CTAC-Treated PVA-Coffee Parchment-Based Aerogel for Crude Oil Spill Adsorption

CHAPTER 1

THE PROBLEM AND ITS BACKGROUND

Introduction

Uncontrolled oil spillage, often resulting from marine transportation accidents and processing

activities, imposes an extensive environmental disaster, especially on marine ecosystems. These spills can

destroy wildlife, contaminate water sources, and disrupt regional economies that rely on tourism and

fishing. (Zhang et al., 2018)

When oil enters the water, the most evident effect is the spreading of the oil over the surface due

to the differences in density. This layer spreads rapidly and can go from thin to thicker layers, disrupting

the oxygen exchanges and promoting the ingestion of toxic substances by marine organisms. (Hancock,

2018) While these oils naturally degrade, although they may take a very long time, oil remediation

techniques exist to speed up the process to prevent further water contamination and danger to marine life–

classified as physical, chemical, biological, and thermal remediation. However, most of these techniques

often have limitations—for instance, P. Li et al. (2016) reported that chemical remediations can further

promote harm due to the toxicity of the chemicals used on some marine organisms while biological

methods are disadvantageous in terms of reaction time, and poor economic benefits.

Upon assessing the treatment time, cost, and the pollutants adsorbed, physical adsorption was

revealed to be the most economical and environmentally friendly method of oil remediation with the

utilization of recyclable and natural adsorbents. (Lee et al., 2021) Hence, researchers have explored the

utilization of natural agricultural by-products as oil spill adsorbents due to their porosity, abundance, and

low cost with modifications that further enhance these materials by improving their hydrophobic

properties, resulting in better adsorption efficiency and reusability.

 Combining the concept of sustainable development, implementation of energy conservation, and

emission reduction, the preparation of green bio-based aerogel materials has been focused on. As

cellulose is an abundant component of most agricultural wastes, especially from lignocellulosic biomass,

it has been used to prepare environmentally friendly aerogel composites. (Mai et al., 2024)

Cellulose-based aerogels are advantageous in terms of renewability, biocompatibility, biodegradability,

and low cost making them ideal candidates for a variety of applications–like oil adsorption. (Shi et al.,

2019)

Structurally, the surface of mucilage and coffee parchment is mostly composed of cellulose,

hemicellulose, and pectic polysaccharides with various reactive carboxyl and hydroxyl groups. Given the

abundance of these coffee wastes in the country and their notable cellulose content—approximately

8-30% in coffee mucilage and 40-49% in coffee parchment—they hold significant potential as raw

materials for developing cellulose-based aerogels. (Klingel, 2020)

In addition, in the formation of cellulose-based aerogels, the cellulosic biomass precursor is

treated with a defined concentration of sodium hydroxide (NaOH) that not only purifies the precursor

from impurities but also effectively removes lignin and hemicellulose in lignocellulosic materials, which

results in the exposure of cellulose fibers. This process enhances the material’s surface area which also

enhances its adsorption potential (Ukpong et al., 2024).

While the oil adsorption capacity of cellulose-based aerogels is attributed to their low density,

high porosity, and three-dimensional network structure, they are mostly further modified via

esterification, nanocoating, carbonization, silanization, etc. Shi et al. (2019) synthesized

pomelo-peel-based aerogel using silanization as a modification method and reported 94.66 % of oil

adsorption capacity, which decreased slightly to 93.82 % after 10 repeated cycles. The study by Thai et al.

(2019) used the same modification method in their synthesis of sugarcane bagasse-based aerogel and

showed a maximum oil adsorption capacity of up to 25 g/g with excellent mechanical properties as a

biodegradable adsorbent. Furthermore, Chhajed et al. (2019) modified their nano-fibrillated

cellulose-based aerogel via esterification and found that the maximum absorption capacity of the aerogels

was at least 35 times higher than their dry weight.

However, there were no studies yet found to synthesize cellulose-based aerogel from coffee

parchment and functionalized them with a surfactant coating, particularly of cetyltrimethylammonium

chloride (CTAC) given that it enhances a material’s hydrophobicity as it creates a layer that serves as a

barrier to water while also promotes oil uptake, allowing for a greater oil adsorption capacity (Li et al.,

2023). The coffee parchment’s cellulosic nature and the CTAC modification suggest a promising and

novel approach to synthesizing another yet effective cellulose-based aerogel for oil adsorption, which this

study aims to investigate.

With the intent to address environmental issues and satisfy sustainable development, this study

was in line with several Sustainable Development Goals (SDGs) set forward by the United Nations (UN).

This study contributed to SDG 6: Clean Water and Sanitation by aiming to serve as a physical remediation

to adsorb crude oil spills, SDG 12: Responsible Consumption and Production by utilizing coffee wastes

which reduces environmental impact and saves costs by reusing, and SDG 14: Life Below Water by

promoting its use in reducing crude oil contamination in marine ecosystems. By modifying these waste

materials, this study aimed to produce an efficient and environmentally friendly option for mitigating oil

spills, aiming to promote the utilization of sustainable materials in solving environmental problems.

While several studies have already explored the utilization of cellulose-based aerogels for oil

adsorption, this study offers an innovative approach to modifying the coffee parchment-based aerogel by

the introduction of a surfactant-coating CTAC to improve the hydrophobic properties as an adsorbent for

crude oil spill remediation.

Statement of the Problem

This study focused on investigating the efficiency of the CTAC-treated coffee parchment on a PP

polymer composite matrix for crude oil spill adsorption.

Specifically, this aims to answer the following:

1.) Which concentration of CTAC (0, 2, 4 ? %) yields the highest result in terms of:

a. hydrophobicity

b. oil adsorption capacity

2.) What are the characteristics of the CTAC-treated PVA polymer composite matrix in terms of:

a. surface area,

b. surface morphology, and

c. functional groups?

3.) How does the use of the CTAC-treated PVA polymer composite matrix impact the percentage of

crude oil adsorption, given variations in the following parameters:

a.​ dosage of the coffee parchment in aerogel (50, 100, 150 g/L)

b.​ contact time? (30, 60, 90, s)

4.) How do the changes in the CTAC-treated PVA polymer composite matrix after oil adsorption be

described in terms of:

a.) surface area

b.) surface morphology, and

c.) functional groups?

5.) Which isotherm and kinetic models provide the best fit for understanding the adsorption process of

crude oil on the CTAC-treated PVA polymer composite matrix?

Alternative Hypothesis:

H1: There will be a significant effect on the hydrophobicity of coffee parchment when treated with NaOH

and CTAC, resulting in a more hydrophobic sorbent.

H2: A composite matrix formed by mixing Polyvinyl Alcohol (PVA) as a binder and treated coffee

parchment as an adsorbent in decalin and 1-butanol solvents will enhance the efficiency of collection and

application for oceanic oil spill remediation.

Significance of the Study

This study explores the utilization of the CTAC-treated coffee parchment on a PVA polymer

composite matrix to create a hydrophobic sorbent for crude oil spill clean-up. Specifically, this study will

be beneficial to the following individuals or sectors:

The Community. Communities, particularly those near oil drilling sites, and coastal areas, are

directly impacted by oil spills, which can result in respiratory problems and contaminated water. This

study’s production of an effective oil spill clean-up method can protect community health by reducing the

harmful effects of oil spills on bodies of water and drinking water sources. By promoting cleaner

environments, the research contributes to overall community well-being and resilience.

Fishing Industry. The results of this study will also be significant to the fishing industry because

oil spills can have a harmful effect on fish populations and marine health, this can have long-term

implications on fishing stocks and livelihoods. Since healthy fish populations and safer fishing methods

are crucial for the well-being of individuals who depend on fishing for a living, it is important to maintain

fish populations and marine health by using effective cleanup techniques.

Oil and Gas Industry. By using environmentally friendly sorbent solutions for oil spill cleanup,

the oil and gas sector can greatly profit from the study's results. Using a biodegradable and affordable

sorbent can help the industry address environmental issues while reducing cleaning costs and enhancing

their public image as regulatory pressure for more sustainable practices grows. In the future, sustainable

methods may result in safer operations and lower public health hazards.
 Coffee Farmers. The results of this study are going to help coffee farmers. By showing that

coffee mucilage and parchment can be transformed into valuable sorbents, farmers may increase their

income while reducing agricultural waste. This improves the farmers' livelihoods and encourages

sustainable farming methods.

Future Researchers. Lastly, the results of this research are significant to future researchers who

can improve the findings presented. By establishing a basis for using modified agricultural waste in oil

spill control, this study can serve as a reference for ongoing research and development in oil spill

remediation and the health impacts associated with it.

Scope and Limitations of the Study

This study aims to examine the potential of coffee parchment combined with a polyvinyl alcohol

(PVA) aerogel composite matrix treated with CTAC as an efficient material for adsorbing crude oil spills.

The main goal was the identification of how the hydrophobic properties of coffee parchment are enhanced

by the chemical modification with cetyltrimethylammonium chloride (CTAC) and the eventual

introduction into a PVA aerogel composite [Link] oil pollution is one of the critical environmental

problems that threatens coastal areas and marine ecosystems. The purpose of this study is to create a

composite material that can efficiently absorb and hold onto crude oil without harming the environment in

order to clean up oil spills. It achieves this by combining CTAC with the special qualities of coffee

parchment and PVA aerogels. Characterization techniques such as FTIR and SEM will be used in order to

investigate physical characteristics, chemical structure, and adsorption capacity of the composite under

specially controlled laboratory settings.

However, the study has several limitations. Firstly, the PVA gives the aerogel composite

advantageous mechanical qualities but its inherent hydrophilicity could limit the ability of the composite

to be hydrophobic, and more tuning may be required for optimum performance. Environmental issues

also had to be considered because although PVA is water soluble and biodegradable under certain

conditions, the rate of degradation may not be fast enough for long-term use in oil spill remediation. This
raises concerns on the environmental impact of using synthetic polymers in conjunction with natural

materials like coffee parchment. Furthermore, it is still not yet clear whether mass production of this

composite material can be made cost-effective. The cost of raw materials, processing methods, and

possible market acceptability would need to be evaluated to determine the feasibility of using this oil spill

cleanup. Last but not least, the study may focus on certain types of crude oil for the adsorption test that

limits the scope of application for the results to other kinds of mixtures that can be present in an actual

spill situation. various oils have different chemical compositions and viscosities that could impact the way

they can adsorb substances.

Conceptual Framework

The aim of this research is to create a crude oil sorbent material from CTAC

The current methods for oil spill treatment are often insufficient due to high costs driven by labor

intensity, regulatory constraints, and inefficiencies in existing techniques. This requires an alternative

solution that still aligns with the goal of remediation of oil spills, which this study aims to do: create a

cost-effective, environment-friendly, and efficient biosorbent material for oil spill treatment.

Coffee wastes are ideal materials to create an effective biosorbent material for oil spill treatment,

aside from its convenient availability in Batangas, its structure and properties play a major role, some of

which are easily altered. Its structure contains organic compounds, particularly cellulose, hemicellulose,

and lignin, making the coffee naturally hydrophilic. However, after modification, it shows an increase in

its porosity which creates a higher surface area allowing for more active sites on the coffee and higher oil

retention.

Coffee parchments and mucilage can be modified through various processes, one of these is the

exposure to an alkaline environment such as NaOH, which enhances its porosity and surface area,

allowing for more crude oil retention. However, as mentioned, organic materials are naturally hydrophilic,

which is why the use of cetyltrimethylammonium chloride (CTAC) is highlighted in this study as it

transforms the coffee waste into becoming a hydrophobic material capable of adsorbing and maintaining
crude oil in its surface. CTAC possesses a positively charged ammonium head group, which interacts

favorably with negatively charged or polar surfaces. This electrostatic interaction can displace water

molecules from the surface, promoting hydrophobicity, and instead attracts negatively charged sites of the

crude oil, of which manipulation of surface charges is needed.

NaOH and CTAC-modified coffee wastes should exhibit a higher surface area, hydrophobicity,

and chemical attraction to crude oil through adsorption mechanisms. In this case, it is expected that crude

oil molecules will cling to the surface of modified coffee wastes until they can be easily cleaned up.

While other mechanical and chemical processes for crude oil remediation are effective at the same time,

they are either manpower-demanding or expensive to be executed, or sometimes raise concerns regarding

air pollution and environmental impact, e.g. in-situ burning. Physical adsorption is one of the most

effective alternatives as it offers simplicity while being cost-effective, allowing straightforward

implementation relying on the natural affinity of certain materials for oil, minimizing ecological impact.

In order to determine if our coffee waste modification is successful, various tests can be

implemented to show physical alterations. FTIR and SEM can provide visual representations of

modification such as shift or formation of new peaks in the graph or change in surface morphology

indicating successful chemical modification. Wettability tests can also show enhanced hydrophobic

properties when an increase in contact angle is observed, a desirable characteristic for oil adsorption

applications.

Overall, utilizing coffee waste for crude oil remediation not only addresses the immediate issue of

oil spills but also promotes environmental sustainability through waste valorization, biodegradability,

energy recovery, cost-effectiveness, and alignment with global sustainability goals.

Theoretical Framework

As mentioned, there is a need for an alternative solution for crude oil treatment, and one best

option is to synthesize a biosorbent material to absorb crude oil spills. Adsorption is a surface

phenomenon where molecules from a gas or liquid adhere to the surface of another material. This is
deemed effective as a mechanism for crude oil adsorption as sorbent materials can have high capacities

for oil retention, allowing them to absorb significant amounts of oil relative to their weight. These sorbent

materials often possess oleophilic (oil-attracting) and hydrophobic (water-repelling) characteristics. This

combination allows them to selectively adsorb oil while repelling water, making them particularly

effective in aquatic environments where oil spills occur. The adsorption characteristics can be identified

with the use of Langmuir Isotherm, which assumes that adsorption occurs on a homogeneous surface with

a finite number of identical sites, where each site can hold only one molecule of adsorbate, which in this

study is crude oil.

Naturally, organic materials are hydrophilic and require modification to be effective in adsorbing

crude oil. Treating coffee wastes with NaOH leads to the removal of lignin and hemicellulose, which

exposes more cellulose fibers and increases the overall surface area of the coffee waste (Ukpong et al.,

2024). Studies have shown that this treatment can increase the specific surface area by over 100 times

compared to untreated samples, facilitating greater adsorption capacity for various substances, including

oils and pollutants (Zamparas et al., 2020; Lee et al. 2021).

On the other hand, CTAC, as a cationic surfactant, interacts with the lignocellulosic components

of coffee waste by adsorbing onto their surfaces. This interaction modifies the surface property, the long

hydrophobic alkyl chains of CTAC orient themselves outward, creating a surface that repels water while

attracting oil. The modification with CTAC can lead to a substantial increase in the water contact angle on

the surface of coffee waste. A higher contact angle indicates enhanced hydrophobicity, which is beneficial

for oil adsorption as it allows the material to preferentially interact with oils rather than water.

The Cassie-Wenzel Model could be a great fit for explaining how CTAC enhances the

hydrophobicity of modified coffee waste for oil adsorption. According to the Cassie-Baxter component of

the model, the rough, CTAC-coated surface traps air pockets when exposed to water, reducing the surface

energy and creating a superhydrophobic effect that helps repel water more effectively, which should

facilitate the attachment of crude oil to the surface area of the coffee waste. It suggests that when a liquid

droplet sits on a rough surface, the apparent contact angle is influenced by the surface roughness.
 These points highlight the development of a modified coffee waste biosorbent for crude oil spill

remediation. Adsorption is an effective mechanism for oil retention, relying on materials that are both

oleophilic and hydrophobic. Traditional organic materials, however, are hydrophilic, requiring

modifications to make them suitable for oil adsorption. By treating coffee waste with NaOH, surface area

is increased and adsorption capacity is enhanced. Further treatment with CTAC introduces hydrophobic

properties by forming a water-repellent surface layer. The Cassie-Wenzel Model supports the theory that

CTAC-treated surfaces trap air pockets, increasing the contact angle and creating a superhydrophobic

surface that selectively absorbs oil. This combination of modifications makes coffee waste a viable,

environmentally friendly alternative to traditional sorbents for oil spill applications.

Definition of Terms

●​ Adsorption. The process by which molecules from a liquid or gas adhere to the surface of a solid

material.

●​ Biodegradability. The ability of a substance to be broken down naturally by microorganisms into

simpler, non-toxic substances.

●​ Bulk Density. The mass of a material per unit volume, including both solids and void spaces.

●​ Cetyltrimethylammonium Chloride (CTAC). A cationic surfactant that increases a material’s

hydrophobicity by changing its surface properties.

●​ Crude Oil Spill. An accident release of crude oil into the environment, often resulting from

transportation or extraction activities.

●​ Contact Angle. A measure of how a liquid droplet interacts with a solid surface, indicating the

wettability of that surface.

●​ Environmental Remediation. The process of removing pollutants or contaminants from

environmental media like soil and water.

●​ FTIR (Fourier Transform Infrared Spectroscopy). An analytical technique used to obtain an

infrared spectrum for identifying chemical compounds.

●​ Functional Groups. Specific groups of atoms within molecules that determine the chemical

properties and reactions of those molecules.

●​ Hydrophobic Sorbent. A substance that effectively absorbs oil spills because it has a strong

affinity for oil and repels water.

●​ Hydrophilic. Having an affinity for water; capable of attracting and absorbing water substances.

●​ Isotherm Models. Mathematical models that describe how adsorbates interact with adsorbents at

constant temperature.

●​ Kinematic Models. Mathematical representations used to describe the rate at which adsorption

occurs over time.

●​ Lignocellulosic Materials. Organic materials made up primarily of cellulose, hemicellulose, and

lignin, commonly found in plant biomass.

●​ Oleophilic. Having an affinity for oil; capable of attracting and absorbing oil substances.

●​ Porosity. A measure of the void spaces in a material that affects its ability to absorb liquids.

●​ SEM (Scanning Electron Microscopy). A type of electron microscope that provides

high-resolution images by scanning surfaces with a focused beam of electrons.

●​ Sodium Hydroxide (NaOH). A strong alkaline substance that is employed in many chemical

reactions, especially when altering materials to improve their characteristics.

●​ Surface Morphology. The study of the surface structure and texture of materials at a microscopic

level.

●​ Sustainable Development Goals (SDGs). A set of 17 global goals established by the United

Nations to address various social, economic, and environmental challenges.

1.)​ What conditions provide the best fit for the CTAC-treated parchment on the PVA polymer

composite matrix in crude oil adsorption given variations in the following parameters:

a.) concentration of the CTAC (0, 2, 4, % )

b.) dosage of the coffee parchment (50, 100, 150 g/L)

c.) contact time (30, 60, 90 s)

2.)​ What are the characteristics of the CTAC-treated parchment on the PVA polymer composite

matrix in terms of:

a. surface area,

b. surface morphology, and

c. functional groups?

3.)​ How do the changes in the CTAC-treated parchment on the PVA polymer composite matrix

after oil adsorption be described in terms of:

a.) surface area

b.) surface morphology, and

c.) functional groups?

4.)​ Which isotherm and kinetic models provide the best fit for understanding the adsorption process

of crude oil on the CTAC-treated parchment on the PVA polymer composite matrix?
 CTAC-Treated PVA Aerogel Composite Matrix Integrated with Coffee Parchment for Crude Oil
Spill Adsorption

CHAPTER 2

REVIEW OF RELATED LITERATURE

This chapter explored the relevant literature for a comprehensive understanding of the current

research topic and its nature, highlighting the importance and relevance of chemically treating PVA

aerogel composite matrix integrated with coffee parchment to be used as a sorbent for crude oil spill

adsorption.​

Conceptual Literature

1.​ Types of Adsorbents (1 person)

1.1 Natural Adsorbents​

1.1.1 Clays

Natural sorbents, which include clay-based materials such as kaolinite, montmorillonite,

and bentonite, play a vital role in environmental remediation and water treatment because of their

unique adsorption properties. These clays are able to remove a wide range of contaminants,

including heavy metals and organic compounds, through mechanisms that are affected by

variables such as pH, temperature, contact time, and contaminant concentration. Their high

surface area and strong affinity for pollutants make them valuable in applications such as water

purification and oil spill cleanup. These natural sorbents, in binding to oil and other contaminants,

make collection easier and are environmentally friendly.

 1.1.2 Zeolites

Natural zeolites are highly effective sorbents for environmental applications, especially in

the removal of pollutants from water and air. These microporous minerals, such as clinoptilolite,

mordenite, and ferrierite, have a special three-dimensional structure that can provide high surface

area and significant cation exchange capacity. This structural feature allows zeolites to effectively

adsorb heavy metals, carbon dioxide, and other contaminants through mechanisms involving both

physical and chemical interactions, including ion exchange and Van der Waals forces. Natural

zeolites are not only a cost-effective alternative to synthetic sorbents but also environmentally

friendly because of their abundance and non-toxic nature. Research has revealed their uses in a

multitude of applications, such as wastewater treatment and carbon dioxide capture, and are,

therefore valuable materials in solving environmental challenges of [Link] ability to

selectively remove ions and molecules, owing to their pore size, further enhances their

applicability in a variety of fields, ranging from industrial processes to ecological remediation

efforts.

1.1.3 Vermiculite

Naturally, a mineral with wonderful expansive properties and flexibility in several

applications, most notably as a sorbent in environmental cleanup, vermiculite expands

dramatically on heating, increasing its volume considerably with formation of lightweight,

worm-like threads able to absorb up to four times their weight in water, making it useful in

horticulture for improving soil moisture retention and nutrient delivery. Its high cation exchange

capacity allows it to retain critical nutrients, and its pH neutrality and fire resistance make it

appealing. In the environment, vermiculite effectively adsorbs contaminants like oils and

hydrocarbons, hence increasing the quality of petroleum products by adsorptive treatment.

Overall, vermiculite's combination of absorbency, lightweight nature, and thermal stability

position it as a key material in both agricultural and environmental applications.

 1.1.4 Perlite

Perlite is a natural volcanic glass that expands extensively upon heating and is one of the

most effective and versatile natural sorbents, which can be applied in different environmental

purposes. Due to its light, porous structure, perlite is highly effective at absorbing and retaining

liquids, such as oils and toxic chemicals, and thus has great applicability in spill cleanups and

stabilization of pollutants. As a natural stormwater filter, perlite helps preserve waterways while

conserving local ecosystems. Moreover, its non-toxic and inert nature prohibits it from releasing

harmful chemicals into the environment, which adds to its long-term sustainability. Perlite mining

has low environmental impact, with less than 1% of known reserves exploited in the last 60 years,

and it is often processed without chemicals.

1.1.5 Agricultural Wastes

Due to their natural properties and wide availability, Agricultural waste have gained

interest as efficient and reasonably priced adsorbents for the removals of pollutants. Functional

groups such as carboxyl and hydroxyl in these waste, which include materials like banana peels,

rice husk, coir pith, and tea leaves, enhance their ability to adsorb a variety of pollutants,

including organic colors and heavy metals. The ability of several agricultural wastes to adsorb

varies with factors such as contact time, dosage of the adsorbent, and type of contaminant.

Characteristics of Agricultural Waste as Sorbents

Agricultural Pollutant Type Adsorption Contact Time Isotherm Model

Waste Capacity (mg/g) (min)

 Coir Pith Ash As(V) 36.50 60 Langmuir

isotherm model

Pine Saw Dust Cu, Pb 9.59 5 Freundlich

isotherm model

Carnauba Straw Cu 9.5 5 Freundlich

Powder isotherm model

Rice Husk Cr(III) 30.0 120 Langmuir

isotherm model

Banana Peel Methylene Blue 52.1 30 Langmuir

isotherm model

Coffee Waste MCPA 340 5 Langmuir

isotherm model

●​ Coffee Waste

Because of its potential as a green adsorbent, especially on oil adsorption, there is an

increasing recognition that coffee waste, including coffee grounds, coffee husk, and coffee pulp

discarded during the coffee-processing activities, is useful agricultural waste. Huge amounts of

this litter are generated during the coffee processing process, and it has been discarded or burned

on-site, which has boosted environmental problems. Despite its high organic content, which

includes polyphenols and other beneficial substances, it is suitable for a number of applications,

especially in pollution management. In addition to solving waste disposal-related environmental

problems, the use of coffee waste as an adsorbent provides a long-term solution to oil
contamination. The coffee industry can enhance efforts to control pollution and use resources

more efficiently by transforming this agricultural by-product into a useful item.

1.2.1 Activated Carbon​

Activated carbon is a highly porous material that effectively traps compounds, usually

organic. Its efficiency has made it a trusted purifying agent by humans. In addition to its role in

purification, its pores and large surface area enables its use as a medium in absorption. In

comparison with the traditional remediation process, it is better in removing various contaminants

present in water including the removal of organic contaminants. (Singh et. al. 2020).

1.2.2 Polymeric Sorbents​

A polymer sorbent is a material designed to capture specific substances from liquids or

gases through either adsorption or absorption. Polymer adsorbents operate through surface

sorption, where substances adhere to the material's surface, while polymer absorbents utilize bulk

sorption, drawing substances into their interior. (IUPAC, 2019) These materials are widely used

in separation and purification processes due to their numerous advantages, including a

well-developed surface area, high thermal stability, and resistance to chemicals such as organic

solvents and solutions with extreme pH levels. Additionally, their porosity and surface chemistry

can be tailored to meet specific requirements, enhancing their versatility and effectiveness.

(Zhang, 2022)

1.2.3. Nanomaterials ​

Nanomaterials are materials that measure on the nanoscale (1–100 nm) or contain

nanoscale structures either internally or on their surfaces. They can be engineered with various

chemical compositions, structures, and surface properties, and their magnetic, electronic, and

optical characteristics can also be tailored. The small size of nanomaterials allows for unique
 properties, such as enhanced permeability through tissues like skin, hair, and nails, as well as

selective accumulation within these tissues. Additionally, the surface of nanomaterials can be

modified to target specific molecular structures and cell types. For example, coating a

nanomaterial with a monoclonal antibody that binds to a particular cell receptor enables targeted

delivery to specific neoplastic, infected, or inflammatory cells. (Mordorski et. al., 2016)​

1.2.4 Aerogels​

Aerogels are a unique class of nanoporous materials with exceptional properties, first

invented by S. Kistler in the early 1930s. The term "aerogel" refers to a group of materials with

specific structures and remarkable characteristics, not a single material. These materials are

typically created through sol–gel chemistry, where the liquid in a gel is replaced with gas using

specialized drying techniques. The result is an ultra-light, porous solid, sometimes transparent,

with up to 99.2% of its volume consisting of empty space. Aerogels are made by assembling

nanoparticles, derived from organic or inorganic precursors, into an interconnected nanostructure.

(Maleki et. al., 2016)

2.​ Aerogels​

2.1. Types of aerogels​

Aerogel is a state function, meaning its value depends only on its current state, not the

process used to achieve it. To qualify as an aerogel, a material must have a porosity of at least

50% by volume, with the majority of its pores being mesoporous. The specific type of aerogel is

determined by the material used in its production. ([Link], 2019)

2.1.1. Silica aerogel​

Silica aerogel is the most common type of aerogel. Thus, this is the type most

frequently shown in photographs and what people think when the word “aerogel”,
 without an adjective to describe what its type is mentioned. ([Link], 2019). Silica

aerogel is a highly translucent material consisting of a nanostructured SiO2 network, with

porosities of up to 99.8% and low thermal conductivity values. They are commonly used

as thermal insulation materials, however its commercial availability is very limited.

(Villasmil [Link]., 2019)

2.1.2. Metal aerogel​

Metal aerogels are formed by supercritical dried gels composed of metal

nanoparticle networks, combining the unique properties of metals and aerogels. They

have high specific surface areas (100-500 m²/g) and electrical conductivity, making them

ideal for high-surface-area electrodes in supercapacitors, fuel cells, batteries, and water

desalination. Moreover, their nanosized metal particles enhance catalytic activity,

enabling efficient catalytic reactions like CO oxidation and carbon nanotube growth.

Metal aerogels could potentially replace expensive, scarce metals (e.g., Pd, Rh, Pt) in

catalytic converters with more abundant options like Fe or Ni, offering a cost-effective,

sustainable alternative. ([Link], 2019)

2.1.3. Cellulose aerogel​

Cellulose aerogels’ characteristics, which include having a wide range of sources,

its biocompatibility,and its porous properties gives it a potential to be a multifunctional

material. However, the functions of a pure cellulose aerogel is not enough to meet the

demands of an actual production. Thus, its preparation must include functional

modification to improve its properties, this way, the product will be more profitable (Mai

et. al., 2024)

2.2. Materials for Cellulose-Based Aerogel Formation

 Materials are crucial in the formation of aerogels, as they define the characteristics and

type of the final aerogel product. In addition to the primary material, solvents and binders are

essential components required for aerogel creation. The careful selection of these materials

ensures the desired properties, such as porosity, mechanical strength, and thermal stability, in the

final product.

2.2.1. Solvents

Solvents play a crucial role in the production of cellulose-based aerogels by

serving as a medium to dissolve the cellulose powder and binders, ensuring uniform

mixing and gel formation. Commonly used solvents include water, ethanol, acetone, and

ionic liquids. Solvents influence the drying process, as their removal during supercritical

drying or freeze-drying affects the porosity and structural integrity of the aerogel.

[Link]. Ionic Liquids​

Ionic liquids (ILs) are solvents with low volatility, flammability, and

wide liquid-state window making them a greener alternative to traditional organic

solvents. These solvents have features, particularly, being tunable and can be

utilized to extract an analyte by the proper selection of their constituent ions. that

gives them a broad application in analytical sample preparation. (Llaver et. al.,

2021)​

[Link]. Inorganic Solvents​

Inorganic solvents are non-aqueous solvents that lack organic

components. They function based on a solvent system that facilitates the

dissolution of solutes. Typically, they are polar in nature, thus, inorganic solvents
 do not mix well with organic or non-polar solvents. Solutions formed using this

often have high electrical conductivity. Common examples include ammonia,

sulfuric acid, and sulfuryl chloride fluoride.

[Link]. Organic Solvents​

Organic solvents are volatile compounds widely used across various

industries, making human exposure to them almost unavoidable. They play a

critical role in chemical synthesis and are commonly found in numerous

applications, such as dry cleaning (e.g., tetrachloroethylene), paint thinners (e.g.,

toluene, turpentine), nail polish removers, glue solvents (e.g., acetone, methyl

acetate, ethyl acetate), spot removers (e.g., hexane, petroleum ether), detergents

(e.g., citrus terpenes), and perfumes (e.g., ethanol). (Litbarg, 2018) ​

[Link]. Water Based System

Water-based system refers to the use of water as a solvent in the

formation of cellulose-based aerogels. In this process, water facilitates the

dissolution of cellulose, facilitating the subsequent gelation and formation of the

aerogel structure. The natural gelation process of a water-based system is

generally advantageous with the simplified preparation procedure and enhanced

sustainability. (Onwukamike et al., 2019)

2.2.2. Binder

Binders are used to enhance the structural integrity and stability of

cellulose-based aerogels by promoting the adhesion between cellulose fibers or particles

during the gel formation process.

 ​

[Link]. Starch

Starch is a natural carbohydrate, and a lightweight porous material used

as a binder in the formation of cellulose-based aerogels. It helps hold the

cellulose fibers together, facilitating the creation of a stable gel. It helps maintain

tiny air pockets and enhances the strength and flexibility of the aerogel.

(Rodríguez et al., 2019)

[Link]. Silica Sol

Silica sol is another lightweight and highly porous material, and is a

liquid form of silica. It is mixed with cellulose to form a gel through a method

called sol-gel, where aerogel is obtained when this sol-gel is dried under optimal

conditions. The addition of silica sol as a binder enhances the material’s

mechanical strength and thermal insulation properties, improving the over-all

performance of the cellulose-based aerogels. (Silviana et al., 2022)

[Link]. Poly-vinyl Alcohol (PVA)

PVA is a water-soluble synthetic polymer mixed with cellulose fibers or

particles to form a gel through hydrogen bonding and physical interactions. This

undergoes partial hydrolysis and cross-linking during the drying process where

this cross-linking enhances the mechanical strength of the aerogel, making it

more resilient to deformation and breakage. (Yi et al., 2024)

2.3. Methods for Cellulose-Based Aerogel Modification

To achieve better oil adsorption efficiency, cellulose-based aerogels are usually further

modified via different methods as cellulose-based aerogels often have limitations when left
unmodifed.​

2.3.1. Silanization

During silanization, silane compounds such as methyltrimethoxysilane (MTMS),

react with the hydroxyl groups present on the cellulose fibers or particles. The

introduction of silane compounds in cellulose-based aerogels modifies the surface

characteristics of the cellulose particles and enhances their water-repellency. Silanized

cellulose aerogels can achieve superhydrophobic properties, with water contact angles

exceeding 150°. (Iskandar et al., 2022)

2.3.2. Nanocoating

Nanocoating is a method used to improve the performance of cellulose-based

aerogels by adding a thin layer of nanoparticles or nanomaterials to their surface. This

can be done in different ways, such as using sol-gel processes, dip-coating, spray coating,

or layer-by-layer assembly. The nanoparticles stick to the cellulose, either by bonding

chemically or through physical attraction, improving the surface without really changing

the aerogel’s overall structure. (Zhao et al., 2023)

2.3.3. Functionalization

Functionalization usually involves chemical reactions that add new functional

groups to the cellulose structure. For instance, adding hydrophobic groups can turn a

water-absorbing aerogel into a superhydrophobic one, making it perfect for things like

separating oil from water. Similarly, surfactants can be mixed into the cellulose solution
 or gel during the production process. These surfactants change the surface chemistry of

the aerogels, boosting their ability to repel water or oil.

3.​ Methods for Oil Spill Remediation

3.1 Physical Remediation

Physical remediation, the oldest method of oil spill remediation, involves mechanically

removing oil from the environment. It is known for its efficiency and eco-friendliness, because it

does not involve the use of chemical compounds, it eliminates the need for prior governmental

approval before initiating cleanup operations. In addition, unlike chemical or thermal remediation

techniques, physical methods exert minimal to no negative environmental impacts. Common

physical remediation techniques include booms, skimmers, and sorbent materials. Booms are

used to contain oil spills, preventing their spread, while skimmers and sorbents are employed to

collect and remove the oil, often in conjunction with other remediation methods. (Dhaka et. al.,

2021)

3.2 Chemical Remediation​

Chemical methods for treating oil spills are often used in combination with physical

techniques due to their ability to alter the physical and chemical properties of oil. These methods

are generally more cost-effective and require less manpower than mechanical recovery. However,

since they modify the oil's properties, it becomes unsuitable for reuse. Furthermore, while

chemical methods can be applied to various oil types and are effective in diverse weather

conditions, they pose significant environmental risks due to residual chemicals that can harm

marine ecosystems. The primary chemicals used in these methods are dispersants and solidifiers.

(Hoang, 2018)
 3.3 Thermal Remediation​

The thermal remediation method involves burning oil to remove it from the environment.

Although the removal of large quantities of oil can be achieved with minimal specialized

equipment, such as fire-resistant booms or igniters, this technique is particularly advantageous in

calm wind conditions and is best suited for fresh spills or refined products that burn quickly

without causing significant harm to marine life. Fire-resistant booms are used to collect and

concentrate the oil into a thick slick suitable for burning, with the remaining residue removed

using mechanical methods. The success of this method depends on factors such as the thickness

of the oil slick, adequate oxygen supply, water temperature, wave amplitude, wind direction, oil

type, and the extent of weathering and emulsification. (Tewari et. al., 2016)

3.4 Bioremediation

Advances in genetic engineering have enabled the development of genetically modified

microorganisms that act as bioremediation agents. Bioremediation is a collection of biological

processes used to treat environmental contaminants through living organisms, such as plants and

microorganisms (particularly bacteria and fungi), that degrade or transform harmful substances. It

is generally more cost-effective than chemical methods, but its large-scale application in field

conditions faces challenges. Key limitations include the availability and specific interactions

between contaminants and microorganisms, as well as the difficulty of isolating microorganisms

with high degradation potential using conventional techniques. (Landa-Acuna, et. al., 2020)

4.​ Factors Influencing the Oil Adsorption Capacity of an Adsorbent

4.1 Adsorbent’s Hydrophobicity​

Adsorption is a process in which contaminants attach to the surface of an adsorbent due

to its hydrophobic and electrostatic interactions with the adsorbate. In the context of oil spill

remediation, materials with high hydrophobicity are particularly effective because they repel

water, which allows them to interact and absorb greater oil. This technique is widely used in oil

spill remediation, since hydrophobic materials tend to float on water, it allows for the efficient

separation of oil from water. (Ukpong et. al., 2024) ​

4.2 Specific Surface Area ​

The specific surface area of a porous material is defined as the interstitial surface area of

the pores per unit of bulk or solid volume within the porous system. This parameter is crucial for

determining fluid conductivity or permeability. One of the main factors in estimating specific

surface area is the ratio of the grain particle perimeter to the area of each grain in a 2D section,

known as the specific parameter (Rocha, 2019).

4.3 Surface Morphology​

The morphology of a surface refers to the nature and extent of its roughness, which can

describe either the overall surface or specific surface features. It encompasses the

three-dimensional shapes and structural characteristics that define the surface's appearance and

texture. Surface morphology is a key factor in understanding how a material interacts with its

environment, influencing properties such as adhesion, friction, and wear. This morphology is

typically evaluated using advanced imaging techniques, such as optical microscopy, which

provides detailed surface images at lower magnifications, or scanning electron microscopy

(SEM), which offers higher-resolution, three-dimensional images of surface structures. These

imaging methods allow for a comprehensive analysis of surface topography at the microscopic

level. (Mehralizadeh et. al., 2020)

 4.4 Functional Groups​

Functional groups are structural components of organic compounds that go beyond

simple carbon-carbon and carbon-hydrogen single bonds. These include multiple bonds between

carbon atoms and bonds linking carbon to elements such as oxygen, nitrogen, sulfur, and

halogens. Functional groups exhibit predictable chemical behaviors based on the number and

types of bonds they form with carbon. The chemical properties and reactivity of organic

molecules are largely determined by the functional groups they contain, influencing their

interactions and transformations in various chemical reactions. (Ouellette et. al., 2015)

4.5 Amount of the Adsorbent​

As the amount of adsorbent increases, the adsorption capacity per unit weight of the

adsorbent decreases. This is because the adsorption is defined based on the amount of adsorbate

per unit mass of adsorbent, and with more biosorbent present, the adsorption per unit mass

diminishes. However, the total adsorption still increases with the quantity of adsorbent, leading to

a higher overall biosorption efficiency. Despite the reduction in adsorption per unit mass, the

removal efficiency rises significantly from 25.64% to 95.47% as the amount of biosorbent

increases. (Kamseh, et. al, 2023)

4.6 Contact Time

Contact time is a critical factor that influences the oil adsorption capacity of an adsorbent.

In the study of Aswadi et al. (2023), it was observed that a significant increase in the oil

adsorption capacity of rubber seed kernels activated carbon (RSKAC) took place between the

period of 120 and 150 minutes–during which the time the oil has successfully diffused into the

available sites of the adsorbent. This shows that oil may diffuse into the available active sites of

the adsorbent during the initial stages and achieve maximum capacity rapidly beyond the initial

stage. However, some adsorbents may not exhibit the same behavior due to the adsorbent’s
 available sites. For instance, modified sawdust achieved its highest oil sorption capacity at around

10 minutes before the saturation of the available sites. While the increased contact time generally

enhances the oil adsorption capacity of the adsorbent and eventually reaches the maximum,

prolonged contact time can lead to a decrease in the efficiency of the oil adsorption due to

desorption mechanisms where the previously oil-bound molecules start to detach from the surface

of the adsorbent. (Ibe et al.,2024)’

5.​ Crude Oil Spills as an Environmental Problem

6.​ Sources of Crude Oil in Contaminated Water (Add more if possible)

6.1 Marine Transportation

6.2 Pipeline Leakages

6.3 Industrial Discharges

6.4 Road Run-Off

7.​ Analytical Testing

7.1 Optical Tensiometry

7.2 Gravimetric Method

7.3 Brunauer-Emmett-Teller (BET) Method

7.4 Scanning Electron Microscopy (SEM)

7.5 Fourier Transform Infrared Spectroscopy (FTIR)

7.6 Testing of Reusability

7.7 Response Surface Methodology

7.8 Adsorption Kinetics

 7.9 Adsorption Isotherms

Related Literature

Environmental Impact of Oil Spill

Marine ecosystems are seriously threatened by oil spills, which specially harms shorelines. The

article by Asif [Link] (2022) offers an in-depth review of the environment's effect and difficulties posed by

oil spills, which outlines the vulnerability of the shorelines and the difficulties associated with handling

this situation. As the oil spreads across the aquatic surface causing destruction to marine organisms and

disrupting the exchange of oxygen, all causing long-term ecological impacts.

Oil Spill Issues

Oil spills are some of the disasters which have devastating social, economic, and environmental

effects. The number of cases of oil spills and the amount of oil spilled by tankers has had a huge impact

in the past few decades. It resulted from the discharge of crude oil or refined petroleum products from

tankers, rigs, wells, and offshore platforms. These spills mostly occur in maritime areas but can also occur

on land (Ritchie et al., 2022). They can cause extreme effects on local ecosystems and are expensive

because of the loss of oils as well as the cost involved in cleaning them up.

Existing Oil Spill Remediation​

Because oil spill has a negative effect on the ecosystem, cleaning is a great concern. Aquatic

organisms experience adverse effects of the petroleum spills, causing damages to their habitats and food

chains. Therefore, proper remediation must be done after oil spillage.

Physical Method

According to the study of Sharma et al. (2024), one of the best and most environmentally

friendly methods for cleaning up oil spills is the physical method of remediation. Since these do

not involve using chemicals for cleanup operations, the government authorities do not have to be
consulted beforehand. Boom, skimmer, and sorbents are the three cleanup methods used in oil

spills on the maritime industry most in practice nowadays.

(a.) Booms are fixed floating devices that help in preventing the spreading of this

oil. It has been deployed by many countries around the world as a primary marine

response measure against the spreading of oil. The main purpose of the boom is to keep

oil contained and not spread it. However, in the process, they can also be used to protect

critical areas for biodiversity, shorelines, or places that are expensive and difficult to

clean up from an oil spill.

(b.) Skimmers are critical tools to clean up oil spills; it can be installed as

permanent and movable, also, typically deployed in conjunction with booms. The

efficiency of skimmers depends on several factors, such as type of water body, oil

properties, and ambient conditions. They perform better on heavier oil slicks. And their

efficiency declines as the oil thins due to weathering, so there is a need for multiple

skimmer types for varied spill circumstances to ensure effective recovery and minimal

environmental impact.

(c.) Sorbent is the most common naturally occuring item used to clean up oil

spills. Although natural inorganic sorbents have been found to be effective, their broader

uses are limited by their cost. Synthetic sorbents have much higher absorption rates

because of their superior properties; on the other hand, they entail different material

choices and environmental effect considerations. These materials should thus be

developed and compared constantly to improve remediation techniques for oil spills.

Chemical Method

Nonetheless, one of the greatest remediation strategies for both onshore and offshore

environments is chemical remediation. They safeguard delicate maritime ecosystems in addition

to preventing oil spills from spreading. In the rehabilitation of marine oil spills, they are typically

utilized in conjunction with physical techniques (Tewari, Dr. & Sirvaiya [Link] 2015).
 Chemicals called dispersants help oil mix with water and biodegrade more rapidly by

dispersing the slick into smaller droplets. Although dispersants can effectively reduce oil's surface

tension, they could pose a threat to marine life if they are not used carefully. The chemical-based

approaches increase the speed at which oil degrades and introduce toxins into the environment,

raising ecological concerns.

Thermal Method

Additionally, another process for burning oil to clean up spills is called thermal

remediation, based on the study of Tewari, Dr. & Sirvaiya [Link] 2015, it uses minimal specialized

equipment, such as igniters and booms that can withstand fire. This method of remediation was

best to use on fresh spills or refined compounds that can be burned without harming marine life,

and to ensure effective burning, oil is concentrated into a thick slick using fire-resistant booms.

Thick oil and adequate oxygen supply, as well as others like water temperature, wave speed, wind

direction, slick thickness, and degree of weathering and emulsification are the key factors for the

effectiveness of thermal remediation.

Significance of Developing Biosorbent Materials

Biosorbents

Biosorbents are biocompatible products that may absorb or concentrate pollutants from

aqueous solutions. They are mostly made up of natural biomass. Toxic wastes that include such

elements as heavy metals and dyes are released into the environment as a direct result of

industrialization and technological progress, as stated by Tripathi et al. (2023). The biosorption of

contaminants utilizes a variety of biomaterials. Biosorbents can adsorb toxic pollutants on their

surface through various mechanisms like complexation, precipitation, etc. The quantity of

sorption sites that are accessible on the surface of the biosorbent affects its effectiveness.
 Moreover, the removal of hazardous dyes and heavy metals from wastewater using biosorbents is

a strategy that is both efficient and sustainable.

In the study of Skorupa et al. (2022) One of the most significant consumables and

agricultural products in the world is coffee. Coffee bean processing byproducts are now a

valuable raw resource in other aspects of life, according to the circular economy theory. Making

adsorbents out of waste from the coffee bean processing industry is a crucial approach to control

it. Laboratory studies have demonstrated the potential for using by-products from the agro-food

industry in the production of low-cost and effective adsorbents for the removal of contaminants

from wastewater and the aquatic environment.

Thus, adsorption on adsorbents has been considered a flexible and economical means of

eliminating heavy metals from the environment. The process of adsorption on the surface of

materials acting as adsorbents, followed by the removal of the adsorbents from the water, is a

reasonably easy way to remove heavy metals from the aquatic environment. Consequently, the

level of heavy metals in the water body under investigation reduces. Adsorption is the process

whereby fluids, gasses, vapors, and even an entire substance is taken outside to be absorbed. The

whole surface of the adsorbent is covered by the material that is absorbed during the process of

adsorption. Activated carbon is widely utilized as an adsorbent material due to its excellent

qualities. The presence of a large number of functional groups and micropores on the adsorption

surface makes activated carbon effective in removing heavy metals from an aqueous

environment.

Discussion of Oil Sorbent Materials

Oil spills are inevitable. Even with all of the precautions in place, oil leaks still happen by

mistake, thus they cannot be completely prevented. The prevalence of such incidents has shown their
negative impact on water quality, which in turn triggers a negative domino effect on marine life, coastal

areas, and human communities. As a result, numerous remediation techniques have been developed.

However, many of the methods we have used tend to be expensive, inaccessible, less effective, and

harmful to the environment.

Among these methods, the use of sorbent materials stands out. Sorbents are materials that do not

dissolve in water, therefore they can be used to recover liquids through absorption, adsorption, or both. A

lot of sorbents are naturally abundant, readily available, and can even be derived from waste materials.

These qualities make sorbents a more eco-friendly and cost-effective solution compared to other

remediation methods. (Kaur, et. al., 2024).

Types of Sorbent Materials

Sorbent materials are classified as inorganic, synthetic, and organic, each offering unique

characteristics, advantages, and limitations for oil spill remediation. Inorganic and organic

sorbents, being naturally occurring, are readily available, cost-effective, and biodegradable. In

contrast, synthetic sorbents, which are man-made, are associated with high production costs,

complex manufacturing processes, non-biodegradability, and disposal challenges, thereby limiting

their environmental sustainability and practicality (Kaur et al., 2024).

Synthetic sorbents, however, remain the most effective for oil spill remediation due to

their oleophilic and hydrophobic properties, enabling them to absorb up to 70 times their weight

in oil. In comparison, inorganic and organic sorbents struggle with having poor buoyancy and

lower oil sorption capacity thus adsorbing only 4 to 20 and 3 to 15 times their weight in oil,

respectively, making them less effective for use on water surfaces. To enhance their efficiency,

chemical or physical modifications are often required (EPA, 2016).

Characteristics, Properties, and Structure of Ideal Sorbent for Oil Spills

 An ideal sorbent for oil spill remediation balances practicality, efficiency, and

environmental sustainability, making it suitable for large-scale applications. In terms of

properties, the most effective sorbents are highly oleophilic and hydrophobic, which when

combined with enhanced swelling capacity, greatly improves oil retention and overall

performance. (Zamparas et. al., 2020)

Considering morphology, sorbents with fibrous structures tend to exhibit greater

hydrophobicity compared to those with open-cell, spherical structures. This difference arises

because oil diffuses along the length of fibrous materials, providing more extensive coverage, in

comparison to porous materials, through which oil primarily penetrates. This variation influences

how effectively the material captures and retains oil on its surface. (Songsaeng et. al. 2019)

Hydrophilicity is another key factor in adsorption that influences the materials’

wettability. By lowering a sorbent’s hydrophilicity, oil can wet the material in preference to water.

We can do this by ensuring that the oil's surface tension is lower than the material's critical

surface tension. (ITOPF, 2014) Additionally, the specific surface area (SSA) is one of the most

important properties of a sorbent. Since adsorption is a surface-driven phenomenon, a higher SSA

increases the number of active sites available, directly enhancing the material’s adsorption

performance. (Iwouzor, 2021)

Natural Sorbents and Their Key Properties for Effective Oil Adsorption

Various natural sorbents, such as banana fibers, corn stalks, and cotton, have shown

promising potential as candidates for oil spill remediation due to their availability, affordability,

and biodegradability. However, their use is still limited because of their poor oleophilic and

hydrophobic properties, which hinder their effectiveness in oil absorption.

As a response, bio-based aerogels are made from these materials which have

demonstrated comparable or even superior oil sorption capacities compared to commercial

synthetic sorbents. These aerogels, known for their high porosity and hydrophobic nature, can be

recycled through methods such as distillation, combustion, or mechanical squeezing. Despite their

recyclability, multiple times of reusing can degrade the aerogel’s structure, which diminishes its

overall performance. The synthesis of bio-based aerogels can be environmentally friendly when

produced through water dispersion, freeze-drying, and sometimes pyrolysis—methods that avoid

the need for additional chemicals or reagents. With their multifunctional properties, including

superhydrophobicity, high oil uptake efficiency, recyclability, and cost-effectiveness, bio-based

aerogels represent a promising and sustainable solution for oil spill cleanup. (Zamparas, et al.,

2020)

Potentiality of Coffee Waste as a Raw Material for Biosorbent Material

Utilizing agricultural and food waste as biological adsorbents is an innovative and

sustainable approach. Coffee waste, produced in millions of tons annually, is a promising

candidate. Although some of this waste is repurposed as animal feed, most is incinerated,

contributing to greenhouse gas emissions. Recent research has explored alternative applications

for spent coffee grounds (SCG), such serving as a raw material D-mannitol for the food industry,

biodiesel, and bio-sorbents. (Coban et. al., 2021)

I. Properties & Composition

Spent coffee grounds (SCG) possess valuable properties, including water-holding

capacity, oil-holding capacity, emulsifying activity, and antioxidant potential. These attributes

make coffee waste suitable for various applications, such as adsorbers, polymer composite fillers,

animal feed additives, and soil fertilizers. Furthermore, SCG have been extensively studied for

their effectiveness in removing metal ions from aqueous solutions, attributed to favorable

electrostatic interactions between metal ions and the negatively charged surface groups (e.g.,

hydroxyl and carboxyl groups) of lignocellulosic biomass. (Malara, et. al., 2018)
 II. Factors Influencing Feasibility as an Effective Oil Biosorbent

Raw lignocellulosic sorbents are abundant, inexpensive, non-toxic, reusable, and

biodegradable, making them appealing for oil spill cleanup. However, their limitations—low

hydrophobicity, reduced buoyancy, and compromised sorption performance—pose challenges.

Modifications with specific agents can enhance these properties, improving their overall

effectiveness. Research into the performance of lignocellulosic materials as sorbents focuses on

key indicators such as sorption capacity and reusability under specific application conditions.

Despite certain drawbacks, the inherent eco-friendliness and availability of these materials make

them competitive with synthetic alternatives, particularly when modifications are applied to

enhance their properties. (Tzivras et. al., 2020)

Discussion of Agricultural Wastes as Sustainable Sorbents

Agricultural wastes, especially coffee by-products have emerged as an emerging sustainable

sorbent for environmental remediation. Increasing production of coffee all over the world leads to large

amounts of waste that can be used in order to remove the pollutants from wastewater. Oil pollution is a

serious environmental problem. Among the various methods developed to counter this serious pollution,

the agricultural wastes have recently emerged as oil absorbents. The physical and chemical treatment

modifications to improve the oleophilic/hydrophobic properties are usually carried out on sorbents.

However, the advantages of agricultural wastes are lost once it surpasses the cost with energy-intensive

processes and environmental unfriendliness.

Based on Quyen et al. (2021), it investigated the feasibility of utilizing coffee husks as

biosorbents for extracting heavy metal ions from wastewater; some of the considered ions were Pb2+ and

Cd2+. Biochar made from coffee waste was further activated with sodium hydroxide to enhance its

specific surface area and functional groups present at its surface. The final products obtained were well

characterized using several analytical techniques, such as zeta potential analysis, surface functional group,

specific area, and scanning electron microscopy. Coffee husk-derived biosorbent may be regarded as
being both cheap and effective in extracting heavy metal ions from wastewater since it was effective in

removing 89.6% of Pb2+ and 81.5% of Cd2+ ions from wastewater.

Comparison with Synthetic Sorbents

Oil spills can be disastrous for the environment, often affecting marine life, coastal

communities, and ecosystems for years. In the quest to mitigate damage from these incidents,

synthetic sorbents have emerged as a rather effective tool for oil containment and recovery.

Synthetic sorbents are materials engineered to absorb liquids, with special affinity for oil. Once

introduced to an oil spill, these sorbents absorb oil from the water, therefore, eliminating it from

the environment. The product is usually made of synthetic materials, such as polypropylene,

polyester, or even polyurethane. These synthetic materials are used because they have

hydrophobic (repel water) and oleophilic (attract oil) properties. Since synthetic adsorbents can

absorb high amounts of oil relative to their own weight, they have an extremely high absorption

capacity. High-quality sorbents could absorb as much as 70 times their weight in oil, offering

extremely high efficiency. (wizard marketing, 2024).

Composition and Properties of Coffee Waste

The Philippines is located in the “Bean Belt,” where coffee is predominantly grown. As such, the

country tends to be one of the top producers of high-quality coffee, producing approximately 37,000

metric tons annually. This coffee production process, starting from the cultivation to the processing of

coffee cherries, generates a significant amount of waste, much of which is often disposed of improperly,

adding to the country’s overall waste challenges. (Almario, [Link], 2023)

The coffee cherry is composed of several distinct layers, each contributing to its overall

composition and quality of the coffee. The outermost layer, known as the exocarp or skin, is smooth and

glossy. Beneath the exocarp lies the mesocarp, a pulpy layer rich in sugars that significantly determine the

flavor profile of the coffee. Just under the mesocarp is the mucilage, a gelatinous layer primarily
composed of pectin and sugars. The thin protective layer that encases the coffee beans is the endocarp, or

parchment, which also aids the beans to retain their moisture. The innermost layer known to be the

silverskin, is a delicate membrane that clings tightly to the coffee beans– which are the heart of the cherry

and the primary component used for brewing coffee. (Steele, 2024)

Large quantities of byproducts are generated throughout the cultivation, harvesting, drying, and

processing of coffee cherries. Cherry husks are produced during the dry processing method, while the wet

processing method generates cherry pulp and parchment skins as byproducts. After processing, the

obtained green coffee beans are roasted, during which silverskin is produced as another byproduct.

Additionally, other parts of the coffee plant—such as flowers, leaves, twigs, and wood—are considered

byproducts and are typically generated during cultivation. (Klingel et al., 2020)

Cherry pulp is the largest part of the coffee cherry– and generally refers to both the skin and

mesocarp. It is the major by-product during wet processing methods and is reported to have 75 %

moisture content. (Olievera, 2015) According to Sugebo (2022), cherry pulp has 35 % wt cellulose, 46 %

hemicellulose, and 19 % lignin.

Conversely, cherry husks are produced during dry processing where coffee cherries are dried in

the sun separating the beans from the husks (skin, pulp, and parchment). Cherry husk is a lignocellulosic

product that contains 24.5 % of cellulose, 29.7 % of hemicellulose, and 23.7 % of lignin. Likewise,

silverskin comprises 60-80 % of dietary fiber, comprising cellulose, hemicellulose, and lignin. Spent

coffee grounds are similarly rich in cellulose, accounting for approximately 12 /100 g dry weight, (dw),

and hemicellulose with 39/100 g dw. (Klingel, 2020).

Another lignocellulosic byproduct of coffee is parchment where the hemicellulose content ranges

from 25- 32 %, 40- 49 % of cellulose, and 33- 35 % of lignin which is nearly two times higher than for

husk and pulp. However, it is also noted that the crop varieties, growing location, way of processing and

cultivation, and soil type significantly influence the lignocellulosic composition of each of the coffee

cherry’s components. (Sugebo, 2022)

 These lignocellulosic materials have aldehyde, methoxyl, phenol, ether, alcohol, aromatic rings,

and carbonyl groups in their chemical structure, which are present and crucial in various chemical

interactions—especially during adsorption or desorption mechanisms, depending on the conditions of the

process. (Gómez-Aguilar [Link], 2022)

Previous Applications of Coffee Waste as a Sorbent Material

These bioactive and chemical compositions of coffee byproducts broaden their potential

applications, especially in health and food disciplines. However, much of these wastes have also been

utilized and explored in different specializations, highlighting their potential as sorbent materials.

For instance, Gómez-Aguilar et al. (2022) studied the efficiency of untreated coffee pulp for the

desorption and adsorption mechanisms of Cr (III and VI) ions in synthetic wastewater, and established the

predominance of the composition of lignin and cellulose of the sorbent, given that the functional groups

that compose them react with the Cr (III and VI) ions. Additionally, Kim and Kim (2020) investigated the

use of spent coffee grounds as an adsorbent for Cd in an aqueous solution where untreated spent coffee

grounds were compared with zeolite and presented that the greater amount of functional groups in the

spent coffee grounds implied the higher chances of Cd adsorption than with zeolite. Both of these studies

highlighted the use of biodegradable lignocellulosic material i.e. coffee wastes’ potential to effectively

remove the pollutants in wastewater, due to the presence of the functional groups.

Moreover, Mariana et. al (2021) investigated the capacity of a raw bio-adsorbent derived from

coffee waste (endocarp) that underwent no chemical modification and showed 57.7 % of Pb removal

efficiency. However, when this adsorbent was treated with NaOH and HCL, the removal efficiency

showed 63.9 % and 89.86 %, respectively, highlighting the necessity of chemical modifications to

enhance the surface properties and pore sizes of the coffee waste for better adsorption. This is further

supported by the study of El-Azazy et al. (2021) who conducted a comparative study between the biochar

derived from spent coffee grounds per se and TiO2-impregnated, where the former showed a 68.34 %

balofloxacin removal efficiency, while the latter has 91.78 %.

 These studies, although they showcased the use of a biodegradable lignocellulosic material’s

potential to effectively remove pollutants in wastewater, also highlighted the role of chemical activators

that significantly increased the efficiency of the adsorption capacities of the material, i.e., coffee wastes.

Challenges in the Utilization of Unmodifed Coffee Waste as Adsorbents

Carboxyl (-COOH), hydroxyl (-OH), and amino (-NH2) are the active functional groups that have

the adsorption capabilities for pollutants in lignocellulosic biomass. However, the presence of the

complex and dense fiber limits the adsorbate diffusion and lowers the number of active sites of the

adsorbent. The lignin in the biomass hinders and limits the material for adsorption as the lignin inactivates

the cellulolytic enzymes (Amin et al., 2017). Generally, while lignin does contribute to the hydrophobicity

of the lignocellulosic biomass due to its structure, the overall composition of the biomass, when untreated

will still be in the predominance of cellulose and hemicellulose which are hydrophilic groups. (Zoghlami

& Paës, 2019) This makes biomass like coffee wastes with abundant amounts of cellulose and

hemicellulose, although possess functional groups necessary for the organic binding for adsorption,

exhibit hydrophilic characteristics when untreated. (Sugebo, 2022)

This necessitates the pretreatment or modification of the biomass to modify or eliminate the

lignin to allow the enzymes to interact with the cellulose component of the biomass for enhanced

adsorption efficiency. These modifications can reduce the amount of lignin and hemicellulose in the

biomass, which can also increase the surface area and porosity of the adsorbent allowing more active

functional groups for adsorption. Among the pretreatment or modification, chemical treatment is the most

extensively used. (Akindolie & Choi, 2022) This is because the chemical activation releases impurities on

the adsorbent, increases the pore-active sites, and promotes the formation of functional groups necessary

for adsorption. (Mariana et al., 2021)

Another factor that affects the adsorption efficiency of unmodified and untreated biowaste is

heterogeneity in the surface of a material– due to the presence of various functional groups which results

in an inconsistent adsorption behavior. (Sen, 2023) In the study of Młynarczykowska and Orlof-Naturalna
(2024), it is observed that unprocessed coffee material has a rough surface with small channels, giving it a

low sorption area. The same study also pointed out that chemical and physical treatments can improve its

ability to bind ions by creating better active sites.

The adsorption capacity of an adsorbent is also highly influenced by the pH of the solution. For

instance, heavy metals can be adsorbed in optimal conditions at specific pH levels. When deviations occur

or the solution reaches higher pH levels, metal ions may precipitate rather than be adsorbed. (Sen, 2023)

This is evident in the study conducted by Kim and Kim (2020), where it was assumed that the

inconsistent pH-dependent Cd removal was due to the lack of pretreatment of the spent coffee grounds.

Moreover, according to Sen (2023), 60 % of adsorption systems depend on the cost of the

adsorbent and emphasized that adsorbent regeneration must be given top priority in this age of sustainable

development. However, the potentiality for regenerating used unmodified coffee waste is another

challenge when utilizing these raw materials as adsorbents. Apart from the aforementioned results from

the studies of Młynarczykowska and Orlof-Naturalna (2024), it was also noted that the used unmodified

coffee grounds showed low efficiencies for the desorption of copper ions, indicating the strong

interactions between the unmodified adsorbent and the adsorbate that aren’t reversible– making

unmodified coffee waste to have lower potentials in reusability or regeneration. While the previously

mentioned studies showed that unmodified coffee wastes can be effective in the removal of pollutants in

wastewater, these also show that with chemical modifications and pretreatment, the adsorption efficiency

and sustainability of the coffee waste can be enhanced.

Modification Processes or Techniques for Enhancing Adsorption in Sorbents

Sorbents are materials that have an affinity to sorb, evenly distribute, and trap liquid oil within

their unique structure (Quek et al., 2020). Recently attention has been given to agro-based natural

sorbents because they are environmentally friendly, non-toxic, degradable, and inexpensive materials and

usually are abundant in nature. It also gives considerable latitude for various low-cost materials, which

can be used as sorbent may it be modified forms as per the requirement or not, one of which includes
organic materials. Numerous known materials such as zeolites, polymers, biomasses, waste sources, and

carbon-based organic materials or products were reported as sorbents for the oil/water separation. Out of

the sorbents studied, organic materials are the most versatile materials used in oil pollution control and

their efficiency depends on the properties such as active surface area, dimension, stability, and

considerable attention placed on cost and availability. For the better sorbent material, oil uptake and oil

recovery processes by sorption desorption cycle should be more efficient which is directly related to the

recyclability of the materials for next consecutive cycles. However, most of the organic materials are

lignocellulose which are made up of lignins, hemicellulose, and cellulose composed of hydroxyl groups,

which means that organic materials are hydrophilic in nature. Major requirements for crude oil adsorbents

include oleophilic and hydrophobicity, of which coffee parchment fails to meet, hence modification is

required. Apart from oil sorption affinity, sorbent materials need the ability to retain oil in their structure

and give enough time to be recovered and reused (Quek et al., 2020).

Surface modification of sorbents can be carried out by a number of methods using physical and

chemical modification. Most of the chemical treatments involve mercerization, acetylation, benzoylation

treatment, grafting and others. Hydrophobic-oleophilic properties depend on the chemical constituent of

the sorbent, the amount of the surface active sites, the physical configuration of the material, surface

roughness and its porosity. These characteristics also depend on the oil properties like concentration,

specific gravity, temperature and the amount of the oil (Se et al., 2018; Belhaj et al., 2019). Natural

organic sorbents are mainly carbon (C), hydrogen, oxygen, and nitrogen in the form of cellulose,

hemicellulose, and lignocellulose (Aqsha et al., 2017). lignocellulose can effectively sorb oil, but the

hydroxyl groups (OH) located on its surface provide hydrophilicity, which can limit its application for oil

cleanup from water. By replacing the OH groups, the surface of sorbent could be modified and become

more hydrophobic (Quek et al., 2020). Modification can improve strength, dimensional stability, decay

resistance, and eliminate the moisture absorption of cellulose.

Physical modifications like mechanical pressing or grinding affects the oil removal efficiency as

it demonstrates high oil sorption capacity and the contact surface or binding sites are more available and
accessible on smaller sorbent particles, but it has no impact on hydrophobicity improvement of the natural

sorbent. While high temperature thermal treatment like pyrolysis is deemed effective in improving both

hydrophobicity and active sites for rice husks (Maxwell et al., 2019), carbonization through pyrolysis is a

costly and time-consuming operation (Wahi et al., 2013). Which is why chemical modification is utilized

as it maximizes output at no expense of extra resources, aside from the chemical used, while being

time-efficient. In this study, NaOH is used as a surface area modifier while CTAC for the hydrophobicity

of the natural sorbent.

NaOH as a Surface Modifier

The chemical modification of coffee parchment is a crucial step to achieve an effective natural

crude oil sorbent. Sodium hydroxide (lye, caustic soda) is widely recognized for surface structure

alteration in many organic materials (Wang et al., 2020; Ates, 2023; Sidik et al., 2012; Shi et al., 2022),

where successful exposure of higher surface area and porosity was observed. NaOH interacts with organic

materials primarily through alkaline hydrolysis, which breaks down complex molecular structures, such

as lignocellulose in biomass. This reaction disrupts the intermolecular bonds, particularly those involving

lignin and hemicellulose, leading to a more porous structure. In the study of Lin et al. (2015), the use of

NaOH enhanced the clinoptilolite mesoporosity and cation exchange capacity (CEC) for removals of K+,

Al3+, and Si4+ ions, and as observed, surface area increased with increasing NaOH concentration of 0.05

to 1.50 mol/L. In a related study of Foo and Hameed (2012), durian shell was converted into activated

carbon (DSAC) via microwave-assisted NaOH activation. Similarly, the acetylation of mercerized

pineapple leaves (M-PAL) with acetic anhydride and catalysts improved hydrophobicity, replacing

hydroxyl groups with acetyl groups for superior oil sorption in dissolved oil-contaminated water (Cheu et

al., 2015). Building upon the established role of NaOH in surface modification, further studies highlight

its versatility in enhancing the sorption capabilities of natural [Link] is an economically viable

option for surface modification due to its low cost and wide availability. Compared to alternative
chemical treatments like acids or specialized reagents, NaOH offers similar or superior results at a

fraction of the expense.

Synthesis
 CTAC-Treated PVA Aerogel Composite Matrix Integrated with Coffee Parchment for Crude Oil

Spill Adsorption​

CHAPTER 3​

METHODOLOGY

Research Design

This study adopts an experimental research design as the framework for addressing the research

questions. It focuses on systematically evaluating the efficiency of CTAC-treated coffee parchment on a

PP polymer composite matrix to create a hydrophobic sorbent for crude oil spill clean-up. Specifically,

the research investigates how the dosage of adsorbent and contact time affect the percentage of crude oil

adsorption. The experimental setup consists of nine combinations of adsorbent amounts and contact times.

The independent variables in the study are the dosage of adsorbent and contact time, while the dependent

variable is the percentage of crude oil adsorption. Data will be collected at the end of the designated

contact time for each experimental setup. Statistical analysis using Analysis of Variance (ANOVA) will be

employed to determine whether significant differences in crude oil adsorption exist across the groups.

Design of Experiment

The design of experiments (DOE) serves as a structured methodology for planning, conducting,

and analyzing controlled tests to explore the relationship between independent and dependent variables.

In this study, a 3-level, 2-factor Central Composite Design (CCD) based on Response Surface

Methodology (RSM) is utilized to optimize the process. The CCD specifies the experimental conditions

for each run, allowing for the systematic evaluation of the effects of adsorbent amount and contact time

on crude oil adsorption while also considering their interactions.

 The CCD framework includes factorial points and axial points, each with three replications, and

central points with six replications, resulting in a total of 30 experimental runs. The alpha parameter is set

to ensure rotatability, providing uniform prediction precision across the design space. The study evaluates

variations in the amount of adsorbent, and contact time, and the experimental parameters include

minimum, intermediate, maximum, and extended values documented in accompanying tables.

Data from these experiments will be analyzed using ANOVA, which facilitates the identification

of significant differences between group means. This analysis provides critical insights into which

experimental factors most significantly affect crude oil adsorption, thereby enabling process optimization

and improved performance of the sorbent materials.

LEVEL

Parameters Units -1 0 1

Dosage of Adsorbent g/L 50 100 15

Contact Time s 30 60 90

Runs Amount of Adsorbent Contact Time

1 29.2893 60
2 100 102.4264

3 100 60

4 50 90

5 100 17.5736

6 170.7107 60

7 100 17.5736

8 50 30

9 50 30

10 50 90

11 100 102.4264

12 150 30

13 150 30

14 100 60

15 100 60

16 150 90

17 150 90

18 29.2893 60

19 100 60
 20 170.7107 60

21 100 102.4264

22 150 90

23 170.7107 60

24 29.2893 60

25 150 30

26 100 60

27 100 60

28 100 17.5736

29 50 30

30 50 90

Process Flowchart​

This study incorporates the experimental research design to evaluate the potentiality and capability of

adsorbent material made from NaOH and CTAC–modified coffee wastes. A sample of crude oil from

various sources will be utilized by the researchers in order to execute the adsorption process of the

product. The experimental design will include outsourcing of chemicals to be used, formulation of

solutions under defined concentrations, synthesis of chemically–modified oil–adsorbent coffee wastes,

testing and evaluation of materials, and assessment of its reusability. This design integrates Response
Surface Methodology (RSM) and Central Composite Design (CCD) and other characterization methods

(e.g. FTIR, SEM, etc.). RSM will allow the researchers to optimize the conditions for modifying coffee

waste and achieving ideal hydrophobicity, maximum adsorption capacity, and increase in water-contact

angle. These two statistical methods, along with the adsorption mechanisms, will identify the optimum

conditions of the NaOH and CTAC–modified coffee wastes to provide insights on the potentiality and

capability of adsorption process for crude oil.

Material Specifications

The experiment would use the CTAC-treated coffee parchment on a PVA polymer composite

matrix to create a hydrophobic sorbent for crude oil spill clean-up. Coffee mucilage and parchment

would serve as the base materials for the sorbent which are locally abundant, biodegradable, and

cost-effective. To prepare the modified sorbents, the coffee mucilage and parchment would be treated

with Sodium Hydroxide (NaOH) solution. NaOH would be used to enhance the porosity and surface area

of the fibers by removing lignin, hemicellulose, and other impurities. Diesel, a product of crude oil, would

be used as the adsorbate for adsorption testing. For making cellulose based aerogel, deionized water will

be used to wash the NaOH treated coffee parchment powder. Water will be used as a solvent, while PVA

as a binder. To make it an aerogel, it will be freeze dried. Finally, CTAC, a cationic surfactant, would be

used to modify the surface properties of the aerogel, improving its hydrophobicity.

For the testing process, the study will utilize various equipment/testings. A drying oven would be

used to dry the treated materials before testing. A Scanning Electron Microscope (SEM) would be used

to analyze the surface morphology and chemical composition of the modified sorbents; Fourier

Transform Infrared Spectroscopy (FTIR) would help identify functional groups introduced by NaOH

and CTAC treatments; Brunauer-Emmett-Teller (BET) analysis would be conducted to measure the

specific surface area and porosity improvements; Optical tensiometry would measure the contact angle,

quantifying the hydrophobicity of the modified materials.

Additional testing would involve gravimetric analysis to determine adsorption capacity.

Analytical balances would be required for accurate weighing of materials, while glassware such as

beakers, flasks, and test tubes would facilitate chemical reactions and testing. This setup ensures a

thorough evaluation of the sorbent's effectiveness in crude oil spill remediation.

Bill of Materials

Component Source of Material Type Unit Cost Quantity Total Cost

Material

Materials

NaOH Quadmed Liquid 100mL 650 400mL 2600

CTAC Dalkem Liquid 250mL 210 450mL 550

Coffee Farm Solid - 0 21kg 0

Parchment

Crude Oil Caltex Liquid 1L 57.90 1L 58

PVA pellet DLK Solid 100 g 140 250g 350

Deionized DLK Liquid 1L 75 3L 225

water

Testing

SEM DLSU Service Per sample 880 2 1760

FTIR BSU-ALANGIL Service Per sample 500 2 1000

 AN

BET UPLB Service For 8 hours 4000 2 8000

Optical UPD Service Per sample 2000 3 6000

Tensiometry

Apparatus

Freeze-Drying DOST-ITDI Heat 1 day 3613 12 43356

Exchanger

Misc 50000

Allowance 10000

Total 123,899
Proper Handling and Waste Disposal

a.​ Contaminated Water

According to the Philippines’ Republic Act 6969, also known as the Toxic Substances

and Hazardous and Nuclear Wastes Control Act, any waste that imposes a potential hazard to

human health or the environment when improperly managed, is considered hazardous. This

includes crude-oil-contaminated water which contains toxic components that may cause

significant harm if not handled or disposed of properly. Water contaminated with crude oil must

be contained in leak-proof containers and labeled correctly. These should be disposed of by

depositing them to the DENR-EMB accredited reception facility for oil recovery treatments or

permitted dumping areas. (Supreme Court E-Library, n.d)

b.​ Chemical Solutions

Intending to chemically modify the coffee mucilage and parchment, this study utilized

sodium hydroxide and cetyltrimethylammonium chloride as chemical reagents. Additionally,

ethanol is used for the chemical regeneration technique for the adsorbent’s reusability.

The proper handling and disposal of sodium hydroxide waste includes the use of

appropriate personal protective equipment when worked with and ensuring that it is placed in a

suitable container that prevents leaks or spills. High-density polyethylene is an ideal container as

it has excellent resistance to withstand the heat of the solution and is sturdy enough to be a

durable, and safe container for NaOH. (Containers for Lye Solution | Soapy Stuff, n.d.) To

dispose of the NaOH waste, neutralization, and pH adjustments are crucial and often used. These

methods involve adding substances such as weak acids like acetic acid to adjust the pH level to a
 safe range. Afterward, the neutralized NaOH waste can be disposed of in an appropriate treatment

or disposal facility. (Moshiri & Moshiri, 2024)

Cetyltrimethylammonium chloride is usually disposed of similarly. It has to be

neutralized with an appropriate acid or base, to adjust its pH. Likewise, acetic acid is

recommended to neutralize smaller quantities of CTAC. The neutralized CTAC is also collected

and contained in HDPE and disposed of similarly to the disposal of NaOH.

The use of ethanol is crucial in the desorption of adsorbates to regenerate the coffee waste

adsorbent. However, unlike NaOH and CTAC, ethanol requires more careful handling due to its

flammable nature. Ethanol must be placed in leak-proof containers like HDPE, clearly labeled,

and must be stored in well-ventilated areas until such time that it is handed over to a waste

management facility that handles hazardous waste. (Ethanol Disposal in Laboratories | Collect

and Recycle, 2024)

c.​ Chemically Modified Coffee Waste Adsorbents

One of the main objectives of this study is to develop a chemically modified reusable and

biodegradable adsorbent derived from coffee waste. Hence, the product can be reused as long as it

is sufficiently effective to fulfill its intended function, reducing the need to dispose of the

adsorbent material.

However, when the adsorbent approaches its end use, it still has to be disposed of to

prevent any environmental contamination. Landfill disposal is one of the methods that many

researchers have utilized in the disposal of saturated sorbents where sorbents are buried in

sanitary or hazardous waste landfills. (Renu & Sithole, 2024)

d.​ Glassware and Equipment

 The oil adsorption capacity testing of the adsorbent will utilize laboratory glassware and

items, hence, it is essential to ensure that the items to be used are free of any contaminants to

expect accurate results.

All the items to be used will be first rinsed with tap water. After use, glassware items that

had contact with crude oil will involve additional steps to clean. The use of an organic solvent

like ethanol or acetone is essential to help dissolve and remove any residue of crude oil.

Afterward, it will be washed with a detergent and rinsed with warm tap water. To ensure that any

residue is removed, glassware will be rinsed with deionized water several times. (JoVE, 2024)

The initial rinse with the organic solvent and crude oil-contaminated water will be

collected, labeled, and disposed of in an appropriate treatment or disposal facility. These will be

contained in non-leaking containers and highly resistant to organic solvents like HDPE.

Testing and Performance

Characterization of the Chemically Modified and Unmodified Coffee Mucilage and Parchment

The following analytical tests are to be performed for the characterization of the chemically

modified and unmodified coffee mucilage and parchment as adsorbents. As this study aims to compare

their properties, the same tests are to be performed for more accurate and comparable results. However,

reusability will not be included in the scope of comparison, as this study prioritizes evaluating the

comparison between the key characterization parameters.

1.​ Water Contact Angle

 One major characteristic of an adsorbent material is its hydrophobicity which will

significantly influence its adsorption capacity with better interactions with non-polar

substances. One of the most widely used analytical methods to measure the material's

hydrophobicity is the assessment of contact angle measurements. This will involve the

utilization of an optical tensiometer, where a liquid droplet will be in contact with the

powdered coffee waste adsorbent. The contact angle will then be measured from the

image captured and processed with algorithms based on the Young-Laplace equation.

Laboratory testing service for this purpose is available at the University of the

Philippines–Diliman.

2.​ Oil Sorption Capacity

The evaluation of the oil sorption capacity is essential to determine the efficiency

of the coffee waste as an adsorbent for crude oil spill remediation. The oil sorption

capacity is measured through the gravimetric method, where the adsorbent is first

weighed and recorded. It will then be immersed in a defined volume of crude oil and

water mixture for a set duration of time. Afterwards, the adsorbent is filtered or

centrifuged to remove the excess un-adsorbed oil on its surface, and dried if necessary. It

will then be measured again, to determine the mass after oil adsorption. The oil sorption

capacity will be measured through the equation q = (Wf - Wi) /Wi; where q is the

sorption capacity, Wf is the weight of the adsorbent after adsorbing oil, and Wi is the

weight of the adsorbent before adsorbing oil.(Ababneh & Benamor, 2019) The laboratory

testing for this characterization can be done at Batangas State University-Alangilan.

3.​ Surface Area

 The surface area of an adsorbent correlates with the active sites available for

adsorption; hence, a high surface area indicates a high adsorption capacity. To measure

the surface area of the coffee waste adsorbent, the Brunauer-Emmett-Teller (BET)

Method is to be utilized. This method uses a nitrogen gas as an adsorbate under its boiling

point (77 K). The pressure of the nitrogen gas is gradually increased, and the adsorbed

gas at relative pressures will be measured. The adsorption data collected is plotted and

will be used to determine the specific surface area of the sample. (Mercer, n.d) The BET

testing is to be carried out at the University of the Philippines-Los Baños.

4.​ Surface Morphology

The shape, size, and arrangement of the pores of the adsorbent influence the

accessibility of the active sites for adsorption. The surface morphology of the coffee

waste adsorbent can be assessed and evaluated through high-resolution images from the

scanned surface of the adsorbent using the Scanning Electron Microscope. The images

are generated in an external monitor, that correlates the beam’s position with the electrons

that scanned the surface of the adsorbent. (Scanning Electron Microscopy | Nanoscience

Instruments, n.d.) De La Salle University offers laboratory services for powdered

adsorbents for the aforementioned analysis.

5.​ Functional Groups

The functional groups present on the surface of the adsorbent material impact

their adsorption properties and mechanisms. They dictate the chemical interactions

between the adsorbent and the adsorbate; and influence the hydrophobicity of the

material. To identify the functional groups present on the surface of the coffee waste
 adsorbents, FTIR will be utilized. The generated spectrum of the FTIR spectrometer will

yield absorption patterns that correspond to the structure of the functional groups which

can be identified using reference materials. (Mathias, 2024) The FTIR testing is to be

performed at the University of the Philippines-Diliman.

6.​ Reusability

The regeneration and reusability of the adsorbent allow the material to be

environmentally viable as the regeneration process reinstates the initial characteristics of

the adsorbent for it to be used multiple times. (Renu & Sithole, 2024) This study will

utilize decantation for the collection of the used coffee waste adsorbents. Afterward, it

will be subjected to a chemical regeneration technique where ethanol is used as a solvent

to desorb the inorganic or organic desorbates. To evaluate the effectiveness of the

regenerated adsorbent, its oil adsorption capacity will be reanalyzed using the same

analytical methods and equations applied during initial testing. All laboratory

experiments, including the regeneration and adsorption capacity assessment, will be

conducted at Batangas State University–Alangilan.

Proposed Operational Procedure​

The purpose of the Proposed Operations Procedure (POP) is to create a consistent and sufficiently

systematic methodology for preparing, modifying, and characterizing coffee waste as a hydrophobic

sorbent for crude oil spill remediation. The SOP provides the reproducibility and reliability of the

experimental process and clear guidelines regarding the transformation of coffee waste into an effective

sorbent material.

That procedure comprises this thesis since it meets the environmental problem of oil spills by using

sustainable, inexpensive, and readily available materials. It modifies coffee waste by NaOH and

cetyltrimethylammonium chloride (CTAC), for which procedure this SOP provides an increase in

hydrophobic properties for oil spill recovery-associated employment. The expected sorbents will have

efficiency gains, better environmental compatibility, and practical applicability so that they help to create

sustainable scalable solutions toward the cleaner environment.​

The POP assumes that the audience has a foundational understanding of laboratory techniques and

chemical safety protocols. This POP is designed for:

●​ Thesis Group Members involved in the preparation, modification, and testing of the coffee

waste sorbent for their thesis project.

●​ Thesis Advisers and Co-Advisers who will be supervising the implementation of this SOP and

ensuring the integrity and reproducibility of the experimental procedures.

●​ Researchers and Students in the fields of chemical engineering, environmental science, and

materials science, focusing on sustainable technologies and oil spill remediation.

●​ Industry Practitioners exploring low-cost, sustainable solutions for oil spill management.

While the POP covers extensive methodology for the research, the following limitations are applied:
 1.​ Scale: The procedure is designed for laboratory-scale experiments and may require adjustments

for industrial-scale applications.

2.​ Inconsistency in Coffee Waste Composition: The chemical and physical properties of coffee

waste varies depending on factors such as the coffee bean type, processing methods, and

environmental conditions.

3.​ Oil Type Specificity: This POP is optimized for crude oil spills and may not directly apply to

other types of oil or contaminants.

Resources and Materials​

The following resources and materials are required to carry out the experiments and data collection for the

thesis on NaOH and Cetyltrimethylammonium Chloride-Modified Coffee Waste as a Hydrophobic

Sorbent for Crude Oil Spill Remediation:

Software Tools

●​ Statistical Analysis Software: For potential data analysis using Response Surface Methodology

(RSM) and Central Composite Design (CCD), software such as R or Minitab may be used if

required for optimization and statistical testing of results.

Data Sources

●​ Journal Databases: The primary data sources for this study are literature and research papers

accessed through Elsevier and various related journals. These sources provide foundational

knowledge for the methodology, and the performance of similar materials in the context of oil

spill remediation.

●​ Internal Data: The study will mainly rely on data generated from the experiments conducted,

focusing on comparing the initial (unmodified) and final (modified) states of the coffee waste

sorbent.
 ●​ Characterization Data: The study will also utilize the results from characterization to further

discuss the mechanism of the successful modification and oil adsorption of oil.

Equipment and Materials

Materials to be used to execute our research include but are not limited to (subject to changes and

updates):

●​ Drying Oven

●​ Beakers

●​ Decanters

●​ Analytical Balance

●​ Gloves and Lab Coats

●​ PPE (Personal Protective Equipment)

○​ Characterization Equipment:

○​ Scanning Electron Microscope (SEM)

○​ BET Surface Area Analyzer

○​ Fourier Transform Infrared Spectroscopy (FTIR)

○​ Optical Tensiometer

Procedure

Preparation Phase​

The preparation phase of this research involves conducting a literature review on organic materials,

including coffee waste, rice husks, coconut husks, and spent coffee grounds, as oil sorbents. The review
highlights gaps in the use of coffee parchment and mucilage, and the lack of research on the synergistic

effects of combining NaOH and CTAC treatments, which is the main inspiration for this topic. Most

studies rely on theoretical results for hydrophobic transformation, without advanced characterization

methods like optical tensiometry, which this research also aims to address.

The hypothesis is that modified coffee waste will have superior oil sorption capabilities compared to

unmodified waste. Treatment conditions, including concentrations, reaction times, and temperatures, will

be based on the optimal results from prior studies. This phase sets the groundwork for the experimental

procedures.

Data Collection

Data Gathering comprises both qualitative and quantitative data from various experimental methods that

are designed to test the performance of NaOH and CTAC-modified coffee wastes as hydrophobic sorbents

for crude oil spill remediation.

1.​ Collection of Coffee Waste:

○​ Coffee wastes will be obtained from local suppliers or businesses where the actual type of

coffee waste (whether parchment, mucilage, or others) will confirm by the time of

collection. The pre-treatment will also remove impurities from the waste so that the

material will be comparable in the future modification processes.

2.​ Sample Preparation:

○​ After collection, coffee wastes will be pre-treated (by drying, crushing) and subsequently

treated with NaOH and CTAC, following the protocols defined earlier. The modified and

unmodified coffee waste will then be stored in separate lots for comparison.

3.​ Characterization of Modified Sorbents:

○​ A set of characterization techniques will be employed, including:

 ■​ Scanning Electron Microscopy (SEM): To observe surface morphology and

any structural changes in the sorbent.

■​ BET Surface Area Analysis: To measure the surface area and pore

characteristics of the sorbent.

■​ Fourier Transform Infrared Spectroscopy (FTIR): To analyze functional

group changes that may result from NaOH and CTAC treatments.

■​ Optical Tensiometry: To assess the hydrophobicity of the modified sorbent,

specifically the contact angle measurements with water.

4.​ Crude Oil Sorption Test:

○​ The test will involve subjecting the modified coffee waste to crude oil. Important

parameters such as crude oil amount, sorbent's weight, and sorption time will be defined.

Efficiency of the sorption measures will be estimated through oil uptake and sorbent

capacity or tenancy to absorb crude oil.

5.​ Waste Management and Disposal:

○​ Proper disposal of used sorbents and chemical waste will be recorded to ensure

compliance with environmental regulations.

Data Analysis

Data analysis will be conducted in the data from the experimental tests on the modified coffee waste

sorbent in order to find out its effectiveness in crude oil sorption.

1.​ Characterization Data:

 ○​ SEM images will be analyzed for morphological changes due to the NaOH and CTAC

treatments. BET data would then be used to specify the surface area and porosity, which

are important factors that would give ideas to determine the sorption capacity. Changes in

functional groups will be determined through FTIR in order to indicate successful

modification and introduction of hydrophobic characteristics.

○​ Optical tensiometry data will give quantitative results regarding the hydrophobicity of the

sorbents which have been treated; it will also measure the contact angle of water on the

surface which is directly correlated with oil sorption potential.

2.​ Crude Oil Sorption Efficiency:

○​ The oil sorption test will be evaluated in terms of oil sorption by modified and

unmodified sorbents. The sorption capacity can be quantified in terms of sorption

capacity: mass of crude oil adsorbed per unit mass of the sorbent.

○​ Data collected from the experimental study will be compared with theoretical or baseline

data derived from previous studies to assess the modified sorbents' effectiveness. To

ascertain if differences exist among groups (such as between modified and unmodified

coffee waste), appropriate statistical methods, such as Analysis of Variance (ANOVA),

might be applied.

3.​ Response Surface Methodology (RSM):

○​ In applying the effective treatment parameters concentration, time of reaction and

temperature, Response Surface Methodology (RSM) will be used to optimize these

factors which come from the standard experimental data. This will enable identification

of the best conditions that provide maximum sorption efficiencies.

Statistical Evaluation

With an experimental research design, this study utilized statistical results to assess the efficiency

of the chemically modified coffee mucilage and parchment in the adsorption of crude oil under varying

conditions and set parameters: the amount of the adsorbent, and contact time. The simulations conducted

in this study yield results that must be statistically evaluated for a better understanding and assessment of

the performance of the coffee wastes as an adsorbent material.

Analysis of Variance (ANOVA)

This study employed an analysis of Variance to evaluate the statistical significance of the

variations in the adsorption capacity of the adsorbent material. This statistical treatment determined the

factors and conditions that influence the adsorption capacity by highlighting the statistically significant

differences among them.

Response Surface Methodology (RSM)

Response Surface Methodology is a statistical method that analyzes the statistical influence of

independent variables on the response variable. It helps determine the optimal conditions of an outcome

through the relationships between the set parameters and the adsorption capacity of the coffee wastes.

RSM reduces prediction errors and improves estimation using polynomial equations, which are

referred to as regression models. RSM employs the first-order and second-order polynomial models

which will be used to effectively describe the relationship between the parameters and the adsorption

capacity.
 First Order Polynomial

𝑘
𝑦 = 𝜷0 + ∑ 𝜷𝑖𝑥𝑖 + ɛ ​ (eq. )
𝑖=1

Second Order Polynomial

𝑘 𝑘
2
𝑦 = 𝜷0 + ∑ 𝜷𝑖𝑥𝑖 + ∑ 𝜷𝑖𝑖Σ𝑥𝑖 + ∑ ∑ Σ𝜷𝑖𝑗𝑥𝑖𝑥𝑗 + ɛ ​ (eq. )
𝑖=1 𝑖=1 𝑖 𝑗

Where y is the response function, 𝜷𝑖, 𝜷𝑖𝑖, 𝜷𝑖𝑗, are the coefficients of the linear, quadratic, and interaction

terms respectively, with 𝑥𝑖 and 𝑥𝑗 being the independent variables.

Design Consideration

This study, focusing on coffee mucilage and parchment modified with sodium hydroxide (NaOH)

and cetyltrimethylammonium chloride (CTAC) as hydrophobic sorbents for the remediation of crude oil

spills, is based on several design considerations that ensure the materials' efficiency and sustainability.

The reason for choosing coffee mucilage and parchment is their inherent availability and biodegradability,

which complements the increasing demand for environmentally friendly remediation techniques. During

the modification procedure, these materials are treated with CTAC to increase their hydrophobicity and
NaOH for the improvement of structural integrity. This is an essential dual modification since it changes

the surface characteristics of the sorbents and enhances oil absorption capacity.

The efficacy of these modifications can be evaluated through laboratory tests measuring oil

absorption capacity using the formula Q = ( Wf − Wi )/ms, where Wf is the final weight after oil

absorption, Wi is the initial weight, and ms is the mass of the sorbent. Hydrophobicity will also be

evaluated using contact angle measurements; a higher contact angle indicates a greater oil absorption

capacity. To ensure that there are minimal ecological risks during cleanup, environmental impact

assessments willlso be conducted to establish how biodegradable these altered materials are after use. By

considering these factors, our study aims to prove that coffee mucilage and parchment treated with NaOH

and CTAC can be used as efficient, environmentally friendly substitutes for cleaning up crude oil spills.

Basis and Assumption

●​ Basis

This study is based on the desire for sustainable and efficient materials for oil spill cleanup.

Agricultural by-products, such as parchment and coffee mucilage, are utilized in this regard with a chance

to make use of waste materials and improve their qualities through chemical treatment. CTAC increases

the hydrophobicity of lignocellulosic materials and enhances their crude oil absorption capacity, while

NaOH is used to strengthen the materials' structural integrity. Literature indicating that chemical

treatments may significantly enhance the sorption capabilities of natural sorbents by altering their surface

properties and wettability supports this dual modification approach.

●​ Assumption

Several key assumptions underpin this research. As evident from the fact that a significant

increase in contact angle with water indicates a reduction in wettability, this study first hypothesizes that

the chemical alterations that use NaOH and CTAC will be effective at increasing the hydrophobic nature

of coffee mucilage and parchment. Second, the improved sorbents are likely to exhibit a higher capability
of sorption of oil compared to unmodified ones and would allow efficient oil recovery in spill cleanup

operation. Moreover, it is likely that environmental factors, such as salinity and temperature, would not

significantly interfere with the functionality of the novel sorbents under conditions in reality. Last but not

least, it is anticipated that the biodegradability of these natural materials will positively affect

environmental sustainability once they are used in cleaning up the oil spills.

By establishing these basis and assumptions, the study aims to explore the possibilities of

modified coffee mucilage and parchment as workable alternatives for traditional synthetic sorbents in

efficiently cleaning up crude oil spills and encouraging environmentally responsible behaviors.

Design Calculations

To evaluate the efficiency of coffee mucilage and parchment treated with sodium hydroxide

(NaOH) and cetyltrimethylammonium chloride (CTAC) as hydrophobic sorbents for cleaning up crude oil

spills, our research methodology involves primarily design calculations. Such calculations can measure

important properties such as the oil absorption capacity. It can collect valuable information regarding the

performance properties of the modified materials through the use of a specific formula to ensure the

accuracy and reliability of our results. This quantitative analysis will assist in creating long-term solutions

to restore the environment in oil spills, as well as test the validity of our modified sorbents.

●​ Oil Adsorption Capacity Calculation

This formula calculates the amount of oil that a specific mass of sorbent can absorb. It is essential

for determining the efficiency of modified coffee mucilage and parchment in absorbing crude oil.

𝑄 = (𝑊𝑓 − 𝑊𝑖𝑧) /𝑚𝑠