UTILIZING WASTE RUBBER-DERIVED ACTIVATED CARBON MODIFIED

WITH FISH SCALE (WRAC-FS) ADSORBENT FOR AQUEOUS DYES REMOVAL

A Chemical Engineering experimental Project Report

Presented to the

DEPARTMENT OF CHEMICAL & PROCESS ENGINEERING

SCHOOL OF ENGINEERING

MOI UNIVERSITY

In Partial Fulfillment of Requirements for the Award of the Degree of

Bachelor of Engineering

In

Chemical and Process Engineering

PRESENTED BY:

Name Registration no. Sign

NIXOM CHERUIYOT CPE/06/19
ITSURA ANNETTE CPE/11/19
FELIX MOBUTU CPE/24/19
FATUMA KASSIM CPE/29/19

SUPERVISOR:

DR ANTHONY MULIWA

1
DECLARATION

The report presented is our original work. It is being submitted to Moi University in hopes of
receiving a bachelor's degree in chemical and process engineering. It has never been turned in
for a test or degree at another college or university.

Sign………………

NIXON CHERUIYOT CPE/06/19

Sign………………

ITSURA ANNETTE CPE/11/19

Sign………………

FELIX MOBUTU CPE/24/19

Sign………………

FATUMA KASSIM CPE/29/19

2
ACKNOWLEGEMENT

We would like to sincerely thank Dr. Anthony Muliwa, our research supervisor, for his
tireless support, insightful remarks, and helpful critiques during the course of our study.
Above all, we are grateful to God for providing us safety, excellent health, and the power,
wisdom, and capacity to complete our endeavour to this point.

3
 ABSTRACT

Dyes are complex organic compounds which are used by various industries to color their
products. These dyes enter the water which make them polluted. Today, colour removal from
wastewater has been a matter of concern, both in the aesthetic sense and health point of view.
Extensive use of synthetic dyes in textile industry has created a major pollution problem.
Among various treatments, adsorption has been considered as a better process due to its
effectiveness of removing color from wastewater. In this work, the efficiency of adsorbent
material prepared from Waste Rubber Derived Activated Carbon (WRDAC) and activated
Fish Scales (FS) for removal of dye from textile wastewater will be studied. WRDAC will be
chemically activated with KOH after carbonizing in a furnace. Adsorption of dye stuff will be
carried out by preparing dye samples in laboratory and taking dye wastewater from RivaTex.
Adsorption was carried out under different factors namely contact time, adsorbent mass, pH,
initial dye concentration and their effects on adsorption will be studied.

4
Table of Contents
CHAPTER ONE: INTRODUCTION....................................................................................8
1.1 BACKGROUND.............................................................................................................8
1.2 PROBLEM STATEMENT............................................................................................9
1.3 OBJECTIVES...............................................................................................................10
CHAPTER TWO: LITERATURE REVIEW.................................................................11
2.1 DYES.............................................................................................................................11
2.2 CURRENT TECHNOLOGIES USED IN DYE REMOVAL..................................13
2.3 ADSORPTION WITH ACTIVATED CARBON......................................................13
2.3.1 Properties of Activated Carbon............................................................................14
2.3.2 Forms of Activated Carbon..................................................................................14
2.3.3 Methods of Activation...........................................................................................15
2.4 FISH SCALES..............................................................................................................16
2.4.1 Fish Scale Preparation and Activation methods.................................................18
CHAPTER THREE: MATERIALS AND METHODOLOGY.........................................19
3.1 INTRODUCTION........................................................................................................19
3.2 MATERIALS AND EQUIPMENT.............................................................................19
3.2.1 MATERIALS.........................................................................................................19
3.2.2 EQUIPMENT.........................................................................................................19
3.3 PREPARATION OF FISH SCALES POWDER......................................................19
3.4 PREPARATION OF WASTE RUBBER ACTIVATED CARBON........................20
3.5 PREPARATION OF STANDARD STOCK SOLUTION........................................20
3.7 BATCH ADSORPTION STUDIES.......................................................................21
3.7.1 EQUILIBRIUM STUDIES.............................................................................21
3.7.2 ISOTHERM STUDIES.........................................................................................23
3.8 COLUMN STUDIES....................................................................................................23
3.8.1 EFFECT OF BED HEIGHT.................................................................................24
3.8.2 EFFECT OF INITIAL CONCENTRATION.....................................................24
3.8.3 EFFECT OF FLOWRATE...................................................................................25
CHAPTER FOUR: RESULTS AND DISCUSSION..........................................................26
RESULTS............................................................................................................................26
4.1 WRAC-FS DESCRIPTION.........................................................................................26
4.1.1 YIELD AND PARTICLE SIZE......................................................................26
4.2 CALIBRATION CURVE.......................................................................................26

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 4.3 COMPARATIVE ANALYSIS....................................................................................28
4.4 BATCH STUDIES........................................................................................................29
4.4.1 EQUILIBRIUM STUDIES...................................................................................29
4.4.2 ADSORPTION ISOTHERMS..............................................................................33
4.5 COLUMN STUDIES....................................................................................................36
4.5.1 MODELLING OF THE BREAKTHROUGH CURVES...................................36
CHAPTER FIVE: WORKPLAN AND BUDGET..............................................................42
5.1 WORKPLAN................................................................................................................42
5.2 BUDGET.......................................................................................................................44
7.0 RECOMMENDATIONS.................................................................................................46
8.0 REFERENCES.................................................................................................................47

6
List of Tables

Table 1; Summary of recent reviews on fish scale preparation methods.................................19

Table 2: 2cm, 3cm and 5cm bed height...................................................................................25
Table 3: 50mg/l, 100mg/l, 150mg/l..........................................................................................26
Table 4: 2ml/min, 4ml/min and 6ml/min flowrates..................................................................26
Table 5: Yield of Raw Materials..............................................................................................27
Table 6: Data to plot calibration curve.....................................................................................27
Table 7: COMPARISON ANALYSIS OF WRAC-FS COMPOSITE....................................29
Table 8: Effect of Contact Time on adsorption of RB171.......................................................30
Table 9: Effect of adsorbent dosage on adsorption..................................................................31
Table 10: pH of dye solutions and absorbance results.............................................................33
Table 11: Data used to plot Freundlich isotherm....................................................................34
Table 12: Data used to plot Langmuir Isotherm......................................................................35
Table 13: Data to plot effect of bed height on Breakthrough curves.......................................37
Table 14: Data to plot effect of flowrate on Breakthrough Curves..........................................39
Table 15: Data to plot Initial Concentration Breakthrough Curves.........................................41
Table 16: Work plan.................................................................................................................43
Table 17: Budget......................................................................................................................45

List of Figures

Figure 1 Classification of textile industries dyes.....................................................................11

Figure 2 Forms of Activated Carbon.......................................................................................14
Figure 3 Raw Fish Scales.........................................................................................................16
Figure.4: Dye Samples.............................................................................................................20
Figure 5: UV-VIS Spectrophotometer.....................................................................................21
Figure 6: Set-up investigating effect of Contact time..............................................................21
Figure 7: pH meter...................................................................................................................23
Figure 8: Column studies setup................................................................................................24
Figure 9: Calibration curve......................................................................................................27
Figure 10: Bar Chart showing color removals of WRAC-FS components and the composites
..................................................................................................................................................28
Figure 11: A Graph of color removal against adsorbent dosage..............................................30
Figure 12: Adsorbent Capacity against Adsorbent Dosage.....................................................31
Figure 13: Effect of pH on adsorption.....................................................................................32
Figure 14: Freundlich Isotherm................................................................................................34
Figure 15: Langmuir Isotherm.................................................................................................35
Figure 16: Effect Of Bed Height on Breakthrough curves......................................................37
Figure 17: Effect of Flowrate on Breakthrough Curves...........................................................39
Figure 18: Effect of Initial Concentrations on Breakthrough Curves......................................41

7
CHAPTER ONE: INTRODUCTION
1.1 BACKGROUND
The textile dyeing and finishing industry has created a huge pollution problem as it is one of
the most chemically intensive industries on earth and among the top polluters of clean water.
More than 3600 individual textiles dyes are being manufactured by the industry today many
of which contain toxic chemicals (Singha et al., 2021). The presence of these dyes in the
environment has effects on human health, including carcinogenic, mutagenic, allergic, and
dermatitis effects, kidney disease. The direct disposal of untreated dye-containing effluent
into natural water bodies has an adverse effect on the photosynthetic activity in aquatic
ecosystems (Dutta et al., 2021). Thus, the disposal of dyes in the environment contaminates
the water bodies, subsequently affecting the water quality, aquatic life, and human health.

The escalating concerns over water pollution, driven primarily by the discharge of effluents
loaded with dyes and other pollutants, have propelled the development of innovative and
sustainable water treatment methods. Traditional methods of wastewater treatment often fall
short in addressing the challenges posed by the removal of these persistent dye molecules.

In the treatment of textile waste water, physicochemical, membrane processes,

electrochemical, biological processes and advanced oxidation techniques are often used.
However, some of these processes have been found to have many disadvantages such as high
energy demand, formation of flocs together with dye, low adsorption capacities for dyes,
large amount of sludge produced, and uneconomical. In fact, some are not effective at all for
dye removal and they also have short half-life.

Among these methods, adsorption process has been identified as the most economical
feasible and effective method for removal of dyes due to its wide range of applications,
simplicity and low cost of operation (Yagub et al., 2014). In addition to the mentioned
advantages, adsorption is also able to recover adsorbent for reuse and to prevent creation of
secondary problems with dye-bearing sludge which is very difficult to dispose.

Adsorption employing recycled materials is a better option due to its low cost, sustainability,
and environmental friendliness (Sheth et al., 2021). Since the performance of any adsorption
process depends on the chemistry of the adsorbent and adsorbate, a variety of adsorption
media have been developed and tested in the removal of dyes from aqueous solutions. These

8
include commercially activated carbon (CAC), activated alumina, silica, clays, activated
biochar and zeolites.

However, most of these adsorbents have been linked with many limitations such as low
capacity for dyes, slow reaction kinetics, high costs and difficulties in separation from
wastewater (Younas et al., 2021). Because cost is a very crucial pre-requisite of any
adsorption media, lately interest has been directed towards the development and innovation
of low-cost, sustainable and ecofriendly adsorbents for dye pollutants removal from
wastewater (Sheth et al., 2021).

To address this pressing issue, we present an approach that harnesses the unique
characteristics of two distinct yet complimentary materials – tilapia fish scales and water
rubber-derived activated carbon. By combining the natural and synthetic aspects of these
materials, we aim to investigate the use of fish scales and tire-derived activated carbon as
adsorbent for the efficient removal of dyes from wastewater, thus contributing to the
mitigation of water pollution and preservation of ecosystems.

1.2 PROBLEM STATEMENT

Textile industries discharge millions in liters of effluents as hazardous toxic waste, full of
color and organic chemicals from dyeing salts. These effluents are also often of a high
temperature and pH, both of which are extremely damaging to an ecosystem. The colloidal
matter present along will lead to coloration and oily scum increases the water turbidity,
giving it a bad appearance and foul smell.

The waste water that flows in the drain corrodes the sewage pipes. If allowed to flow in
drains and rivers, it affects the quality of drinking water making it unfit for human
consumption. It also leads to leakages in drains increasing their maintenance cost. Such
polluted water can be a breeding ground for bacteria and viruses. Textile effluents is a cause
of significant amount of environmental degradation and human illness.

Another major source of toxin release into the environment is waste rubber tires. Once rubber
tires reach their end-life, lack of sustainable disposal methods often leads to the leakage of
toxins, like lead, present in most synthetic tires. The main difficulty in the disposal of waste
tires is that they occupy a large amount of environmental space and are difficult to compress,
collect and eliminate. In view of the uncertainty in the time required for the decomposition of
old tires, they are not biodegradable and their composition includes some dangerous elements

9
like chromium, cadmium and other heavy metals. If not handled or properly managed, they
will threaten the natural environment and human health.

It is estimated that in Kenya, about 34,000 tonnes of waste tires have been burnt haphazardly,
dumped, destroyed, or reused by methods that pollute the air, soils, and groundwater since
2010 (The Tyre Mamas - People Daily, 2019). Nairobi is expected to have 1.35 million
vehicles by 2030. The number is expected to be even more going by the current rate of
registration. The National Transport and Service Authority (NTSA) registers 7,000 vehicles
monthly and 90,000 every year. As the number of vehicles on our roads continues to rise, the
problem of scrap tire disposal presents serious waste management challenges for society
(Dabic-Miletic et al., 2021)

Tilapia fish scales, also typically considered a waste product in the fish processing industry,
present an opportunity to repurpose a readily available resource for environmental
remediation. Some of the common methods for fish scale waste disposal are throwing them in
landfills, incineration, composting and repurposing for biosorption.

1.3 OBJECTIVES
General objectives

To prepare and use waste rubber-derived activated carbon modified with carbon fish scale
(WRAC-FS) for removal of aqueous dyes in textile industry effluent.

Specific objectives

1. To prepare WRAC-FS adsorbent for aqueous dyes removal

2. To conduct preliminary batch adsorption tests of WRAC-FS on various dye-polluted
water under various conditions.
3. To perform fixed-bed column adsorption studies using WRAC-FS for removal of
aqueous dyes.
4. To fit adsorption data in various mathematical models and derive important adsorber
design parameters.

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CHAPTER TWO: LITERATURE REVIEW
2.1 DYES
Dyes may be defined as substances that, when applied to a substrate provide color by a
process that alters, at least temporarily, any crystal structure of the colored substances. The
dyes can adhere to compatible surfaces by solution, by forming covalent bonds or complexes
with salts or metals, by physical adsorption, or by mechanical retention.
Dyes are classified according to their application and chemical structure, and are composed
of a group of atoms known as chromophores, responsible for the dye color. These
chromophore-containing centers are based on diverse functional groups, such as azo,
anthraquinone, methine, nitro, aril methane, carbonyl and others. In addition, electrons
withdrawing or donating substituents so as to generate or intensify the color of the
chromophores are denominated as auxochromes. The most common auxochromes are amine,
carboxyl, sulfonate and hydroxyl (Manzoor & Sharma, 2020).
Types of dyes used in the textile industries (Jesudoss, n.d.).

Figure 1 Classification of textile industries dyes

It is estimated that over 10,000 different dyes and pigments are used industrially and over 7 x
105 tons of synthetic dyes are annually produced worldwide. Textile materials can be dyed

11
using batch, continuous or semi-continuous processes. Among these processes, the batch
process is the most common method used to dye textile materials (Maheshwari et al., 2021).
In the textile industry, up to 200,000 tons of these dyes are lost to effluents every year during
the dyeing and finishing operations, due to the inefficiency of the dyeing process.
Unfortunately, most of these dyes escape conventional wastewater treatment processes and
persist in the environment as a result of their high stability to light, temperature, water,
detergents, and other parameters. However, environmental legislation obliges industries to
eliminate colour from their dye-containing effluents, before disposal into water bodies.
The textile industry consumes a substantial amount of water in its manufacturing processes
used mainly in the dyeing and finishing operations of the plants. The wastewater from textile
plants is classified as the most polluting of all the industrial sectors, considering the volume
generated as well as the effluent composition. In addition, the increased demand for textile
products and the proportional increase in their production, and the use of synthetic dyes have
together contributed to dye wastewater becoming one of the substantial sources of severe
pollution problems in current times (Raja et al., 2019).
Textile wastewaters are characterized by extreme fluctuations in many parameters such as
chemical oxygen demand (COD), biochemical oxygen demand (BOD), pH, colour and
salinity. The composition of the wastewater will depend on the different organic-based
compounds, chemicals and dyes used in the dry and wet-processing steps. Recalcitrant
organic, colored, toxicant, surfactant and chlorinated compounds and salts are the main
pollutants in textile effluents.
In addition, the effects caused by other pollutants in textile wastewater, and the presence of
very small amounts of dyes in the water, which are nevertheless highly visible, seriously
affects the aesthetic quality and transparency of water bodies such as lakes, rivers and others,
leading to damage to the aquatic environment (Bakar et al., 2020).
With respect to the number and production volumes, azo dyes are the largest group of
colorants, constituting 60-70% of all organic dyes produced in the world. The success of azo
dyes is due to their ease and cost-effectiveness for synthesis as compared to natural dyes, and
also their great structural diversity, high molar extinction coefficient, and medium-to-high
fastness properties in relation to light as well as to wetness. They have a wide range of
applications in the textile, pharmaceutical and cosmetic industries, and are also used in food,
paper, leather and paints. However, some azo dyes can show toxic effects, especially
carcinogenic and mutagenic events.

12
One of the most difficult tasks confronted by the wastewater treatment plants of textile
industries is the removal of the colour of these compounds, mainly because dyes and
pigments are designed to resist biodegradation, such that they remain in the environment for a
long period of time. For example, the half-life of the hydrolyzed dye Reactive Blue 19 is
about 46 years at pH 7 and 25°C (Khan et al., 2023).
2.2 CURRENT TECHNOLOGIES USED IN DYE REMOVAL
To treat textile wastewaters, methods such as: Physicochemical processes (sorption, reverse
osmosis, ion exchange), biological processes (aerobic and anaerobic treatment, microbial
reduction, bacterial treatment), nuclear treatments (irradiation by nuclear radiations),
acoustical, electrical, and electromagnetic processes (ultrasonic treatment) are available (D.
Singh, 2023).
However, most of these systems have disadvantages such as the creation of hazardous sludge
and significant operating and maintenance costs. Adsorption employing recycled materials,
such as WRAC-FS, is a better option due to its low cost, sustainability, and environmental
friendliness.
2.3 ADSORPTION WITH ACTIVATED CARBON
Activated carbon is a group of porous carbon produced by carbonizing carbonaceous
elements filled with dehydrated chemicals. The base materials that comprise activated carbon
include wood, peat, coconut, shells, saran, and recycled tires. Activated carbon is the most
popular that has been efficiently used for water and industrial wastewater treatment.

However, it is most cost-effective and environmentally conscious to produce activated carbon

from alternative materials because their application is limited, due to their relatively high
costs and regeneration and disposal problems (Afroze and Sen, 2018).

2.3.1 Properties of Activated Carbon

Due to its inherent properties (e.g., high surface area, microporous structure, high porosity,
and high adsorption capacity; it has been used widely for water treatment purposes. It
exhibits high surface areas ranging from 700 to 1800 m2 g−1 (Jeguirim et al., 2018; Manocha,
2003).

The surface area is created during the process of activation in which higher temperatures burn
holes in carbonized raw materials. This produces multiple holes and pores in the carbon
matrix, and phosphoric acid is used to build a porous system. The surface area may vary

13
greatly depending on the raw material and the condition of carbonization for making active
carbon. It is also characterized by its micropore structures. AC has a porous amorphous
structure with cylindrical, rectangular, or irregular shapes pores of diameters ranging from
0.8 to 10 nm (micropores), 10–50 nm (mesopores), and 50–2000 nm (macropores)
(Mcdougall, 1991).

Its pore volume typically ranges from 0.20 to 0.60 cm3/g and has been found to be as large as
1 cm3/g. (Bansal, 2005). The activated carbon is required to have a high particle strength and
a resistance to attrition (the breakdown of material into fines). This accounts for its
hardness/abrasiveness.

2.3.2 Forms of Activated Carbon

Figure 2 Forms of Activated Carbon

Powdered Activated Carbon (PAC)

PAC has small AC particles with an average size of 0.075mm and a mean particle diameter
of 0.045mm. It shows the high surface area and high micro porosity which are the
characteristics of their adsorption capacity. Several factors such as contact time, PAC dose,
behavior and molecular structure of the targeted compound, and the composition of
wastewater markedly influence the removal performance of PAC (Boehler et al., 2012).
PACs are typically used in liquid-phase adsorption applications and offer reduced processing
costs and flexibility in operation. They are typically employed in batch mode. They cannot be
regenerated because of their difficulty in separating them from the liquid phase.

Granulated Activated Carbon (GAC)

Granular activated carbons generally range in particle sizes from 0.2 mm to 5 mm and can be
used in both gas and liquid phase applications. GAC significantly removed numerous micro

14
contaminants from wastewater in a dose-dependent manner (Piai, Blokland, van der Wal, &
Langenhoff, 2020). They offer clean handling and tend to last longer than PACs.
Additionally, they offer improved strength (hardness) and can be regenerated and reused.
They remove color, Odor, turbidity, micro plastics, micro pollutants, and heavy metals.

2.3.3 Methods of Activation

There are two approaches for preparing activated carbon that can be used in water
purification processes: physical activation and chemical activation.

i. Physical Activation

This process involves the use of hot gases to generate AC from the source material. Physical
activation is a two-step process that involves the process of carbonization (pyrolysis) in a
neutral atmosphere and then activation in atmospheric oxidizing gases such as steam, carbon
dioxide, carbon dioxide, and nitrogen or air mixtures with increasing temperature in the range
of 800–1100°C (Bouchelta et al. 2008).

ii. Chemical Activation

In chemical activation, the carbon material is impregnated with a chemical agent prior to
carbonization. This process increases carbon yield and better control of porosity (Bergna, T.,
Romar, & Lassi, 2018). Typically, the sub-stance infused is one of the following: phosphoric
acid (25%), potassium hydroxide (5%), sodium hydroxide (5%), calcium chloride (25%), and
zinc chloride (25%). (Beguin, 2010).

Acidic Activation Agent

Nitric acid could develop pores, increase the contact area, and finally facilitate mass transfer
during the adsorption process. An increase in the ratio of the activating agent is proportional
to the efficiency until the optimal condition is achieved, then creating higher pore volume.
Phosphoric acid could be used for breaking chemical bonds, protecting the internal pore
structure, and causing development in porosity.

The main purpose of adding hydrochloric acid as an activating agent during the synthesis of
activated carbon is to remove lignin to enable symmetric pore creation. Acidic treatment of
activated carbon resulted transform crystalline cellulose to amorphous. This activating agent
can remove zinc, sodium, and calcium from the tire char, resulting in lower ash content

Basic Activation Agent

15
The use of KOH resulted in improved porosity due to potassium interaction and the stretching
of carbon layers. KOH is more effective in creating micropores when the temperature is
above 800°C. When the temperature is in the range of 230 to 650°C, the use of KOH can
produce a high char yield.

Because of the lower temperatures, improved uniformity in quality, and smaller activation
times required for the material, chemical activation is favored over physical activation.

2.4 FISH SCALES

Fish scales, often overlooked and discarded as waste materials by the fish processing
industry, have recently piqued interest due to their exceptional physical and chemical
properties, rendering them a compelling candidate for the treatment of dye effluents. These
unique biomaterials consist primarily of type I collagen and hydroxyapatite, making them
one-of-a-kind. Unfortunately, the lack of commercial value has limited their practical
application, leading to the wastage of valuable resources and environmental harm.
Repurposing and reusing fish scales could not only alleviate the strain on the natural
environment but also generate commercial value (Qin et al., 2022).

Figure 3 Raw Fish Scales

The careless disposal of fish scales, whether into landfills or the ocean, has a detrimental
impact on the ecosystem. These scales are generated as a by-product of the fish processing
industry's fillet processing. According to Arvanitoyannis and Kassaveti, fish processing can
result in scales weighing between 20 to 40 kilograms for every 1,000 kilograms of fish during
the filleting process (Arvanitoyannis & Kassaveti, 2008).

16
In light of the environmental challenges posed by conventional wastewater treatment
methods, there has been a growing interest in unconventional and environmentally friendly
approaches. One such innovative, environmentally sustainable method for mitigating the
impact of industrial effluents, particularly in terms of colour removal, involves the use of fish
scales as a biosorbent. This strategy not only effectively addresses the issue of dye
wastewater but also offers an economical, sustainable, and ecologically friendly alternative
(Shaikhiev et al., 2020).

Fish scales' remarkable physical and chemical attributes make them an enticing prospect for
dye wastewater treatment. As by-products of the fish processing industry, fish scales exhibit a
unique composition, boasting a collagenous matrix and hydroxyapatite crystals, which render
them excellent candidates for dye adsorption. Furthermore, their abundance and
biodegradability further enhance their desirability as a sustainable solution.

Integrating fish scales into existing wastewater treatment infrastructure holds the promise of
efficient dye removal and provides an opportunity for sustainable resource utilization and
economic benefits. By transforming what was once considered a waste product into a
valuable resource, the fish processing sector can contribute to a more circular and
environmentally sustainable approach (Coppola et al., 2021).

It's important to note that using fish scales in dye wastewater treatment is a relatively new
and emerging field of study. While laboratory experiments have yielded promising results,
further research is needed to refine and scale up the process for industrial applications. This
journey toward a more sustainable and eco-friendly solution for dye wastewater treatment is
driven by the quest for cleaner and more environmentally responsible practices in the textile
and fish processing industries.

Tilapia fish scales, typically considered a waste product in the Kenyan fish processing
industry, present an opportunity to repurpose a readily available resource for environmental
remediation. Some of the possible methods for local fish scale waste disposal are; Landfills
where in many cases, fish scales may be disposed of along with other organic and non-
recyclable waste materials, a method that is not environmentally stable considering the
biodegradable nature of fish scales; Incineration where they can be used to generate heat and
energy, making it a more suitable option than landfills. However, it can release pollutants into
the atmosphere, so proper emissions control is necessary; Composting applied especially in
agricultural settings, fish scales being organic can provide nutrients to the soil to improve its

17
quality; Fish scales can be repurposed for biosorption applications, such as the removal of
contaminants from wastewater.

2.4.1 Fish Scale Preparation and Activation methods

Table 1; Summary of recent reviews on fish scale preparation methods

Pretreatment 1st Washing 2nd stage Preparation Reference

stage technique
Rising with - Oven drying at 650C Basin et al (2007)
deionized water and sieve to 35-
and soaking for 40µm or drying for 2
24Hrs days
Soaking for 2hrs at Washing with Sun drying for 2 Ooi et al (2017)
300C with 100 rpm deionized water days or oven drying
stirring. at 700C
Chemicals used: Mechanical grinding
HCL, NaOH, with motor before
H2SO4 pretreatment roughly
to 150µm
Washing with Soaking for 24hrs Size reduction with Das et al (2016)
distilled water. and 250C in NaOH knife mill.
Air drying for 2
days.
Soak in 15% NaOH Soak in distilled Mechanical grinding Othman et al (2016)
for 24Hrs water for 24Hrs using motor to
150µm
Oven drying at 600C
Washing with Oven dying at 600C Neves et al (2017)
distilled water No grinding or
sieving.

CHAPTER THREE: MATERIALS AND METHODOLOGY

18
3.1 INTRODUCTION
The main objective of this experiment is to prepare and use waste rubber-derived activated
carbon modified with carbon fish scale (WRAC-FS) for removal of Reactive Blue 171 dye in
textile industry effluent. The physical parameters varied were pH, adsorbent dosage and
contact time for batch studies; and bed height, initial concentration and flowrate for column
studies. The experiment was performed at room temperature.

3.2 MATERIALS AND EQUIPMENT

3.2.1 MATERIALS
KOH pellets, distilled water (used in making solutions and cleaning of materials), ethanol
(used to disinfect the fish scales). Fresh fish scales were obtained from a local market in
Eldoret town, waste rubber tire samples from an exhausted tire were collected from a local
cobbler in Moi University and the dye stuff sample from RivaTex, Eldoret.

3.2.2 EQUIPMENT
 Weighing scale
 Milling machine
 UV-VIS Spectrophotometer
 pH meter
 Fixed bed column
 Peristaltic pump

3.3 PREPARATION OF FISH SCALES POWDER

The surface debris on fresh fish scales was cleansed with distilled water, and any potentially
dangerous microorganisms were eliminated by sterilizing the scales with ethanol. After the
fish scales were cleaned and allowed to air dry, a milling machine was used to reduce their
size into a powder. 50% KOH was used to chemically activate the powder for a whole day.
After that, it was neutralized using 0.1M HCL, and the solution removed through vacuum
drying. The filter cake was then dried, crushed, and filtered through a number of meshes.
After being weighed, the fine powder was designated as FS.

19
3.4 PREPARATION OF WASTE RUBBER ACTIVATED CARBON
WRAC was prepared by weighing the waste rubber sample and cutting it into smaller chunks.
The size reduced rubber samples were then subjected to thermal activation by pyrolysis at
600°C. Pyrolysis was carried out for 2 hours to achieve a homogenous carbonization, after
which a black residue (char) was obtained. The char was then crushed using a motor and
pestle and subjected to chemical activation with KOH for 24 hours. Once neutralized, the
mixture was allowed to air dry. The powder was screened through a series of meshes and the
fine powder obtained weighed and labeled as WRAC.

3.5 PREPARATION OF STANDARD STOCK SOLUTION

Standard stock solution of the dye was prepared by mixing distilled water with Reactive Blue
171 dye powder. 1 gram of the dye was mixed with 1000ml distilled water to form 1000ppm
stock solution that was used in all subsequent studies throughout the experiment.

Figure.4: Dye Samples

3.6 PREPARATION OF THE CALIBRATION CURVE

Various concentrations of 100ml volumes i.e. 25 ppm, 50 ppm, 75 ppm, 100 ppm, 125
ppm and 150 ppm were prepared by dilution of the 1000ppm stock solution with distilled
water. To construct a calibration curve, absorbance of the various concentrations was
measured using a UV-VIS spectrophotometer run at 605nm wavelength. An aliquot of the
sample dye solution was added to a cuvette up to the mark and data recorded. A plot of
absorbance against concentration was plotted.

20
Figure 5: UV-VIS Spectrophotometer

3.7 BATCH ADSORPTION STUDIES

3.7.1 EQUILIBRIUM STUDIES
3.7.1.1 CONTACT TIME
Solutions with different concentrations of RB 171 were prepared from stock by diluting with
a given amount of distilled water to produce a solution of 50ml for each sample.

To determine the equilibrium time of adsorption of RB 171 onto WRAC-FS, 1.2g of WRAC-
FS was added to a 250ml beaker containing 50 ml of dye solution (50 mg/l). The contents
were mixed, and 5-ml samples were obtained at regular intervals. The absorbance of the
samples was tested until a constant value was obtained for five consecutive samples. At this
point, no more dye could be adsorbed by the WRAC-FS and equilibrium was said to have
been reached. The equilibrium time was determined as 100 mins.

21
Figure 6: Set-up investigating effect of Contact time

3.7.1.2 EFFECT OF ADSORBENT DOSAGE

Accurately weighed amounts of adsorbent (0.2g, 0.4g, 0.6g, 0.8g, 1.0g and 1.2g) were added
to beakers containing 50 ml of the dye solution (50 mg/l) at pH 2.0 ± 0.2. The contents of the
beakers were thoroughly mixed for 100 minutes at room temperature. A 5 ml sample was
taken out after the equilibrium time and filtered using a Whatman filter paper. The dye
concentration in the samples was then measured spectrophotometrically. The amount of
adsorbate adsorbed at equilibrium condition Qe (mg/g) was calculated using the following
equation:

v ( C o−C e )
Qe =
m

C o−C e
Removal= x 100 %
Co

Where Qe (mg/g), Ce (mg/L) and Co (mg/l) are defined as the amount of dye adsorbed per unit
weight of adsorbent, equilibrium concentration and initial concentration respectively.

3.7.1.3 EFFECT OF pH
Optimum pH was determined by batch experiments using an adsorbent dosage of 1.2g at
room temperature. 0.1M HCl and 0.1 M NaOH were prepared in bulk and were added to
adjust the pH dropwise. 50ml solutions of 50 ppm at a pH range of 2-12 were prepared. A pH
meter was used to measure the desired pH. This was then followed by the addition of the

22
adsorbent. After an optimum time of 100 minutes, the samples were filtered through a
Whatman filter paper and 10 mL of the filtrate was poured in different test tubes and
absorbance was recorded at 605 nm.

Figure 7: pH meter

3.7.2 ISOTHERM STUDIES

Isothermal studies were conducted by contacting 0.2–1.2 g of WRAC-FS adsorbent in 50ml
of 50 mg/l solution. The contents of the beakers were thoroughly mixed for 100 minutes at
room temperature. A 5 ml sample was taken out after the equilibrium time and filtered using
a Whatman filter paper. The equilibrium dye concentration (Ce) was then measured
spectrophotometrically, and the amount of dye adsorbed per unit weight of the adsorbents at
equilibrium (Qe) were determined.

3.8 COLUMN STUDIES

Continuous-flow adsorption experiments were conducted in a glass column (3 cm internal
diameter and 30-cm length). To avoid entrapping of air bubbles inside the WRAC-FS
particles, the particles were soaked for 15 hours before packing into the column. The column
was packed with WRAC-FS (particle size,240 μm between two supporting layers of glass
wool. Beads were also placed on top of the adsorbent bed to prevent the bed from being
pulled with the outflow. All the experiments were conducted at room temperature, and the
direction of flow was from bottom to top using a peristaltic pump. The pH of the inlet
solution was set to 2.

23
Figure 8: Column studies setup

3.8.1 EFFECT OF BED HEIGHT

The effect of varying the bed height 2, 3 and 5cm on the column parameters was studied. A
flow rate of 2 ml/min and an initial influent concentration of 50 mg/l were kept constant. 5ml
samples were collected at intervals of 1 hour and their absorbance measured and recorded in
the tables below.

Table 2: 2cm, 3cm and 5cm bed height

2cm, Time 1 2 3 4 5 6 7 8
3cm, (hrs)
5cm
ABS
Ce
3.8.2 EFFECT OF INITIAL CONCENTRATION
Initial influent RB 171 concentrations of 50 mg/l, 100 mg/l and 150 mg/l were examined. A
flow rate of 2 ml/min and a bed height of 3 cm were kept constant. 5 ml samples were
collected at intervals of 1 hour and their absorbance measured and recorded in the tables
below:

24
Table 3: 50mg/l, 100mg/l, 150mg/l

50mg/l, Time 1 2 3 4 5 6 7 8
100mg/l, (hrs)
150mg/l
ABS
Ce
3.8.3 EFFECT OF FLOWRATE
Flow rates of 2, 4, and 6 ml/min were used to analyze the effect on the column performance.
An initial influent concentration of 50 mg/l and a bed height of 5 cm were kept constant. 5 ml
samples were collected at intervals of 1 hour and their absorbance measured and recorded in
the tables below:

Table 4: 2ml/min, 4ml/min and 6ml/min flowrates

2ml/min, Time 1 2 3 4 5 6 7 8
4ml/min (hrs)
and
6ml/min
ABS
Ce

25
CHAPTER FOUR: RESULTS AND DISCUSSION
RESULTS
4.1 WRAC-FS DESCRIPTION

4.1.1 YIELD AND PARTICLE SIZE

Table 5: Yield of Raw Materials

RAW WEIGHT OF PRODUCT WEIGHT YIELD

MATERIAL RAW PRODUCT (%)
MATERIAL
WRAC Waste rubber 640g Char 196.86g 30.38
tires
FS Raw fish 600g Fish Scale 212.3g 35.38
scales Powder
The powders were sieved through mesh sizes up to 160µm that is to say the particle size was
160µm.

4.2 CALIBRATION CURVE

Various concentrations of dye solutions were measured for absorbance and data recorded in
table 6 below to yield calibration curve in figure 9.
Table 6: Data to plot calibration curve

Concentration (ppm) Absorbance

0 0
10 0.138
20 0.293
30 0.458
40 0.6
50 0.771
60 0.922
70 1.05
80 1.232
90 1.387
100 1.497
110 1.696
120 1.73
130 1.967
140 2.087
150 2.136
160 2.334

26
 CALIBRATION CURVE
2.5
f(x) = 0.014644362745098 x + 0.0224509803921571
2 R² = 0.997419468954981
ABSORBANCE

1.5

0.5

0
0 20 40 60 80 100 120 140 160 180
CONCENTRATION

Series2 Linear (Series2)

Figure 9: Calibration curve

27
4.3 COMPARATIVE ANALYSIS
COMPARATIVE ANALYSIS
COMPONE MA VOLU CO ABSORBAN CF(PP COLOR ADSORPTI
NT SS ME (PP CE M) REMOV ON
(g) (ml) M) AL (%) CAPACITY
FISH 5 50 10 0.020 1.307 86.928 0.0869
SCALES
ACTIVATE 5 50 10 0.057 3.725 62.745 0.0627
D CARBON
1:1 5 50 10 0.046 3.007 69.935 0.0699
2:1 5 50 10 0.035 2.288 77.124 0.0771
3:1 5 50 10 0.022 1.438 85.621 0.0856
4:1 5 50 10 0.011 0.719 92.810 0.0928
Table 7: COMPARISON ANALYSIS OF WRAC-FS COMPOSITE

COMPARATIVE ANALYSIS
100.000

90.000

80.000

70.000
COLOR REMOVAL (%)

FISH SCALES
60.000 ACTIVATED CARBON
50.000 1:1
2:1
40.000 3:1
4:1
30.000

20.000

10.000

0.000
COLOR REMOVAL (%)

COMPONENT

Figure 10: Bar Chart showing color removals of WRAC-FS components and the composites

It is seen in figure 10 that FS has a higher removal efficiency as compared to WRAC. This
means that FS ought to be the main element in the WRAC-FS composite.

28
WRAC-FS in the ratio of 4:1 (FS: WRAC) had highest removal and was considered in the
preparation of the composite.

4.4 BATCH STUDIES

4.4.1 EQUILIBRIUM STUDIES
4.4.1.1 CONTACT TIME
Contact time is one of the most effective factors in batch adsorption process. The adsorption
rate initially increased rapidly, and the optimal removal efficiency was reached within 100
minutes. Further increase in contact time did not show significant change in equilibrium
concentration; that is, the adsorption phase reached equilibrium.

This is as a result of rapid sorption at the initial stages as there was abundance of active sites
on the external surface of the adsorbent which resulted in the rapid dye removal. The slower
rate in the later stages is due to the dyes being diffused into the interior of the adsorbent.

Table 8: Effect of Contact Time on adsorption of RB171

Time 10 20 30 40 50 60 70 80 90 100
(minutes)
ABS
Ce (mg/l)

4.4.1.2 EFFECT OF ADSORBENT DOSAGE

The effect of WRAC-FS dose on the color removal of dyes is shown in Fig. 9. It was
observed that in all cases the dye uptake increased with increasing dose of carbon (K. Santhy,
2005).

The increase in adsorbent dosage from 0.2 to 1.2 g/ 50 ml led to a rise in adsorption
percentage from 87.32% to 90.98%. The increase in the dye removal percentage was as a
result of increase in adsorbent active sites as the adsorbent mass increases. The highest

29
removal of 90.98% of dye effluent was achieved with an adsorbent dosage of 1.2g (24g/l)
where an optimum is reached and no more adsorbate can be adsorbed because of saturation.

This decrease in adsorption capacity with increase in adsorbent dosage mainly attributed to
non-saturation of the adsorption sites during the adsorption process.

The results were tabulated as follows:

Table 9: Effect of adsorbent dosage on adsorption

Absorbent Co Absorbanc Cf (PPM) Color removal Adsorption

dosage (g) (PPM) e (%) capacity
0.2 50 0.097 6.340 87.320 10.915
0.4 50 0.081 5.294 89.412 5.588
0.6 50 0.074 4.837 90.327 3.764
0.8 50 0.072 4.706 90.588 2.831
1.0 50 0.070 4.575 90.850 2.271
1.2 50 0.069 4.510 90.980 1.895
Figure 11: A Graph of color removal against adsorbent dosage

EFFECT OF ADSORBENT DOSAGE

92.000

91.000 90.850 90.980

90.588
90.327
90.000
COLOR REMOVAL

89.412
89.000

88.000
87.320
87.000

86.000

85.000
0.2 0.4 0.6 0.8 1.0 1.2
ADSORBENT DOSAGE

Color removal (%)

Figure 12: Adsorbent Capacity against Adsorbent Dosage

30
4.4.1.3 EFFECT OF pH
Point of Zero Charge (PZC) is the pH at which the adsorbent surface has a net neutral charge.
At a pH lower than the PZC, the surface becomes positively charged due to the presence of
acidic functional groups like carboxylic groups that gain a positive hydrogen ion (H+).
Conversely, at a pH higher than the PZC, the surface becomes negatively charged because the
functional groups lose their hydrogen ions and become negatively charged.

For efficient adsorption, the opposite charges between WRAC-FS and the dye molecule are
preferred. This creates a strong attraction that drives the molecule towards the adsorbent
surface. The optimum pH obtained was 2, above which, the percentage dye removal was seen
to decrease.

At neutral and alkaline pH (pH 7 and above), reactive blue dye molecules are negatively
charged. In contrast, at a pH of 2, the dye becomes protonated, meaning it acquires a positive
charge. Adsorbent materials used in wastewater treatment often have negatively charged
surfaces at acidic pH. This creates a strong electrostatic attraction between the positively
charged dye molecules and the negatively charged adsorbent surface, promoting adsorption.

The percentage removal slightly increased between pH 8 to 10. While electrostatic attraction
might be weaker at pH 8, the adsorbent can still interact with some organic molecules
through mechanisms like Van der Waals forces and π-π interactions, regardless of charge.
These forces, though weaker than electrostatic attraction, can contribute to some level of dye
adsorption.

Table 10: pH of dye solutions and absorbance results

pH Co (PPM) Absorbance Cf (PPM) Color removal (%)

2 50 0.011 0.719 98.562

4 50 0.172 11.242 77.516
6 50 0.174 11.373 77.255
8 50 0.169 11.046 77.908
10 50 0.114 7.451 85.098
12 50 0.110 7.190 85.621

31
 EFFECT OF pH
120.000

100.000
COLOR REMOVAL

80.000

60.000
Color removal (%)
40.000

20.000

0.000
2 4 6 8 10 12

pH

Figure 13: Effect of pH on adsorption

4.4.2 ADSORPTION ISOTHERMS

For solid-liquid system, adsorption isotherm is important in description of adsorption
behavior. In this work, two well-known models of Freundlich and Langmuir isotherms were
evaluated.

4.4.2.1 Freundlich Isotherm

The Freundlich isotherm is an empirical equation employed to describe heterogeneous
systems. The linear form of Freundlich equation is given by

1
ln Qe = . ln C e + ln K f
n

Where Qe (mg/g) and Ce (mg/L) are defined as the amount of dye adsorbed per unit weight of
adsorbent and equilibrium liquid-phase concentration, respectively.

Kf (mg/g) is defined as an adsorption or distribution coefficient, representing the amount of

adsorbate adsorbed on an adsorbent for a unit equilibrium concentration.

The slope 1/n is a parameter of the adsorption intensity or surface heterogeneity.

32
To determine the validity of this isotherm in describing the adsorption process, a plot of ln Qe
vs ln Ce was constructed.

Table 11: Data used to plot Freundlich isotherm

Ce (mg/l) Qe (mg/g) lnQe lnCe

6.340 10.915 2.3901 1.847
5.294 5.588 1.7208 1.667
4.837 3.764 1.335 1.576
4.706 2.831 1.041 1.549
4.575 2.271 0.8202 1.5206
4.510 1.895 0.6881 1.5063

FREUNDLICH ISOTHERM
2
1.8
f(x) = 0.194827159263573 x + 1.3532622888701
1.6 R² = 0.958832142860654
1.4
1.2
1 ln Ce
ln Qe

0.8 Linear (ln Ce)

0.6
0.4
0.2
0
0.5 1 1.5 2 2.5
ln Ce

Figure 14: Freundlich Isotherm

1
is the slope of the line=0.1984
n

ln Kf is the Y-intercept = 1.3466, therefore K f =log 1. 3466=0.12924 mg / g

33
4.4.2.2 Langmuir Isotherm
The Langmuir isotherm assumes uniform energies of adsorption onto the surface and no
transmigration of the adsorbate in the plane of the surface. This model is expressed in the
linear form by;

1
=
1
( 1
. +
1
)
Qe Qm . K l C e Qm

Where Qm (mg/g ) is a constant related to the area occupied by a monolayer of adsorbate,

reflecting the maximum adsorption capacity. Kl (mg/l ) is a direct measure of the intensity of
the sorption.

Table 12: Data used to plot Langmuir Isotherm

Ce (mg/l) Qe (mg/g) 1/Qe 1/Ce

6.341 10.917 0.0916 0.1577
5.266 5.590 0.1789 0.1899
4.838 3.764 0.2657 0.2067
4.706 2.831 0.3532 0.2125
4.575 2.271 0.4403 0.2186

4.511 1.895 0.5276 0.2217

LANGMUIR ISOTHERM
0.25
f(x) = 0.134953110554867 x + 0.159408597961074
0.2 R² = 0.835258161884403

0.15 1/Ce
1/Qe

Linear (1/Ce)
0.1 Linear (1/Ce)

0.05

0
0 0.1 0.2 0.3 0.4 0.5 0.6
1/Ce

Figure 15: Langmuir Isotherm

34
 1
is theY −intercept=0.1594
Qm

Qm =6.2735 mg/g

Kl can be calculated from

1
=gradient =0.135
Qm . K l

1
¿ =0.135
6.2735 x K 1

k 1=1.1807 mg/l

4.5 COLUMN STUDIES

The most important parameters for a breakthrough curve study are the bed height, flow rate,
and initial inlet concentration. The effects of these parameters on the shape of the
breakthrough curve and column performance were investigated.

4.5.1 MODELLING OF THE BREAKTHROUGH CURVES

The performance of a column was evaluated based on the shape of the breakthrough curve
obtained from the plot of Ce/Co versus time t, where Ce and Co are the effluent RB171 dye and
inlet concentrations in mg/l, respectively. This is very important for determining the
operation of adsorption columns. The total weight of RB171 adsorbed by WRAC-FS in the
column for a given feed concentration and flow rate, is equal to the area under the plot of the
adsorbed RB171 concentration.

4.5.1.1 EFFECT OF BED DEPTH ON BREAKTHROUGH CURVES.

Using a constant influent concentration of 50mg/L and a flow rate of 2ml/min, the shape and
slope of each curve was different with the variation of the bed depth. It was observed that the
breakthrough and exhaustion time increases with bed depth. The higher bed column resulted
in a decrease in the effluent concentration at the same service time. The slope of the
breakthrough curve decreased with increasing bed height, which resulted in a broadened mass
transfer zone (Han et al., 2009). As the bed height is increased from 3 to 5 cm, a decrease in
the slope of breakthrough curve is observed, which resulted in a rapid mass transfer zone.

35
When the bed height is decreased, the removal percentage is decreased and the total weight of
RB 171 adsorbed by WRAC-FS in the column is also decreased. A higher dye uptake was
also observed at a higher bed height due to the increase in the specific surface of the
adsorbent which provided more fixation binding sites for the dye to adsorb. The increase in
the adsorbent mass in a higher bed provided a greater service area which would lead to an
increase in the volume of the solution treated (Tan et al., 2008).

Table 13: Data to plot effect of bed height on Breakthrough curves

TIME CF/CO
2cm 3cm 5cm
25 0.051 0.025 0.020
50 0.061 0.046 0.031
75 0.098 0.054 0.041
100 0.116 0.064 0.048
125 0.255 0.075 0.054
150 0.393 0.146 0.061
175 0.613 0.275 0.073
200 0.767 0.393 0.084
225 0.875 0.669 0.127
250 0.903 0.719 0.167
275 0.923 0.799 0.256
300 0.940 0.915 0.349
325 0.954 0.463
350 0.984 0.569
375 0.995 0.724
400 0.812
425 0.861
450 0.876
475 0.928
500 0.941

36
 BED HEIGHT BREAKTHROUGH CURVES
1.000

0.900

0.800

0.700

0.600
CF/CO

0.500 2 cm
0.400
3 cm
0.300
5 cm
0.200

0.100

0.000
0 100 200 300 400 500 600
time (mins)

Figure 16: Effect Of Bed Height on Breakthrough curves

4.5.1.2 EFFECT OF FLOW RATE ON THE BREAKTHROUGH CURVES

To investigate the effect of varying the flow rate (2, 3, and 4 ml/min) on breakthrough
curves, a bed height of 5 cm and an initial RB 171 concentration of 50mg/l were kept
constant.

It can be seen that the breakthrough generally occurs faster with a higher flowrate. Similarly,
the exhaustion times were increased with decrease in flow rate. This is because at a low
flowrate of influent, WRAC-FS had more time to contact with the influent, which resulted in
higher removal of the dye. At higher flow rate, the mass transfer rate gets increased, namely
the amount of dye adsorbed onto unit bed height gets increased with increasing flow rate
leading to faster saturation. The adsorption capacity was lower due to insufficient residence
time of the solute in the column and diffusion of the solute into the pores of the adsorbent,
and therefore, the solute left the column before equilibrium occurred (Tan et al., 2008).

Table 14: Data to plot effect of flowrate on Breakthrough Curves

TIME 5cm, 2ml/min 5cm, 4ml/min 5cm, 6ml/min

25 0.020 0.027 0.035
50 0.031 0.046 0.056
75 0.041 0.073 0.090
100 0.048 0.088 0.125

37
125 0.054 0.106 0.161
150 0.061 0.115 0.280
175 0.073 0.196 0.451
200 0.084 0.331 0.566
225 0.127 0.424 0.757
250 0.167 0.507 0.826
275 0.256 0.702 0.915
300 0.349 0.829 0.963
325 0.463 0.869 0.979
350 0.569 0.927 0.984
375 0.724 0.962
400 0.812 0.970
425 0.861 0.982
450 0.876
475 0.928
500 0.941
525 0.980
550 0.988
575 0.992

38
 FLOWRATE BREAKTHROUGH CURVE
1.000

0.900

0.800

0.700

0.600
2 ml/min
CF/CO

0.500
4 ml/min
0.400
3 ml/min
0.300

0.200

0.100

0.000
0 100 200 300 400 500 600 700
time (mins)

Figure 17: Effect of Flowrate on Breakthrough Curves

4.5.1.3 EFFECT OF INITIAL INLET CONCENTRATION ON BREAKTHROUGH

CURVES.
The effect of the initial inlet concentration on breakthrough curves was evaluated using three
initial feed solutions, i.e. 50, 100 and 150 mg/l of RB 171, while a bed height of 5 cm and a
flow rate of 2ml/min were used. lt is illustrated that the breakthrough time decreased with
increasing influent concentration. At lower inlet concentrations, breakthrough curves were
dispersed, and breakthrough occurred slowly. This can be explained by the fact that more
adsorption sites were being covered as the concentration of RB 171 dye increases and
therefore more dye can be adsorbed per unit mass of adsorbent (Han et al., 2009).

Table 15: Data to plot Initial Concentration Breakthrough Curves

TIME CF/CO(50mg/l) CF/CO(100mg/l) CF/CO(150mg/l)

25 0.020 0.046 0.051
50 0.031 0.048 0.054
75 0.041 0.055 0.077
100 0.048 0.072 0.099
125 0.050 0.089 0.153
39
 150 0.058 0.144 0.281
175 0.073 0.248 0.376
200 0.084 0.458 0.603
225 0.127 0.549 0.767
250 0.167 0.664 0.844
275 0.256 0.863 0.953
300 0.349 0.894 0.965
325 0.463 0.942 0.980
350 0.569 0.965
375 0.724 0.969
400 0.812 0.984
425 0.861
450 0.876
475 0.928
500 0.941

INITIAL CONCENTRATION BREAKTHROUGH CURVE

1.000

0.900

0.800

0.700

0.600
50 mg/l
100 mg/l
CF/CO

0.500
150 mg/l
0.400

0.300

0.200

0.100

0.000
0 100 200 300 400 500 600
time (mins)

Figure 18: Effect of Initial Concentrations on Breakthrough Curves

40
41
CHAPTER FIVE: WORKPLAN AND BUDGET
5.1 WORKPLAN
Table 16: Work plan

WEEK DATES ACTIVITIES

1 Discussion on various available project ideas
4/09/23 – 8/09/23 Determination of the optimum idea based on
feasibility
2 Familiarization with final project idea by conducting
11/09/23 – 15/09/23 preliminary research in preparation for project
proposals
3 18/09/23 – 22/09/23 Project Proposals to coordinator and supervisor

4 Compilation of useful references gathered during

25/09/23 – 29/09/23
5 2/10/23 – 6/10/23
6 9/10/23 – 23/10/23
7 16/10/23 – 20/10/23
8 23/10/23 – 27/10/23
9 30/10/23 – 3/11/23
preliminary research
Documentation of the report's Chapter One:
Introduction on the project
Extensive review of the compiled references to
develop Chapter Two: Literature Review
Presentation of progress report to project supervisor
Documentation of Chapter Three: Materials and
Methodology
Visit to the Chemical labs to account for any
reagents/materials to be used
Brief session with project supervisor for progress
report and discussion on the results to be expected
based on his past experiences and published
literature
Documentation of Chapter Four: Expected Results
and Discussion
Review of project report compiled so far

10 6/11/23 – 10/11/23 Research on market prices of reagents/materials to

be used and development of a budget

42
11 13/11/23 – 17/11/23 Project progress report to supervisor and adjustment
of report according to feedback received
12 20/11/23 – 24/11/23 End of Semester final report compilation

13 08/01/24 – 12/01/24 Collection of materials

14 15/01/24 – 19/01/24 Collection of materials

15 22/01/24 – 26/01/24 Preparation of Fish Scale Powder

16 29/01/24 – 02/02/24 Preparation of Activated carbon

17 05/02/24 – 09/02/24 Preparation of dye solution and calibration curve

18 12/02/24 – 16/02/24 Investigating effect of pH on absorption of RB171

19 19/02/24 – 23/02/24 Investigating optimum adsorbent dosage rate

20 26/02/24 – 01/03/24 Preparation of fixed bed column setup

21 04/03/24 – 08/03/24 Preparation of fixed bed column setup

22 11/03/24 – 15/03/24 Investigating effect of column bed height on the rate

of adsorption
23 18/03/24 – 22/03/24 Investigating effect of flowrate on the rate of
adsorption
24 25/03/24 – 29/03/24 Investigating effect of initial concentration on the
rate of adsorption
25 01/04/23 – 05/04/24 Final report documentation

43
5.2 BUDGET

Table 17: Budget

Materials Description Price (Ksh.)

*KOH pellets 500 grams 1300.00

*Absolute ethanol 1 liter 1900.00

Distilled water 5 liters 600.00

Molds Medium/small 750.00

*Beakers 500ml (3) 1395.00

Thermometer Mercury 705.00

*Magnetic Stirrer Digital 18,500.00

Mortar and pestle 3” size 396.00

Filter papers 110mm diameter size 880.00

*pH indicator Universal 1250.00

Fish Scales Tilapia fish 0.00

Waste Rubber tires Recycled tires 0.00

Total 27676.00

Data obtained from (Science Lab Ltd, n.d.)

44
6.0 CONCLUSION

In this work, WRAC-FS composite beads were prepared and examined for the continuous
removal of RB171 dye from water using a fixed bed column. The composite components had
relatively low yields from source materials. Fish scales exhibited a higher removal of RB171
as compared to waste rubber derived activated carbon. However, when combined, the
composite exhibits higher removal than FS and WRAC. Optimum adsorbent dosage was
found to be 24g/l. The composite beads were more efficient at lower pH as compared to
higher pH. Llinear regression showed experimental adsorption data fitted well with the
Freundlich isotherm model than the Langmuir model. Breakthrough behavior was highly
dependent on process variables such as bed height, influent flowrate and inlet concentration.
The results suggest that a WRAC-FS composite beads fixed bed column presents a great
potential in removing aqueous dyes from waste water.

45
7.0 RECOMMENDATIONS

46
8.0 REFERENCES
Arvanitoyannis, I. S., & Kassaveti, A. (2008). Fish industry waste: Treatments,
environmental impacts, current and potential uses. International Journal of Food
Science & Technology, 43(4), 726–745. https://doi.org/10.1111/j.1365-
2621.2006.01513.x
Bakar, N. A., Othman, N., Yunus, Z. M., Daud, Z., Norisman, N. S., & Hisham, M. H.
(2020). Physico-Chemical Water Quality Parameters Analysis on Textile. IOP
Conference Series: Earth and Environmental Science, 498(1), 012077.
https://doi.org/10.1088/1755-1315/498/1/012077
Coppola, D., Lauritano, C., Palma Esposito, F., Riccio, G., Rizzo, C., & de Pascale, D.
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