• Biomass disposal issue: harvested plants containing heavy metals become hazardous waste

• Limited applicability in industrial-scale or emergency treatment scenarios

Due to the challenges listed above, adsorption has emerged as a superior alternative, particularly
when locally sourced adsorbents are used. Adsorption is cost-effective, reusable, effective at
trace metal levels, and generates minimal sludge.
Hence, recent research has focused on waste-derived adsorbents, especially activated carbon
produced from agricultural by-products like coconut shells, sawdust, sugarcane bagasse, and
palm kernel shells.

2.3 Adsorption Method and Activated Carbon Basics

Adsorption is a mass transfer process that involves the accumulation of substances at the
interface between two phases—typically a solid and a liquid. It has emerged as one of the most
effective and economical technologies for removing heavy metals from industrial wastewater
due to its high efficiency, simplicity, low energy requirements, and the potential for regeneration
and reuse of the adsorbent (Mohan & Pittman, 2024).

The adsorption process is classified into two main types: physical adsorption (physisorption) and
chemical adsorption (chemisorption). Physisorption involves van der Waals forces and is
generally reversible, while chemisorption involves covalent bonding and is often irreversible.
The efficiency of the adsorption process is influenced by several factors such as the surface area,
pore size distribution, surface functional groups, contact time, temperature, and solution pH.

Activated carbon (AC) is the most widely used adsorbent due to its high porosity, large surface
area, and abundance of functional groups. It can be produced from a variety of carbonaceous
materials through physical or chemical activation. Physical activation involves carbonization
followed by gasification with steam or carbon dioxide, while chemical activation involves
impregnation with chemical agents like KOH, H₃PO₄, or ZnCl₂ followed by thermal treatment.

The effectiveness of activated carbon for heavy metal removal lies in its ability to interact with
metal ions through ion exchange, surface complexation, electrostatic attraction, and precipitation.
The development of activated carbon from low-cost agricultural wastes provides a sustainable
and environmentally friendly alternative to commercially available activated carbon.

2.4 Agricultural Wastes as Precursors for Activated Carbon

Agricultural wastes are abundantly available and are often underutilized or discarded, leading to
environmental pollution. These wastes, which are rich in lignin, cellulose, and hemicellulose, can
be converted into activated carbon through thermal and chemical treatments. Utilizing
agricultural by-products for activated carbon production is not only cost-effective but also
contributes to waste management and environmental sustainability (Ioannidou & Zabaniotou,
2024).

Some common agricultural wastes used for activated carbon production include coconut shells,
rice husks, sawdust, sugarcane bagasse, corn cobs, bamboo, and palm kernel shells. These
materials differ in their carbon content, porosity, and structural properties, which affect the
quality and performance of the resulting activated carbon.

Palm kernel shell (PKS), a by-product of the palm oil industry, is particularly attractive due to its
high carbon content, hardness, and availability in palm-oil-producing countries. Studies have
shown that activated carbon produced from PKS has comparable, and sometimes superior,
adsorption capacity to commercial activated carbon for the removal of heavy metals and organic
pollutants (Ahmad et al., 2021; Auta & Hameed, 2023).

The choice of activation method and conditions (e.g., activation temperature, impregnation ratio,
and activation time) significantly affects the physical and chemical properties of the activated
carbon, including surface area, pore volume, and the nature of functional groups. Therefore,
optimizing these parameters is crucial for enhancing the adsorption performance of PKS-based
activated carbon.

2.5 Palm Kernel Shell (PKS) as a Raw Material

Palm kernel shell (PKS) is a hard, endocarp layer of the oil palm seed and constitutes one of the
most abundant agricultural residues in palm oil-producing countries like Nigeria, Indonesia, and
Malaysia. Due to its hardness, high carbon content, and low ash content, PKS has gained
increasing attention as a precursor for activated carbon production (Tan et al., 2022).

Chemically, PKS is composed primarily of lignin, cellulose, and hemicellulose, with lignin
content contributing to its structural rigidity and carbonization potential. The high fixed carbon
and low volatile matter make PKS ideal for thermal conversion to carbonaceous adsorbents. The
major challenge with PKS is its initial hardness, but this characteristic is also beneficial in
producing high-strength activated carbon with good mechanical stability.

The valorization of PKS into activated carbon not only provides a low-cost adsorbent but also
addresses issues related to biomass waste disposal. It aligns well with the principles of circular
economy and sustainable waste management by converting agricultural waste into a useful
material for environmental remediation.

Numerous studies have demonstrated the efficacy of PKS-derived activated carbon in removing
pollutants from water. For instance, Foo and Hameed (2022) activated PKS using KOH and
reported a surface area of 1134 m²/g and efficient adsorption of Pb²⁺ and Cr³⁺ ions. Similarly,
Yusufu et al. (2024) used H₃PO₄ to chemically activate PKS, achieving over 90% removal
efficiency for Cu²⁺ ions from aqueous solutions.

2.6 Activation Methods for PKS-Based Activated Carbon

Activation is a critical step in the production of activated carbon, as it develops the porosity,
surface area, and surface functionality necessary for effective adsorption. There are two main
activation techniques: physical activation and chemical activation.

2.7 Physical Activation

This involves carbonization of PKS at high temperatures (400–800°C) in an inert atmosphere

(usually nitrogen or argon), followed by activation using oxidizing gases such as steam or carbon
dioxide. Physical activation develops a stable pore structure and enhances the surface area, but it
may be less effective than chemical methods in creating functional groups.
2.8 Chemical Activation

In chemical activation, PKS is impregnated with chemical agents like potassium hydroxide
(KOH), phosphoric acid (H₃PO₄), or zinc chloride (ZnCl₂), and then carbonized at lower
temperatures (400–600°C). This method typically yields higher surface areas and a more
developed pore structure than physical activation. Additionally, chemical activation introduces
functional groups that enhance metal binding through ion exchange and surface complexation.

Among these, KOH and H₃PO₄ are the most frequently used for PKS activation. KOH tends to
produce microporous structures with high surface areas, while H₃PO₄ introduces phosphate
groups that can improve metal adsorption. Studies by Njoku et al. (2014) and Dechapanya and
Khamwichit (2023) showed that H₃PO₄-activated PKS effectively removed Pb²⁺ from
wastewater, following Langmuir isotherm and pseudo-second-order kinetics.

2.9 Combined Activation Techniques

Some researchers have explored combining physical and chemical activation to synergize the
benefits of both. For instance, thermochemical activation involving phosphoric acid
impregnation followed by CO₂ treatment can create hierarchical pore structures and increase
adsorption efficiency.

Optimization of activation parameters such as impregnation ratio, activation time, and

temperature is crucial. Excessive chemical use can clog pores or degrade material, while
insufficient activation may yield low surface areas.

3.0 Material Characterization Techniques for PKS-Based Activated Carbon

The adsorptivity of AC can be justified by its characteristics. There are methods to characterize
AC in terms of proximate and elemental analysis, pore size and its distribution, morphological
view and AC components. Among the method used by many researchers are as listed in Table 4.

Table 4 Characterization method for AC

Characterization Equipment / method Identification References

Proximate analysis Thermogravimetric analyzer (TGA-50, Shimadzu) Volatile matter, fixed

carbon, and ash contents Guo and Lua (2022);

Guo et al. (2022);

Guo et al. (2022)

Mettler Toledo TGA/SDTA851 Thermogravimetric analyzer Yin et al. (2023)

Elemental analysis CHNO/S Analyzer 2400, Perkin Elmer Identify carbon, hydrogen, sulfur,
oxygen and nitrogen content Daud and Ali (2024);
Adinata et al. (2024);

Sumathi et al. (2022)

Elemental analyzer, (CHN-932, Leco) Guo et al. (2023); Guo et al. (2023)

Flash EA 1112 ThermoFinnigan elemental analyzer Yin et al. (2023)

Solid and apparent densities Ultra-pycnometer (UPY-1000, Quantachrome) Densities of AC Guo

and Lua (2022)

Ultrapycnometer (AccuPyc 1330 pycnometer) Solid density of AC Adinata et al. (2023)

Mercury intrusion porosimeter (PoreSizer-9320, Micromeritics) Porosity of AC Guo and Lua

(2023)

Mercury porosimeter (Micromeritics, Autopore III) Pore size distribution for pores greater than
4nm

diameter Daud and Ali (2023)

Barret-Joyner-Halenda (BJH) model Pore size distribution Lua et al. (2024)

Horvath-Kawazoe (HK) method Yin et al. (2024);

Adinata et al. (2024)

Lignocellulosic content Technical Association of Pulp and Paper industry (TAPPI), by using
methods T-13wd-74, T-17wd-70 and T-9m-54. Identify cellulose, halocellulose and lignin
content Daud and Ali (2023); Adinata et al. (2023)

BET surface BET equation and Dubinin-Radushkevich equation Identify micropore surface area
and volume Guo and Lua (2023);

Guo et al. (2023);

Lua et al. (2023);

Guo et al. (2023);

Adinata et al. (2023);

Hamad et al. (2022)

ThermoFinnigan Sorptomatic 1990 Series analyzer BET surface area and pore size distribution
Yin et al. (2024)
Microphoto Scanning electron microscope (S360, Cambridge instruments) Observe the presence
of porosities and

microporosities Guo and Lua (2023); Hamad et al. (2022)

Transmission electron microscope Guo and Lua (2023)

Functional groups Fourier transform infrared spectroscope (FTIR2000, Perkin Elmer Functional
groups exist at the surface of AC Guo and Lua (2022);

Guo et al. (2024);

Guo et al. (2023);

Sumathi et al. (2022)

Perkin Elmer Spectrum RX FTIR Yin et al. (2007)

Textural characteristics N2 adsorption by accelerated surface area and porosimeter (ASAP-2000,

Micromeritics) Identify the textural

characteristics Guo and Lua (2023);

Guo et al. (2023);

Guo et al. (2022;

Sumathi et al. (2023);

Sumathi et al. (2023);

Hamad et al. (2023)

(ASAP-2010, Micromeritics) Daud and Ali (2024);

Lua et al. (2024);

Adinata et al. (2023)

Surface chemistry X-Ray photoelectron spectroscopy (MK-II, Vacuum Generator) Change of

surface chemistry before and after adsorption Guo et al. (2023)

Composition of AC Rigaku RIX 3000 X-Ray fluorescence (XRF) spectrometer Analyze

chemical composition and metal loaded in AC Sumathi et al. (2024)

3.4 Adsorption Studies: Synthetic and Real Wastewater

Adsorption studies of heavy metals using PKS-AC are typically conducted in batch or column
experiments, using either synthetic metal solutions or real industrial wastewater. These studies
evaluate the adsorption capacity, efficiency, and kinetics under varying experimental conditions.

3.4.1 Batch Adsorption Studies

In batch studies, known concentrations of metal ions are treated with fixed doses of PKS-AC
under controlled conditions. Parameters such as contact time, pH, temperature, adsorbent dose,
and initial metal concentration are varied to determine optimal conditions for maximum removal.

3.4.2 Isotherm Models

Isotherm models describe how adsorbates interact with the surface of the adsorbent. The most
common models are:

i. Langmuir Isotherm: Assumes monolayer adsorption on a homogenous surface.

ii. Freundlich Isotherm: Describes multilayer adsorption on heterogeneous surfaces.

Studies have shown that heavy metal adsorption onto PKS-AC often fits both isotherms, with
Langmuir showing better correlation at higher concentrations (Njoku et al., 2024).

3.4.3 Kinetic Models

Kinetic models describe the rate of adsorption. Common models include:

i. Pseudo-first-order model

ii. Pseudo-second-order model (best fit for chemisorption)

PKS-AC adsorption often follows the pseudo-second-order model, suggesting that the process is
governed by chemical interactions.

3.4.4 Thermodynamic Studies

Thermodynamic parameters such as Gibbs free energy (ΔG), enthalpy (ΔH), and entropy (ΔS)
are used to evaluate the feasibility and nature of the adsorption process. Adsorption using PKS-
AC is typically spontaneous and endothermic in nature.

3.4.5 Real Wastewater Applications

Though most studies use synthetic solutions for control, some have investigated real wastewater
from tanneries, battery plants, and electroplating units. PKS-AC has been effective in removing
Pb²⁺, Cd²⁺, Cr⁶⁺, and Cu²⁺ even in complex matrices, though performance may decrease
slightly due to competing ions and organic matter.
4.0 Comparison of PKS-AC with Commercial and Other Bio-Based Activated Carbons

A critical aspect of evaluating palm kernel shell-based activated carbon (PKS-AC) is comparing
its performance with commercial activated carbon (CAC) and other bio-based alternatives. Key
parameters for comparison include surface area, adsorption capacity, regeneration potential, cost,
and availability.

PKS-AC has consistently demonstrated comparable or superior performance to CAC in

removing heavy metals such as Pb²⁺, Cd²⁺, Cr⁶⁺, and Cu²⁺. Foo and Hameed (2022) found that
PKS-AC activated with KOH showed a surface area of 1134 m²/g, which is within the range of
high-grade commercial carbons. Similarly, Auta and Hameed (2024) reported that PKS-AC
could achieve over 90% metal ion removal efficiency under optimized conditions.

When compared with other agricultural waste-derived carbons such as coconut shells, rice husks,
sawdust, or sugarcane bagasse, PKS-AC often shows enhanced thermal stability, better
mechanical strength, and higher fixed carbon content. This is attributed to the unique
composition and hard structure of the palm kernel shell.

Economically, PKS is abundantly available in palm oil-producing regions and is often discarded
as waste, making it a highly cost-effective raw material. Additionally, the regeneration capacity
of PKS-AC through washing or thermal treatment makes it a sustainable option for repeated use.

4.1 Mechanisms of Heavy Metal Adsorption by PKS-AC

Understanding the mechanisms through which PKS-based activated carbon adsorbs heavy metals
is essential for optimizing treatment processes and tailoring surface functionality. Several
physicochemical interactions contribute to the adsorption process, including:

4.1.1 Ion Exchange

This involves the exchange of metal ions in the aqueous phase with hydrogen or other ions
present on the activated carbon surface. The presence of functional groups such as –OH and –
COOH facilitates this ion exchange process.

4.1.2 Electrostatic Attraction

Depending on the pH and the surface charge of PKS-AC (determined by pHpzc), metal cations
can be attracted to negatively charged surfaces, particularly above the point of zero charge.

4.1.3 Surface Complexation

Functional groups on PKS-AC, especially carboxylic, hydroxyl, and phosphate groups, can form
coordination complexes with metal ions, resulting in strong binding. FTIR studies often confirm
the role of these functional groups in metal adsorption.

4.1.4 Pore Diffusion and Physical Adsorption

The porous structure of activated carbon allows metal ions to be physically adsorbed into
micropores and mesopores. This mechanism is more pronounced in carbons with high surface
area and well-developed pore networks.

4.1.5 Precipitation and Co-precipitation

In some cases, metal ions may react with surface-bound hydroxyl groups or other species to form
insoluble hydroxides or salts, which precipitate on the surface of the adsorbent.

5.0 Environmental and Economic Benefits of Using PKS-Based Activated Carbon

The conversion of palm kernel shell (PKS) into activated carbon not only provides a cost-
effective method for wastewater treatment but also contributes significantly to sustainable
environmental management. The integration of PKS-AC into industrial wastewater treatment
systems aligns with multiple Sustainable Development Goals (SDGs), particularly SDG 6 (Clean
Water and Sanitation), SDG 12 (Responsible Consumption and Production), and SDG 13
(Climate Action).

From an environmental standpoint, PKS-AC helps reduce solid waste accumulation by

valorizing agricultural by-products that would otherwise be burnt or left to decompose, leading
to greenhouse gas emissions and environmental degradation. Using PKS for activated carbon
reduces the demand for wood-based carbons, thus conserving forest resources and mitigating
deforestation.

Economically, PKS is a low-cost and readily available material in many developing countries,
especially in Africa and Southeast Asia. The production of activated carbon from PKS can foster
local entrepreneurship, generate employment in rural areas, and support circular economy
initiatives. Moreover, the use of PKS-AC in industries reduces reliance on expensive imported
commercial adsorbents, thereby cutting down treatment costs.

Additionally, the regeneration and reuse potential of PKS-AC makes it a sustainable and long-
term solution for effluent treatment. It can be used multiple times with minimal loss in
adsorption efficiency, particularly when proper regeneration protocols are followed (thermal or
chemical). This significantly reduces the cost per treatment cycle.

5.1 Challenges and Research Gaps

Despite the promising applications of PKS-based activated carbon, several challenges and
knowledge gaps must be addressed to fully commercialize and optimize its use for heavy metal
removal in industrial wastewater.

5.2 Inconsistent Raw Material Quality

Variability in the composition of PKS due to different oil extraction methods or storage
conditions can affect the quality and consistency of the produced activated carbon. Standardizing
pre-treatment and activation protocols is necessary for reproducibility.
5.3 Activation Optimization

Activation parameters such as temperature, time, and chemical ratios greatly influence pore
development and surface chemistry. More research is needed to optimize these variables for
maximum adsorption efficiency specific to different heavy metals.

5.4 Metal Selectivity and Competitive Adsorption

In real wastewater systems, multiple metal ions and organic pollutants coexist, potentially
interfering with each other's adsorption. Research into competitive adsorption behavior and
selectivity under varying conditions is still limited.

5.5 Regeneration and Disposal of Spent Adsorbents

While PKS-AC can be regenerated, the efficiency and environmental impact of different
regeneration techniques require further study. Additionally, safe disposal methods for spent
carbon containing adsorbed heavy metals must be developed.

5.6 Scale-Up and Industrial Application

Most existing studies are limited to laboratory-scale experiments. Pilot-scale and full-scale trials
are necessary to evaluate the operational feasibility, cost-benefit ratio, and long-term
performance of PKS-AC in industrial settings.

5.7 Theoretical Framework

The theoretical framework for the use of palm kernel shell-based activated carbon (PKS-AC) in
the removal of heavy metals from industrial wastewater is grounded in the principles of
adsorption science, surface chemistry, and environmental engineering. At its core, adsorption is a
surface phenomenon where substances (adsorbates) adhere to the surface of a solid (adsorbent).
In this context, heavy metal ions in wastewater are the adsorbates, and the PKS-AC is the
adsorbent.

Several adsorption theories underpin this study. The Langmuir adsorption theory assumes
monolayer adsorption on a homogenous surface with a finite number of identical sites. It is
commonly applied to analyze adsorption equilibrium data and is useful in determining the
maximum adsorption capacity of PKS-AC. The Freundlich isotherm, on the other hand,
considers heterogeneous surfaces and is applicable to multilayer adsorption, which is often the
case with real wastewater containing multiple pollutants.

Kinetic theories, such as the pseudo-first-order and pseudo-second-order models, are also
employed to describe the rate of metal ion uptake. The pseudo-second-order model, which
suggests chemisorption as the rate-controlling step, often provides a better fit for PKS-AC due to
the involvement of surface functional groups like hydroxyl, carbonyl, and phosphate in binding
metal ions.
Furthermore, the point of zero charge (pHpzc) theory plays a crucial role in determining the
surface charge of PKS-AC under different pH conditions, influencing the direction and strength
of electrostatic interactions with metal ions. Surface complexation theory also explains the role
of functional groups on the carbon surface in forming complexes with metal ions.

Overall, this framework integrates surface science, environmental chemistry, and process
modeling to support the development and evaluation of PKS-AC as an effective, low-cost
adsorbent for industrial effluent treatment.

5.8 Conceptual Framework

The conceptual framework guiding this study is centered on the relationship between agricultural
waste valorization, water pollution control, and sustainable development. At its base, the
framework conceptualizes palm kernel shells, an agricultural by-product, as a resource for
producing activated carbon that can adsorb heavy metals from polluted industrial wastewater.

The process begins with the collection and preparation of PKS, followed by activation (physical
or chemical) to enhance surface area and porosity. The resulting PKS-AC is then introduced into
contaminated wastewater, where it binds metal ions through physical and chemical interactions.
These interactions result in the reduction of toxic heavy metals in the effluent to environmentally
safe levels.

This framework incorporates key variables such as activation method, surface properties of the
carbon, metal ion characteristics (size, charge, initial concentration), solution pH, contact time,
and temperature. The outcome measures include adsorption capacity, removal efficiency, and
reusability of the adsorbent.

The conceptual framework also aligns with sustainable development objectives by emphasizing
waste-to-resource transformation, low-cost water purification, and reduction of environmental
pollution. It bridges the gap between laboratory research and real-world application by
considering both scientific and socio-economic dimensions of water treatment.

5.9 Summary of Findings and Future Research Directions

The extensive review of literature on the development and evaluation of palm kernel shell-based
activated carbon (PKS-AC) for heavy metal removal in industrial wastewater has revealed the
tremendous potential of this agricultural by-product in water purification. Numerous studies have
validated the efficiency of PKS-AC in adsorbing toxic metals such as Pb²⁺, Cd²⁺, Cr⁶⁺, and
Cu²⁺ from contaminated water through mechanisms involving ion exchange, surface
complexation, electrostatic interaction, and pore diffusion. These mechanisms are strongly
influenced by the surface chemistry, porosity, and functional groups present on the activated
carbon. Additionally, the activation method—whether physical or chemical (using agents like
KOH or H₃PO₄)—plays a critical role in enhancing the surface area and adsorption efficiency of
the PKS-derived carbon. Overall, the literature affirms that palm kernel shell-based activated
carbon is a cost-effective, sustainable, and environmentally friendly alternative to commercial
adsorbents, aligning with global efforts toward circular economy and the achievement of SDGs
related to clean water, responsible waste utilization, and climate resilience.

Characterization studies consistently show that PKS-AC possesses high surface area, abundant
porosity, and a variety of functional groups, making it an effective adsorbent. The choice of
activation method—physical or chemical—strongly influences these properties, with KOH and
H₃PO₄ activation being the most effective in enhancing surface functionalities and pore
structure.

Moreover, PKS-AC compares favorably with both commercial activated carbon and other
biomass-derived carbons in terms of adsorption capacity, economic feasibility, and
environmental sustainability. Its successful application in treating real industrial wastewater
further demonstrates its practical relevance.

However, several gaps and challenges remain. These include variability in raw material quality,
lack of standardized production protocols, limited understanding of competitive adsorption in
mixed-metal systems, regeneration and disposal concerns, and the absence of large-scale
application data.

Future Research Directions

To fully harness the potential of PKS-AC, future research should focus on the following areas:

i. Optimization of activation parameters tailored to specific metal pollutants.

ii. Comprehensive studies on adsorption mechanisms under real wastewater conditions.

iii. Development of efficient, low-cost regeneration techniques.

iv. Lifecycle assessments and environmental impact evaluations of PKS-AC production and use.

v. Scaling up to pilot and industrial applications to assess long-term performance and operational
challenges.

vi. Exploration of composite materials combining PKS-AC with other low-cost adsorbents or
nanoparticles for enhanced performance.