CHAPTER ONE

INTRODUCTION

1.0 INTRODUCTION

The present era is marked by considerable challenges that greatly impacts the global

landscape. One of which revolves round the disposal of used lubricating oils, which are

known to be toxic and resistant to biodegradation, thus contaminating soil, water bodies,

and the atmosphere (Szyszlak-Bargłowicz et al., 2023).

Spent engine oil, which is the most prevalent kind of waste lubricating oil generated,

consist of hazardous chemicals such as polycyclic aromatic hydrocarbons (PAHs),

which are potentially cancerous (Ani et al., 2023). According to (Bekibele et al., 2022),

high temperature, friction and incomplete combustion in internal combustion engines

causes oxidation, nitration, and polymers breakdown in the chemical components of

engine oil, producing these chemicals together with other hazardous pollutants such as

heavy metals, hydrocarbons, gum, varnish, and polychlorinated biphenyls (PCBs).

These components work together to increase waste lubricating oil's total toxicity,

presenting serious health and environmental problems (Kwakye et al., 2022).

Consequently, the performance of lubricating oil diminishes over time due to the wear

and tear of the engine. Nevertheless, used lubricating oils present opportunity for

recycling, showcasing their potential to be transformed into valuable and beneficial

products through processing and refinement techniques. These recycled resources can

be utilized as a foundational component in the creation of new lubricating oils (Pinheiro

et al., 2021).

Adsorption is regarded as one of the most efficient techniques for used oil recovery

among others due to its high effectiveness, affordability, simplicity, ease of use, quick

1
operation, long-lasting capabilities, and potential for reuse (Nissar et al., 2022). The

availability of an extensive range of inexpensive adsorbents derived from naturally

occurring waste materials such as agricultural waste products, particle organic matters,

serves as a driving force behind the adsorption process (Santos et al., 2022).

The peel of watermelon fruit (Citrullus lanatus) makes up around one-third of the fruit's

overall bulk. This peel, which is often disposed in large quantities owing to its low

market value, is composed of low molecular weight substances like citrulline, amino

acids, and other phytochemicals as well as carbonaceous components like

polysaccharides (e.g. cellSEOse, pectin, and carotenoids) (Bhattacharjee et al., 2020).

These chemicals make the peel an ideal precursor for the manufacture of activated

carbon. The hydroxyl and carboxyl groups (found in cellSEOse and pectin) provide

great binding sites for toxic heavy metals. Chemical activation of these adsorbent

further improves their surface-area for effective contaminants present in spent engine oil

(Altowayti et al., 2021).

1.1 PROBLEM STATEMENT

The disposal of used engine oil presents considerable environmental difficulties due to

its high potential for land and water pollution. As a result, there is an urgent demand for

environmentally friendly and effective waste management systems. Using watermelon

peels not only addresses the issue of agricultural waste, but it also provides an

environmentally beneficial method for recovering spent engine oil.

1.2 AIM

To investigate the adsorptive recovery of spent engine oil using watermelon peel as a

low-cost and eco-friendly adsorbent.

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1.3 OBJECTIVES

 Characterizing the adsorptive properties of modified watermelon peel via FTIR,

SEM and BET.

 Investigation of the adsorption capacity of watermelon peel for spent engine oil.

 Optimization of process parameters such as pH, temperature, adsorbent dosage,

contact time for maximum efficiency in oil recovery.

 Investigate the desorption process to evaluate the reusability of the watermelon

peel adsorbent.

1.4 SCOPE

This project encompasses the development of adsorbent and optimization of process

parameters for the adsorptive recovery of spent engine oil using watermelon peel as an

innovative adsorbent.

1.5 JUSTIFICATION

 Benefit the environment by reducing oil pollution in waterbodies and the soil via

recycling of spent engine

 Repurpose watermelon peels into a useful resource by applying waste

valorization.

 Utilization of knowledge of chemical engineering to streamline the procedure.

 Lessen dependency on virgin oil and encourage a circular economy.

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Used oil, also known as sump oil, should not be thrown away as if the oil gets dirty, it

can be cleaned by removing the contaminants. Disposing the used oil in the

environment or burning it as a low-grade fuel, leads to some hazardous consequences

such as toxic compounds in liver or complete impairment of body functions and

eventually death of organism, carcinogenicity, environmental pollution, etc. (Nissar et

al., 2022)

OBJectives

 Viscosity

 TAN (Acidic content recovery)

 GC-MS or UV spectrophotometer

 FTIR, SEM, BET

Include the classification of lubricating oils in your literature review

Write on the watermelon peel as an adsorbent, activation, carbonaceous material

for the adsorption of PAH

Lubricants are generally subjected to degradation and contamination fromseveral

sources during its long-term operation (Mortier et al.,2010).Contamination

4
can have serious adverse effects on the physical and chemicalproperties of

lubricants. The loss of crucial properties, which are central tothe useful service

life can result in inefficient system performance, acceleratedmechanical and

chemical wear processes, shorten the service life of theequipment, and cause

premature failures (Gustavsson,2013; Speight & Exall,2014). Thus, lubricants

have a lifespan, after which they require [Link], some oils are

consumed during service, and some are partly lostby combustion processes,

evaporation, residues remaining in the containers,etc. Therefore, about 50% of

the fresh lubricants consumed will generatewaste and, consequently, a huge

amount of waste lubricant oil (WLO) is pro-duced every year all over the world

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 CHAPTER TWO

LITERATURE REVIEW

2.1 BACKGROUND

Used engine oil, also known as spent engine oil, is a hazardous residue that emerges

from various sources such as vehicles, machinery, and industrial activities. And as such,

disposing of used engine oil improperly poses significant risks to the environment and

human health due to its high levels of heavy metals, polycyclic aromatic hydrocarbons

(PAHs), and other harmful substances. The concentration of PAHs in used engine oil

can be as much as 670 times higher than that of new engine oil, making it an extremely

dangerous pollutant as it is classified as a carcinogenic compound (Nissar et al., 2022).

Chronic pollution caused by used engine oil amounts to millions of tons annually.

Unlike petroleum pollution, used oil pollution is a global issue as it primarily stems

from automotive traffic and industrial operations. Inappropriately disposal of spent

engine oil can lead to significant economic consequences. The costs associated with

cleaning up environmental contamination from spent engine oil can be substantial, and

the depletion of natural resources and ecosystem services can result in long-term

economic impacts.

Spent engine oil can also have notable health implications which results from reckless

disposal. The heavy metals and PAHs found in spent engine oil can build up in the

human body, posing enduring health risks like cancer, neurological harm, and

reproductive issues (Jock et al., 2023). Oil contamination alters the pH levels of the soil,

impacting its physical, chemical, and biological characteristics. Pore spaces in the soil

may become blocked, reducing soil aeration and water penetration. This elevation in

bulk density subsequently affects plant growth. Additionally, oil contamination

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diminishes and constrains soil permeability, leading to the accumulation of essential and

nonessential elements in the soil and their eventual migration into plant tissues (Swapna

et al., 2021).

Adsorption, a phenomenon where molecules (adsorbate) attach to a surface (adsorbent),

is a valuable technique for removing pollutants from engine oil. This process can be

physical, relying on van der Waals forces, or chemical, involving covalent bonding.

Surprisingly, watermelon peel can function as an efficient adsorbent due to its

affordability, eco-friendliness, and fibrous structure conducive to capturing oil

molecules (Emenike et al., 2022)

Since watermelon peel is a by-product, it is both inexpensive and readily available. As a

natural material, it is biodegradable and non-toxic, while its fibrous nature affords a

substantial surface area for adsorption. Watermelon peel can be processed into powder

or treated chemically to boost its adsorption capacity. The utilization of watermelon

peel as an adsorbent in adsorption presents a sustainable and efficient approach to spent

oil recovery, thereby promoting environmental conservation and resource effectiveness

(Aljeboree et al., 2022).

Lubricating oil

Lubricating oil is a thick, complex mixture of hydrocarbons used to keep machine

components running smoothly by minimizing friction between moving surfaces. It

produces a separating layer between surfaces, limiting direct contact and reducing heat

generated by friction. (Mangas et al., 2014). Typically, lubricant is used to prolong the

life of equipment by reducing wear and friction. Ninety percent of fully prepared

lubricating oil is composed of various functional additives and base oil. There are

several kinds of basic fluid, including synthetic, biological, and mineral base oils.

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Mineral oils generated from petroleum make up between 70 and 90 percent of the fluids

used today (Xia et al., 2018).

Mineral Oils

Mineral oils, also known as white oils, alias paraffin oils, and white oils, are complex

chemicals created during fractional distillation and purification of crude oil. They

consisted of straight-chain alkanes, branched-chain alkanes, cycloalkanes, and

aromatics with carbon chains between C20 and C50 (Ji et al., 2023). Mineral oils can be

paraffinic, naphthenic, or aromatic based on the chemical structure, sulfur

concentration, and viscosity of their crude oil source. Paraffin oil is the most used

mineral oil, accounting for 85-90 percent of global usage. They are widely utilized in

turbines, engines, gearboxes, and bearings. Shahnazar et al. (2016) .

Table 2. Base Oil categories by American Petroleum Institute (API)(Shahnazar et al.,

2016).
Group Properties

I Saturates are <90%, and sulphur is >0.03%, and VI is >80 and <120

II Saturates are >90%, and sulphur is <0.03%, and VI is >80 and <120

III Saturates are >90%, and sulphur is <0.03%, and VI is >120

IV Polyalphaolefins (PAO)

V All other base stocks not included in Group I, II, III, or IV

Synthetic oil

This base oil group closely corresponds to API Group IV. They are constituted of oil

components that have been created synthetically by the reaction of a few well-defined

chemical compounds (albeit typically petroleum-based), rather than refined from

existing petroleum crudes or vegetable oils. Examples are Polyalphaolefins (PAOs),

8
Polyinternalolefins (PIOs). Polyisobutylenes (PIBs), Esters Polyalkylene glycols

(PAGs) etc. (Bart et al., 2013)

Synthetic base oil has appropriate oil qualities that enable greater performance attributes

over mineral oils, such as:

 Improved oxidation and thermal stability leading to longer oil life.

 Lower pour points that provide easy engine startability under colder climates

 High viscosity index (VI) and good viscosity–temperature relationship providing

wide temperature operability

 Good lubricity properties leading to longer engine life due to less wear.

 Wide operating temperature range (low to high).

 Lower volatility providing reduced oil consumption

Synthetic base oils are frequently used in automobile lubricants, such as engine oils and

transmission fluids, and in industrial applications, including hydraulic systems,

compressors, and gears. (zamani, 2023).

Additives

Lubricant additives are chemical substances added to base oils to improve its

performance and longevity. These additions are intended to enhance the natural qualities

of the base oil, add desired features, and decrease bad ones. And as such, making them

are an important part of modern lubricants (Xia et al., 2018).

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Table 2.3 Lubricant additives (Ahmed & Nassar, 2011) , (Mathura, 2024).

Additive type Function Examples

Viscosity Index (VI) Maintain viscosity across Polymethacrylates,
Improvers temperature range Olefin copolymers
Pour Point Depressants Lower the temperature at Polymethacrylates,
which oil flows Alkylated naphthalenes
Detergents Keep engine clean by Calcium, Magnesium
preventing deposits sulfonates
Keep contaminants Polyisobutenyl
suspended to prevent succinimides
deposits
Dispersants
Form protective film to
prevent metal-metal Zinc
contact dialkyldithiophosphates
Anti-wear Additives (ZDDP)
React with metal
surfaces under high loads
Extreme Pressure (EP) to prevent welding Sulfurized fats/olefins,
Additives Chlorinated paraffins
Molybdenum disulfide,
Reduce coefficient of Graphite, Organic fatty
Friction Modifiers friction between surfaces acids
Rust & Corrosion Protect metal surfaces Alkanolamines,
Inhibitors from corrosion Alkylated succinic acids
Prevent oil breakdown Phenolic amines, Zinc
Antioxidants and viscosity increase dithiophosphates
Prevent and break down Silicones, Polymeric
Foam Inhibitors foam in the oil compounds
Prevent catalytic
breakdown of oil by Benzotriazoles,
Metal Deactivators metals Thiadiazoles
Allow oil and water to Alkoxylated fatty
Emulsifiers mix amines, Sulfonated oils
Increase adhesiveness of Polyisobutenes,
Tackiness Agents oil to surfaces Polymethacrylates
Alkoxylated alkyl
Allow oil and water to phenols, Polyalkylene
Demulsifiers separate glycols

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Properties of Lubricants

Spent Engine OIL

This refers to the deterioration of new lubricating oil components that get polluted by

metals, ash, carbon residue, water, varnish, gums, and other contaminating

contaminants, as well as asphaltic compounds that form on the engine bearing surface.

When these additives and foreign chemicals are combined with lubricating oil, they will

likely age, deteriorate, and fail, resulting in mechanical faults and poor performance

(Dabai & Bello, 2019).

During engine operations, lubricants picks up various impurities and is exposed to

thermal, physico-chemical, oxidation, nitration, and polymers breakdown in the

component chemicals. (Bekibele et al., 2022). This eventually causes oil breakdown and

the formation of used engine oil, which, if left unchecked, damages the engine's

components and prevents it from operating properly. In such circumstances, these oils

must be replenished from autos, machinery, or utility equipment after a set length of use

(Raţiu et al., 2021)

Used lubricating oils (SEOs) are designated as hazardous wastes and pose a severe

pollution concern not only for the environment, but also for human health due to the

presence of toxic chemicals such as heavy metals, polychlorinated biphenyls (PCBs),

and polycyclic aromatic hydrocarbons (PAHs) (Botas et al., 2017).

Types of contaminants

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The oil breakdown process generates acids and metallic particles, which cause engine

wear. In turn, the metallic particles produce additional wear, creating more impurities,

which is known as the chain reaction of wear. These impurities can be classified based

on the state of matter into:

 solid contaminants: metallic particles, soot, rubber particles, paint, varnish

particles, tinder, fabrics, fibers

 Liquid contaminants: water/moisture, coolant, fuel, acids

 Gaseous contaminants: air, exhaust gases.

However, the main contaminants based on their source are depicted in Table 2.

Table 2. Main elements and contaminants in lubricating oil (Silva et al., 2021).
Elements Origin Limits (ppm)

Ba Detergent additives <100

Ca Detergent additives 1000-3000

Mg Detergent additives 100-500

Zn Anti-wear additives 500-1000

Fe Engine degradation 100-500

Cr, Ni Engine degradation Traces

Al, Cu, Sn Bearing Traces

Si Additives / water 50 – 100

S Base oil/ combustion 0.2 - 1%

products

Light Hydrocarbon Fuel 5 - 10%

Polycyclic aromatic Incomplete Combustion <1000

hydrocarbon

Effect of spent engine oil (SEO) on environment and human health

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When combined with degraded pollutants, additives, and by-products like water and

sediments, spent engine oil becomes more hazardous than virgin base oil. Poor

management and reckless disposal of spent engine oil can negatively impact the

environment and human health.(Anisuzzaman et al., 2021).

For landfills containing permeable soils, water-soluble substances in lubricants easily

seep through contaminating groundwater through runoff, leaching, and percolation. The

presence of used engine oil hinders the solubility of oxygen in water, thereby

deteriorating the quality of life for aquatic species. Additionally, when exposed to high

temperatures in the presence of air, SEO can evaporate and contribute to air pollution.

Studies have shown that in regions of West Africa, the dispersion of air contaminants

might travel at a speed of 10-12 m/s (Emetere, 2016). This analysis implies that air

pollution caused by the combustion of waste lubricant is not limited to the source of

pollution but can spread over time to other sites. It was recently reported that black soot

enveloped a metropolitan metropolis of Port Harcourt, although the remote origins were

in the suburb settlement (about 22 km away from city)(Oladimeji et al., 2018).

SEO consists of a variety of harmful substances, such as polycyclic aromatic

hydrocarbons, which are known to induce cancer if inhaled or consumed. These

contaminants can result in skin issues like toxicity, eczematous and contact dermatitis,

folliculitis, oil acne, and melanosis. The combustion of SEO can worsen respiratory

problems. Exposure to these contaminants can impact the nervous and immune systems,

potentially leading to long-term health complications. (Okebalama et al., 2024).

Spent Engine OIL Recovery

The recycling and re-refinement process of used engine oil are crucial for the

conservation of valuable resources, the reduction of environmental pollution, and the

promotion of sustainable practices by minimizing waste and limiting the extraction of

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new resources. The reuse of spent engine oil (SEO) can be achieved through three

primary methods: incineration, reprocessing, and re-refinement. Incineration and

reprocessing methods are more energy-intensive and often result in the production of

secondary pollutants that are more harmful to the environment. (Anisuzzaman et al.,

2021).

Alternatively, SEO can undergo re-refinement, where the spent engine oil is treated to

eliminate impurities and enhance its properties to be used as a fresh lubricant. The re-

refinement technology of SEO to lubricating oil requires less energy compared to

incineration and reprocessing, making it a preferred option due to its lower energy

consumption, minimal environmental impact, and reduced waste generation. Table

summarizes the various refining.

Table 2. Spent Oil Recovery methods (Oladimeji et al., 2018)

Method Advantages Disadvantages

Acd-Clay Teatment

Spent Engine Oil Recovery Methods: Advantages and Disadvantages

Method Advantages Disadvantages

- Produces large quantity of

pollutants
- Simple method - Unable to treat modern multigrade
- Affordable capital investment oils
Acid-Clay - Low operating cost - Difficult to remove asphaltic
Treatment - Does not require skilled operators impurities

Solvent Extraction - High recovery rate - High operating cost

- Effective for heavy crude oil recovery - Requires skilled operating system
- Improved sweep efficiency and qualified personnel

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 Method Advantages Disadvantages

- High capital investment

- Produces high Viscosity Index lube oil with well

oxidation resistance and good stable color - High capital investment
- Consumes bad quality feed - Requires high pressure and
- High product recovery with no (or very low) temperature conditions
Hydrotreating disposals - Catalyst regeneration required

- Effective for removing metal and particles from - Expensive membranes

Membrane used lube oil - May get damaged and fouled by
Technology - Improves recovered oil liquidity and flash point large particles over time

- High capital investment

- Requires skilled operating system
- Allows production of mainly base oils and qualified personnel
Catalytic Process - Effective for heavy crude oil recovery - Catalyst regeneration required

- Effective for removing impurities from spent engine - Requires skilled operating system
oil and qualified personnel
- Improves oil quality and reduces environmental - High capital investment
Adsorption impact - Adsorbent regeneration required

2.3 Adsorption
Adsorption involves mass transfer from the fluid to solid. Removal of impurities from

liquid and gaseous effluent is one of the significant applications of adsorption. The solid

must possess certain physical and chemical properties if it is to be used as an adsorbent.

Large surface area per unit weight is the most important criterion in the selection of

adsorbent. This process is identified as a fusion of physical and chemical interactions

15
where materials accumulate at the interface between different phases such as liquid-

liquid, liquid-solid, or gas-liquid (Munene, 2022).

In contrast to absorption, adsorption is the mechanism through which fluid molecules

are concentrated on a surface through either chemical or physical means, whereas

absorption involves the formation of partial chemical bonds with the adsorbed species

or penetration of the absorbate into the channels within the solid material. In more

technical terms, fluid molecules are absorbed by a solid or liquid and then distributed

throughout the material. The adsorbate denotes the material derived from wastewater or

the volume of pollutant attached to the surface of the adsorbent, while the adsorbent

denotes the solid phase accountable for accumulating the contaminant, such as activated

carbon or other biosorption materials. For adsorption to occur, the adsorbate must

exhibit lower free energy on the surface of the adsorbent in the solution (Oladimarun,

2022).

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Adsorption mechanism

According to Munene (2022), adsorption happen in four distinct stages:

Stage 1: The adsorbate diffuses from the bulk fluid to the solid-liquid boundary layer

surrounding the adsorbent particle.

Stage 2: External diffusion. The diffusion of the adsorbate from the border layer to the

adsorbent's outer surface.

Stage 3: Internal diffusion. Diffusion transports the adsorbate from the adsorbent's outer

surface to its inner surface.

Stage 4: Adsorption of the adsorbate on active sites.

Adsorption of molecules to the adsorbent surface occurs in two ways: "physical

adsorption," also known as "physisorption," and "chemical sorption," also known as

"chemisorption." This is determined by the molecules' interactions with the surface.

(Kecili & Hussain, 2018).

Physical adsorption

Adsorption by physisorption occurs on these surfaces due to electrostatic interactions

and natural attractive forces or weak forces such as van der Waals. As illustrated in Fig.,

this type of adsorption consists of numerous layers of adsorbent material on the surface

of the adsorbent material. This sort of adsorption does not require high temperatures or

activation energy, and it happens at low temperatures, comparable to the process of

vapor condensation on liquid substance surfaces. Hussein et al., (2017) discovered that

physisorption is the primary method for removing cadmium from wastewater using

watermelon rind.

Chemisorption

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In contrast to physical adsorption (see Table 2.1), which results in the production of a

thick multilayer on the surface, chemical adsorption is slower than physical adsorption

and often forms a monomolecular layer (monolayer) on the adsorbent surface as shown

in fig. Ion exchange, chelation, and complexation or coordination are the components of

chemisorption. In chemisorption, surface functional groups are crucial for attaching the

adsorbate (Vijayaraghavan & Balasubramanian, 2015).

Electrostatic interactions between the cations in the solution and the negatively charged

groups in the biomass cell wall cause ion exchange (Abdolali et al., 2014). This

chemical process is reversible.

When a ligand binds to a metal ion, a ring structure is formed. This process is known as

chelation. The ring structure created prevents the mineral that is connected from

engaging in unintended chemical reactions.

Complexation is the process of removing a metal from a biomass cell surface by

building a complex with the active groups of the cell wall. Compounds can be neutral,

negatively or positively charged, and the bonding for complexation can be covalent,

electrostatic, or both. proposed metal complexation as a process for removing Sr(II) ions

from aqueous solution during biosorption utilizing sugarcane bagasse and peanut shells.

After interacting with the functional groups in the biosorbent, metal undergoes

reduction biosorption. In this two-step process, the metal first binds to a distinct location

that serves as a nucleation site before the reduction occurs. Numerous factors, including

metal ion characteristics like ionic radius, oxidation state, and molecular weight, as well

as biosorbent characteristics like porosity and surface area, as well as process variables

like pH, temperature, sorbate concentration, and biosorbent concentration, all affect how

effective adsorption is (Escudero et al., 2019).

18
 Figure 1: (A)Monolayer (B) Multilayer adsorption (Kecili & Hussain, 2018)

Table 2.1: Comparison Between physical adsorption and chemical adsorption

Physical Adsorption Chemical Adsorption

Electrostatic interaction and Van der Covalent bonds are formed between the
Waals forces are involved surface and the adsorbed molecules
Fast Slow
Reversible Irreversible
Not very Specific It is specific
Multilayers are formed Monolayers are formed
Activation energy is not required Activation energy are formed
It usually occurs at low temperature High temperature is required
value and decreases with increasing
temperature

FACTORS AFFECTING ADSORPTION

Adsorption is a basic surface phenomenon in which molecules collect on a solid's

surface as opposed to entering its inside. Numerous variables influencing the interaction

between the adsorbent and the adsorbate determine the amount of adsorption.

Optimizing the adsorption process and its applications in a variety of sectors, including

chemical reactions, air purification, water treatment, and crude refining, requires an

understanding of these parameters.

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SOLUTION pH

A solution pH is a crucial operational component that affects the adsorption process and

typically has a significant impact on the process's overall performance. The adsorbent's

surface characteristics, metal speciation, and ultimately the degree of metal adsorption

are all influenced by the pH of the solution. The specific charge of functional groups

and, ultimately, the adsorbent's ability for adsorption are all impacted by pH, which also

determines the degree of protonation of the adsorbent.

The distribution of metal ions, ionization potential, and surface charge of the adsorbent

are all influenced by pH. When the pH of an adsorbent surface is lowered, the presence

of a significant number of H+ ions neutralizes the negatively charged surface, reducing

the diffusion barrier and increasing the rate of adsorption.

Previous research revealed that the adsorption effectiveness rises at higher pH values

and declines at lower pH values (Ugwu et al., 2020).

The severe competition from H+ ions causes cationic metal ion absorption to be

generally low in acidic (low pH) environments. The quantity of H+ ions decreases and

cationic metal species adsorption rises with rising pH. Few studies have looked at how

pH affects biochar's ability to sorb substances, which supports the role of pH on

adsorption potential. The Pb(II) sorption capacity of biochar generated from maize

stalks increased with increasing solution pH, according to Liu et al.'s (2019)

observations. Within the pH range of 4-6, the removal efficacy increased.

The authors proposed that the presence of H+ prevented Pb cations from sorbing in an

acidic environment. However, Senthilkumar et al. (2020) found that when the pH

increased from 2 to 4, the remediation of As(V) using biochar generated from Ulva

reticulata increased from 55% to 93%. As a result, large protonated positively charged

binding sites on the biochar surface caused by saturation of excess H+ ions, which

20
enhanced the sorption of As(V) by electrostatic attraction, were responsible for the

comparatively high As(V) sorption under low pH settings by seaweed-derived biochar

(Mogili & Senthilkumar, 2020).

Effect of Contact Time

For adsorption to be complete, equilibrium between the adsorbent and the solute of the

solution should be attained. Thus, a particular time is required for the interactions of the

equilibrium in order to ensure that the adsorption is achieved. The time required for the

equilibrium to be attained is known as the contact time. Several authors have studied the

effect of contact time on adsorption. According to (Gebreslassie, 2020), the fast

adsorption observed at the initial stage of the adsorption process is probably due to the

copious availability of a negatively charged active site on the surface of the adsorbent.

However, the slow rate of adsorption at later times is due to the electrostatic repulsion

between the adsorbed MG cations and the cationic adsorbate species available in the

solution. In addition, the slow pore diffusion of MG cations into the bulk phase of the

adsorbent makes the adsorption process take a longer time to attain equilibrium. Their

results showed that the rate of adsorption of metal ions increases with time, after a

certain time, an optimum value is reached after which no more removal of metal ion

takes place. The amount of metal ion adsorbed at the contact time is a reflection of the

maximum adsorption capacity achieved by the adsorbent under the operating

conditions. (Ugwu et al., 2020)

TEMPERATURE
Temperature can affect the adsorption capacity of the adsorbent depending on the types

of adsorbent used. In order to find out the spontaneity of the process, the enthalpy,

entropy and Gibbs free energy must be determined. These parameters are computed

from the Gibbs Helmholtz equation: ∆G=∆H−T∆S(Tran et al., 2020). The effect of
21
temperature on adsorption rate is such that it alters the molecular interaction and the

solubility of the adsorbate. The increase or decrease of the adsorption capacity upon

varying the temperature will be useful to establish the type of the sorption process. On

the basis of change in temperature, the process is identified to be endothermic when the

adsorption capacity rises with the increase in temperatures; whereas the process is

exothermic when the adsorption capacity decreases with temperature. Temperature can

change the adsorption equilibrium depending on whether the process is exothermic or

endothermic (Asadullah et al., 2019).

ΔG° = -RT*InKa

The enthalphy, AH° and entropy, AS° changes on the adsorption process can be

estimated from equilibrium constants as the function of temperature via Van't Hoff

equation, as can be referred in Eq. (9):

∆S ° ∆H °
ln K a −
R RT

ADSORBENT DOSAGE

Since the adsorbent determines the adsorbent capacity for a given initial concentration,

the dosage of the adsorbent is an important parameter (Şentürk & Alzein, 2020).

According to Kroeker's rule, the specific adsorbed volume, for a constant initial

concentration, decreases with increasing adsorbent mass. Thus, increasing the adsorbent

dose is positively correlated with the efficiency and performance of dye removal. With

increasing adsorbent dosage, at fixed contaminant concentrations, more active surface

area is available for adsorption and more active adsorption sites are available [189].

22
As the concentration of biomass (the amount of adsorbent) increases, the efficiency of

pollutant removal (E%) increases, but there is no direct proportionality between the

amount of biomass and the amount of pollutant removed (qe).

In contrast, as the concentration of biosorbent increases, the amount adsorbed per

species (qe) decreases. This can be attributed to the fact that the shape of the sorption

isotherm changes with increasing biosorbent concentration. The decrease in the specific

adsorbed amount is probably due to the fact that some of the surface or surface groups

may not be saturated in the more concentrated suspensions (Popa et al., 2021)

During the dye removal process, the capacity may decrease for two reasons:

adsorption sites remain unsaturated while the number of sites available for adsorption

increases; or

aggregation or agglomeration of adsorbent particles may occur, reducing the available

surface area and increasing the diffusion path length(Dehghani et al., 2021)

Particle Size

The particle size is an important parameter in adsorption process. The smaller the

particle sizes of the adsorbent, the higher its adsorption rate. As the particle size

decreases, the adsorption increases. This is because the surface area increases as the

particle size decreases (Ugwu et al., 2020) The small particle sizes result in a higher

specific surface area. Specific surface area (SSA), defined as the total surface area of a

solid material per unit of mass, is an important feature for adsorption processes. SSA is

dependent on the size of the particles, as well as on the structure and porosity of the

23
material. The most common unit of measurement is m²/g (Šljivić-Ivanović & Smičiklas,

2020).

(Aljeboree et al., 2017) posits that the relationship between adsorption capacity to

particle size depends on the chemical structure of contaminants (its ionic charge) and its

chemistry (its ability to form hydrolyzed species); and the intrinsic characteristic of the

adsorbent (its crystallinity, porosity and rigidity of the polymeric chains).

Batch adsorption methods is favored by smaller adsorbent particle sizes result in higher

adsorption capacity and efficiency, since there are more active sites for binding (Nikam

& Mandal, 2020).

Effect of initial Concentration

The initial sample concentration is perhaps one of the most important factors

influencing the adsorption process, as it indirectly affects the efficiency of contaminants

removal by reducing or increasing the availability of binding sites on the adsorbent

surface. In such water treatment systems, the efficiency of dye removal (E) and the

maximum amount of dye bound in equilibrium (q) are directly related to the initial dye

concentration.

Ci −C f
E ( % )= .100
Ci

( Ci −C f ) .V
q=
m

where: E (%) efficiency; q (mg/g)-amount of dye bound in equilibrium; C (mg/L)-initial

dye concentration; C (mg/L)-final dye concentration; m (g)-amount of adsorbent; and V

(L)-volume of aqueous solution ((Rápó & Tonk, 2021)

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Based on the study conducted by (Husein et al., 2017), increasing the initial

concentration of contaminants in a sample increases the mass transfer driving force and

therefore the rate at which contaminants molecules pass from the bulk solution into the

watermelon particle surface. However, removal capacity decreases as the initial

concentration increases resulting from less availability of active sites on adsorbent

surface at higher concentration of sample solutions. And vice-versa at low

concentration.

By examining the effect of initial dye concentration, three trends can be observed:

 the removal efficiency decreases as the initial concentration increases;

 removal efficiency increases as the initial concentration increases; and

 no significant change in removal efficiency. (Rápó & Tonk, 2021).

Effect of coexisting ion

The investigation of the effect of coexisting ions is most important in adsorption studies

as industrial wastewater consists of different anions and cations. There may be rivalry

among the different ions for the same adsorption sites. It is preferable to prepare a

multifunctional sorbent capable of extracting different forms of metal ions. Kesenci et

al. synthesised poly(ethylene glycol dimethacrylate-acrylamide) copolymer for

extraction of (lead mercury and cadmium) metal ions in an aqueous solution and the

order of metal uptake was found to be lead > cadmium > mercury. For a 1.0 mg/L

concentration of each metal, it was discovered that cadmium adsorption was higher in

the mixture (0.52 mmol) than in the individual solution (0.37 mmol) (Gupta et al., 2021)

Adsorption Kinetics

Adsorption kinetic helps predict adsorption rate and identification of underlying

adsorption mechanisms. It is vital to understanding the various reported adsorption

25
kinetic models and isotherm model equations. The significance of adsorption kinetics

lies in its ability to optimizing the conditions for maximum removal efficiency.

Adsorption kinetics models, such as the pseudo-first-order, pseudo-second-order, and

Elovich models, help to determine the rate constants and adsorption capacities under

different conditions like pH, temperature, and initial sample concentrations. These

models provide valuable insights into the adsorption mechanism, allowing identification

of the rate-determining step and the influence of various factors on the adsorption

process (Sen, 2023).

Pseudo-First-Order Kinetic Model

Developed by Largergren, the Pseudo-First-Order Kinetic Model has the following

assumptions:

 Adsorption only occurs at specific binding sites, which are localized on the

surface of the adsorbent

 Adsorption energy does not depend on the formation of a layer on the adsorbent

surface

 No interaction occurs between the adsorbed molecules on the surface of the

adsorbent.

The equation of the pseudo first order kinetic model is given by:

k1
ln ( qe −q t ) =ln q e −( ¿) ×t ¿
2.303

Where qe and qt are the adsorption capacity at equilibrium an d at time t (mg/g)

K1 is the rate constant for the first –order adsorption process (min-1)

(Kecili & Hussain, 2018)

Pseudo-Second-Order Kinetic Model

The pseudo-second-order kinetic model has been widely used to predict adsorption

kinetics and can be expressed as

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 t 1 1
= + t
qt k 2 q e q e
2

Where k2 is the rate constant of pseudo-second-order adsorption model (g/mg min).

t is the contact time (min)

qe and qt are the amount of solute adsorbed at equilibrium and at any time t,

respectively (mg/g).

(Kecili & Hussain, 2018)

Elovich Kinetic Model

The Elovich model equation is a widely used model in describing the kinetics of

chemisorption. It mathematically given as:

qt=1 ⁄ ¿

Intra particle diffusion model

The model is mainly used for the description of the adsorption process if the adsorbate

diffusion to the porous material is the rate limiting step. Weber and Morris have

proposed this kinetic model describing it in using the following formula:

1
2
q t=K id t + C

Where qt = is the amount absorbed at time t (mg/g)

Kid is the rate constant of intra-particle diffusion (mg/g min0.5)

C is the intercept value which gives an idea about the boundary layer thickness

(Ugwu et al., 2020).

Adsorption Isotherm

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The adsorption isotherm of any adsorption system is the curve that shows the number of

adsorbed molecules on the adsorbent surface as a function of the partial pressure or

concentration of the adsorbate at a constant temperature. Adsorption isotherms may be

used to offer qualitative information regarding adsorbent uptake capacity, as well as to

investigate equilibrium adsorption data (Bagal & Raut-Jadhav, 2021).

Langmuir Isotherm

The Langmuir equation makes the assumptions that there is no transmigration of the

adsorbate on the surface of the adsorbent, the adsorption energy is constant, and the

maximum adsorption corresponds to a monosaturated layer of adsorbate molecules on

the adsorbent surface. As one gets farther away from the adsorption surface, the

intermolecular interactions diminish and all adsorption sites are similar in terms of

energy. (Abin-Bazaine et al., 2022).

The linear form of langmuir model is expressed by the following equation:

Ce 1
= C
q e qm e+¿ q 1K ¿
m l

Where qm is the maximum adsorption capacity (mg/g)

KL is the Langmuir constant (L/mg)

Ce is the concentration of molecules at equilibrium (mg/L)

Freundlich isotherm model

The Freundlich model takes into account the heterogeneity of the surface of the

adsorbent and an exponential distribution of the active sites and their energies. It

describes the multilayer adsorption of molecules to an adsorbent surface. The equation

of the model is linearized as:

28
 1
log q e = log C e+¿log K ¿
n F

Where qe (mg/g) represents the amount of adsorbed molecules to the adsorbent surface

at any time.

Ce (mg/L) is the equilibrium concentration

n and KF are the Freundlich constant and Freundlich exponent, respectively.

KF (mg/g) indicates the adsorption capacity of the adsorbent toward the adsorbate and n

is an indicator for the degree of the surface heterogeneity and describes the distribution

of the adsorbed molecules on the adsorbent surface. The range of values of 1/n is

between 0 and 1 showing the degree of nonlinearity between the concentration of the

solution and the adsorption. If the value of 1/n is equal to 1, the adsorption is linear. A

value of n higher than 1 indicates a favorable adsorption of the molecules onto the

adsorbent surface. A value of higher n reflects the higher intensity of adsorption. In

addition, low values of n indicate the existence of a high proportion of high-energy

active sites (Bagal & Raut-Jadhav, 2021).

Temkin isotherm model

Temkin model takes the interaction between the adsorbent and the adsorbing species

into consideration. The Temkin isotherm model is presented in linear form with the

following equation:

q e =Bln C e + Bln K T

Where B = RT/b, b is Temkin’s constant, K T is the Bound Equilibrium Constant (L/g),

a B is related to the heat of adsorption (J/mol).(Abin-Bazaine et al., 2022)

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Dubinin–Radushkevich model
The adsorption of the molecules into the micropores of an adsorbent is described by the

Dubinin-Radushkevich adsorption model. According to this model, molecular

adsorption occurs in the micropores (pore filling) instead of adsorption on the surface of

the adsorbents that leads to monolayer or multilayer formation. The Dubinin–

Radushkevich adsorption model is commonly applied to the adsorption processes of the

subcritical vapors in the pores of the adsorbents such as zeolites and activated carbons.

This model is demonstrated by

2
ln q e =ln q m−β ε

Where qe is the amount of adsorbed molecules per mass of adsorbent (mg/g)

qm represents the adsorption capacity (mg/g)

β is the activity coefficient mol2/J2), which represents the adsorption energy

ε demonstrates the Polanyi potential as given in the following formula:

1
ε =RTln(1+ )
Ce

Where R is the ideal gas constant (J/mol.K)

T is the temperature (K)

Ce is the concentration of the molecules at equilibrium (mg/L).

(Kecili & Hussain, 2018)

2.3 Watermelon
Watermelon (Citrullus lanatus), a member of the Cucurbitaceae family, is a big, oval,

round or oblong tropical fruit that flourishes in warm climates. The pulp, seeds, and

30
liquid content of watermelon are routinely swallowed by people, however the peel,

totaling 30% of the entire fruit, is often thrown as trash with no feasible recycling

applications (Hasanin & Hashem, 2020).

Watermelon peel, as depicted in Figure 1, is typically produced by restaurants, small-

scale fruit juice producers, fruit vendors, and food and beverage processing facilities,

with limited efforts towards reutilization. Consequently, a substantial volume of waste

in the form of peels is generated and subsequently disposed of. The disposal of these

peels presents significant environmental consequences that pose a challenging problem

to address (Elhassaneen et al., 2022).

Figure 1: Watermelon peels (Bamisaye & Rapheal, 2022).

Approximate contents of the skin of mature watermelon include 20% cellSEOse, 23%

hemicellSEOse, 10% lignin, 13% pectin, 7 mg/g silica, and 12% silica-free minerals.

(Ibrahim et al., 2016). The presence of hydroxyl (cellSEOse) and carboxyl (pectin)

groups in watermelon peels makes it a suitable binding agent for heavy metals.

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Need to talk about the following

 constituents of watermelon peel

 Characterization equipments and techniques
 Properties of engine oil
 Review existing literatures

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