WOLLO UNIVERSITY

KOMBOLCHA INSTITUTE OF TECHNOLOGY

SCHOOL OF TEXTILE, LEATHER AND FASHION
TECHNOLOGY
DEPARTMENT OF TEXTILE ENGINEERING
MSc. in Textile Chemistry

DECOLOURIZATION OF TEXTILE WASTE WATER USING EXTRACT FROM

PUMPKIN SEED

Helen Molla Tassew

June, 2019
Kombolcha, Ethiopia
 DECOLOURIZATION OF TEXTILE WASTE WATER USING EXTRACT FROM
PUMPKIN SEED

Helen Molla Tassew

A [Thesis] Submitted to Research and Post Graduate office of Kombolcha

Institute of Technology, WU in partial fulfillment of the requirements for the degree

of

Masters of Science in Textile Chemistry in the School of Textile, Leather and Fashion
Technology.

Advisor Name: Mr. Tamene Wagaw (Asst. Prof.)

June, 2019

Kombolcha, Ethiopia
 DECLARATION

I, the undersigned, declare that the thesis comprises my own work. In compliance with
internationally accepted practices, I have acknowledged and refereed all materials used
in this work. I understand that non-adherence to the principles of academic honesty and
integrity, misrepresentation/ fabrication of any idea/data/fact/source will constitute
sufficient ground for disciplinary action by the University and can also evoke penal
action from the sources which have not been properly cited or acknowledged.

Name of the student: Helen Molla Tassew Signature _____________

Date of submission: ________________
Place: Kombolcha

This thesis has been submitted for examination with my approval as a university
advisor.

Advisor Name: Mr. Tamene Wagaw (Asst. Prof.)

Advisor’s Signature: ______________________________

i
 © 2019
Helen Molla Tassew
ALL RIGHTS RESERVED

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 Wollo University

Kombolcha Institute of Technology

School of Textile, Leather and Fashion Technology

THESIS APPROVAL SHEET

Student:
Helen Molla Tassew________________________________________________
Name Signature Date

The following graduate faculty members certify that this student has successfully presented
the necessary written final thesis and oral presentation for partial fulfillment of the thesis
requirements for the Degree of Master of Science in Textile Chemistry
Approved By:
Advisor:
Mr. Tamene Wagaw (Asst. Prof.) ____
Name Signature Date

External Examiner:
Mr. Adane Haile (Asst. Prof.) ____
Name Signature Date

Internal Examiner:
Dr. Shrirang K. Chinta ____
Name Signature Date

Chair Holder:
Mr. Bezaneh ____
Name Signature Date

Graduate study approval:

____
Name Signature Date

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To my father and mother

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 ACKNOWLEDGEMENTS

First of all, I am grateful to the Almighty God for blessing my life. Next, I would first to
thank my supervisor Mr. Tamene Wagaw (Asst. Prof.), for suggesting, inspiring,
providing, assistanceing and supporting me throughout my thesis work. I would also like to
thank Wollo University Kombolcha Institute of Technology for the sponsorship that allowed
me to study my postgraduate program. I convey my sincere thanks to Kombolcha Textile
Share Company (KTSC), Bahir Dar Institute of Technology Environmental engineering
department and Ethiopian Institute of Textile and Fashion Technology for giving me the
necessary information, Lab equipments and materials to conduct this study. Finally, I wish
to express my deepest gratitude to my families whose guidance, encouragement, wisdom,
motivation, and expectations are indispensable to my achievements and will serve as
a continuous inspiration for my future career.

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 ABSTRACT
The generation of highly coloured wastewater is one of the main environmental problems
of the textile industry. For this reason, many chemical treatment processes have been
used extensively to treat textile wastewaters. Aluminum sulfate (alum), ferrous sulfate,
and ferric chloro-sulfate were commonly used as coagulants. However, a possible link of
Alzheimer’s disease with conventional aluminium based coagulants has become an
issue in wastewater treatment. Hence, special attention has shift towards using natural
coagulants in wastewater treatment, which are more environmental friendly. Moreover,
bio-coagulants are polyelectrolyte of high molecular weight and high charge density
which obtained from natural organic materials. Natural coagulants have been attracting
wide interest of researchers because they have the advantages of biodegradability, safe for
human health, environmental friendly, generally toxic free, less sludge generation and
produce no secondary pollution. This project objectively concerns extraction of coagulant
from pumpkin seed, to decolorize textile waste water. This natural coagulant function by
means of coagulation mechanism followed by charge neutralization or polymeric
bridging effect. Tests of coagulant activity and determination of optimal parameters for
the process were carried out. This is accomplished through the simulation of jar test and
measurement of the percentage of visible color, turbidity and COD removal. The influences
of several parameters such as pH, coagulant dosage and mixing time were tested. In this
study, the maximum colour removal (92 %) was achieved at coagulant dose 8g/l, pH 5 and
45 minutes of mixing time. At these optimum conditions 90% and 82.5 % turbidity
reduction and COD were obtained respectively.

Key words: Coagulation; Pumpkin; Bio-coagulants; Decolorisation; textile waste water

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 TABLE OF CONTENTS

DECLARATION................................................................................................................... I

ACKNOWLEDGEMENTS ................................................................................................ V

ABSTRACT ....................................................................................................................... VI

TABLE OF CONTENTS .................................................................................................. VII

LIST OF ABBREVATIONS............................................................................................... X

LIST OF SYMBOLS.......................................................................................................... XI

LIST OF FIGURES ........................................................................................................... XII

LIST OF TABLES .......................................................................................................... XIII

1. INTRODUCTION ........................................................................................................ 1

1.1. Background ............................................................................................................... 1

1.2. Problem Statement .................................................................................................... 3

1.3. Objective of the study................................................................................................ 4

1.4. Scope of the study ..................................................................................................... 5

1.5. Significance of the study ........................................................................................... 6

2. LITERATURE REVIEW ............................................................................................. 7

2.1. Introduction ............................................................................................................... 7

2.2. Textile waste water .................................................................................................... 7

2.2.1. Characteristics of Textile Waste water............................................................................8

2.3. Effect of textile waste water ...................................................................................... 9

2.3.1. Effects of textile on environmental and human health .............................................10

2.4. Coagulation/flocculation processes ......................................................................... 11

2.5. Coagulation mechanisms ......................................................................................... 16

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 2.5.1. Adsorption and Bridging ...................................................................................................16
2.5.2. Double-Layer Compression..............................................................................................16
2.5.3. Charge Neutralization ........................................................................................................17
2.5.4. Sweep Coagulation .............................................................................................................17

2.6. Natural coagulants ................................................................................................... 18

2.6.1. Nirmali seeds ........................................................................................................................20
2.6.2. Moringa oleifera ..................................................................................................................21
2.6.3. Tannin .....................................................................................................................................22
2.6.4. Cactus......................................................................................................................................23

2.7. Fruit wastes for coagulation .................................................................................... 25

2.7.1. Preparation steps of bio-coagulants................................................................................25

2.8. Factors affecting coagulation processes .................................................................. 27

2.9. Treatment of textile waste water using bio-coagulants ........................................... 28

2.10. Textile waste water disposal standards ................................................................... 31

2.10.1. Environmental legislation .................................................................................................32

2.11. Literature summary ................................................................................................. 33

3. MATERIALS AND METHODS ................................................................................ 34

3.1. Materials and chemicals .......................................................................................... 34

3.1.1. Materials.................................................................................................................................34
3.1.2. Chemicals...............................................................................................................................34

3.2. Methods ................................................................................................................... 34

3.2.1. Pumpkin seed collection and preparation .....................................................................34
3.2.2. Textile waste water collection .........................................................................................36
3.2.3. Characterization of the coagulant and waste water ...................................................37

3.3. Coagulant extraction................................................................................................ 37

3.3.1. Soxhlet extraction ................................................................................................................37
3.3.2. Experimental studies...........................................................................................................38

3.4. Jar test ...................................................................................................................... 39

3.5. Data analysis............................................................................................................ 41

4. RESULTS AND DISCUSSION ................................................................................. 42

4.1. Characterization of coagulant and waste water ....................................................... 42

4.2. Characteristics of textile waste water ...................................................................... 45

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4.3. Factors affecting coagulation process ....................................................................... 46

4.4. Optimization Analysis ............................................................................................. 54

5. CONCLUSION AND RECOMMENDATIONS........................................................ 57

5.1. Conclusion ............................................................................................................... 57

5.2. Recommendations ................................................................................................... 58

REFERENCES ................................................................................................................... 60

APPENDIX ........................................................................................................................ 63

Appendix 1: Textile wastewater discharges to water bodies according to EPA, 2003 ...... 63

Appendix 2: Experimental runs and results to optimize operational parameter ................ 63

Appendix 3: The overall treatment stages of these experimental work with images ......... 65

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 LIST OF ABBREVATIONS
ANOVA………………………………………………………………..Analysis of variance
BOD……………………………………………………………Biological Oxygen Demand

CI……………………………………………………………………………......Color Index

COD…………………………………………………………….Chemical Oxygen Demand

EPA……………………………………… Environmental Protection Authority (Ethiopia)

FTIR…………………………………………………………… Fourier Transform Infrared

KIoT…………………………………………………... Kombolcha Institute of Technology

KTSC…………………………………………………Kombolcha Textile Share Company

NTU………………………………………………………….Nephelometric Turbidity Unit

pH…………………………………………………………………….Potential of Hydrogen

RPM…………………………………………………………………Revolution per Minute

TDS…………………………………………………………………...Total dissolved solids

TSS………………………………………………………………….Total Suspended solids

WTP………………………………………………………………...Water Treatment Plants

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 LIST OF SYMBOLS

Co…………………………………………………Initial concentrations (before treatment)

C.…………………………………………………...Final concentrations (after treatment)

E…………………………………………………………………………………Efficiency

H2SO4………………………………………………………………………….Sulfuric acid

kDa……………………………………………………………………………...Kilo Dalton

NaOH…………………………………………………………………….Sodium hydroxide

pI…………………………………………………………………………...Isoelectric point

Pt–Co…………………………………………………………………Platinum Cobalt Unit

T1………………………………………………………………………….…Final turbidity
T2…………………………………………………………………………...Initial turbidity

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 LIST OF FIGURES
Figure 2. 1 Effects of textile wastewater into the environment ......................................... 11

Figure 2. 2 Coagulation, sedimentation and filtration steps .............................................. 12

Figure 2. 3 Coagulation/flocculation mechanism of bio-coagulant extract....................... 19

Figure 2. 4 Schematic categorization of natural coagulants .............................................. 20

Figure 2. 5 Schematic representation of basic tannin structure in aqueous solution and

possible molecular interactions .......................................................................................... 23

Figure 2. 6 Schematic representation of polygalacturonic acid in aqueous solution and

possible dominant molecular interactions associated with adsorption and bridging.......... 24

Figure 2. 7 General processing steps in preparation of plant-based coagulants ................ 26

Figure 2. 8 Advantages of natural coagulants over chemical coagulants .......................... 30

Figure 3. 1 Coagulant preparation processes ..................................................................... 36

Figure 3. 2 Soxhlet extraction set up and ethanol and oil from soxhlet respectively ........ 38

Figure 3. 3 Jar test apparatus set up ................................................................................... 39

Figure 4. 1 FTIR analysis of Pumpkin seed before extract ................................................ 42

Figure 4. 2 FTIR analysis of Pumpkin seed after extract ................................................... 43

Figure 4. 3 FTIR analysis of Pumpkin seed before and after extract ................................ 44

Figure 4. 4 Effect of coagulant dose on % removal of color, COD and turbidity .............. 48

Figure 4. 5 Effect of pH on color, COD and turbidity percentage removal ....................... 51

Figure 4. 6 Effect of mixing time on color and turbidity percentage removal ................... 53

Figure 4. 7 The response pH at different coagulant doses.................................................. 54

Figure 4. 8 Wastewater samples & results of coagulation at optimum factors……………56

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 LIST OF TABLES
Table 2. 1 Principal existing and emerging processes for textile waste water treatment .. 14

Table 2. 2 Proximate composition determination of the coagulant [35] ........................... 31

Table 4. 1 The physicochemical characteristics of collected raw waste water from

Kombolcha textile industry. ............................................................................................... 45

Table 4. 2 EPA standard for textile wastewater discharge to water

bodies………………Error! Bookmark not defined.

Table 4. 3 Percentage removal of color, COD and turbidity at various coagulant doses. . 46

Table 4. 4 Percentage removal of color, COD and turbidity at different pH .................... 49

Table 4. 5 Percentage removal of color and turbidity at different mixing time ................ 52

Table 4. 6 Comparisons between treatment result with national discharge standard ........ 56

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 1. INTRODUCTION
1.1. Background

Textile wet processing (dyeing and printing) are among the most environmentally
unfriendly industrial processes, because they produce colored wastewaters that are
heavily polluted with dyes, textile auxiliaries and chemicals [1]. Besides, textile
finishing’s wastewaters, especially dye-house effluents, contain different classes of
organic dyes, chemicals and auxiliaries. Thus they are coloured and have extreme pH,
COD and BOD values, and they contain different salts, surfactants, heavy metals,
mineral oils and others. Therefore, dye bath effluents have to be treated before being
discharged into the environment or municipal treatment plant [2]. The extensive use of
chemicals for various purposes in day-to-day life and the growing industrialization led to
unwanted contamination of our existing natural resources by the release of diverse organic
and inorganic pollutants into water system. Nowadays, the public has become more
sensitive towards the protection of the environment and general awareness has now
increased about the potential adverse effects of industrial effluents contaminate with
various pollutants, including dyes on the environment.

Worldwide 280,000 tons of textile dyes are discharged in industrial effluents every year
[4]. Among the different kinds of textile dyes, reactive dyes are widely used in the dyeing
of cotton and other cellulosic fibers since they offer high washing fastness and brilliant
colors. Reactive dyes represent 25% of the total world market [6]. On the other hand, these
dyes have a relatively low degree of exhaustion and fixation. The unfixed dyes are
hydrolyzed and cannot be reused because they are unable to be covalently fixed to the
cellulosic fibers. Consequently, substantial amounts of unfixed dyes are released in the
wastewater. Another environmental concern associated to dyeing with reactive dyes is the
generation of highly saline effluents due to the amount of electrolyte, generally NaCl,
required to increase the dye exhaustion and fixation. About 50–80 g/L of salt is added
during the reactive dyeing [7] which is almost completely discharged into the wastewater
after the dyeing process. The presence of high concentration of salts is very harmful for
aquatic ecosystems. Several research methods developed for removing dyes from waste

1
water and different methods have been developed. For example, adsorption onto materials
as activated carbon and physical and chemical degradation [2]. Coagulation is one of the
effective textile wastewater treatment techniques. This technique is affirmed to remove
dissolved, and suspended matter as well as color from dyes which are responsible for
turbidity as well as, organic matters which contribute to BOD and COD content of
wastewater [9 ]. The method needs adding of chemicals such as salts of aluminum, iron
and polyelectrolytes coagulants in to textile wastewater [10].

These chemical coagulants are acknowledged for their effectiveness on treatment of the
wastewater. However the use of such chemical coagulants is not free from some
limitations. Coagulation-flocculation process has drawback like transfer of toxic
compounds into solid phase and formation of concentrated sludge that has to be treated
subsequently, relatively time consuming process and required chemicals input, detrimental
effects on human health and toxicity to aquatic life, production of large sludge volume
and non-biodegradable, ineffectiveness in low-temperature, change PH value of the
treated water. Besides, such chemical coagulants incur high procurement costs both for
import and sludge disposal [11]. In recent years, there has been a move on the part of
researchers to identify and apply natural materials instead of chemical coagulants [12]. In
industrial wastewater treatment, these natural coagulant/flocculants can be applied in
textile dyeing and finishing processes [3].

On the other hand, using natural coagulants have been attracting wide interest of
researchers because they have the advantages of biodegradability, cost-effective, safe for
human health, environmental friendly, generally toxic free and produce no secondary
pollution. Not only this, the sludge volume generated by the natural coagulants is smaller
than chemical coagulants; it can further be treated biologically or can be disposed safely as
soil conditioners because of their non-toxicity. The raw plant extracts are often available
locally and hence, a low-cost alternative to chemical coagulants. Several studies were
conducted on extraction of bio-coagulants like Moringa, cactus, chitosan, orange peel and
avocado seed to enhance the coagulant ability for removal of water and waste water
effluents. However, lack of studies has been directed towards the characterization of the

2
active component in pumpkin seeds extracted with solvent using soxhlet. Moreover, the
extracted active agent after de-oiling (defatted seed) were used as a coagulant.

This work is focused on the use of the waste extracted from bio-coagulant to decolorize
textile dye effluents. In recent years, some studies have been published about the treatment
of acid dye, Congo red dye and for adsorptive removal textile waste water as activated
carbon and coagulant using different types of natural coagulants [5]. But to our knowledge
there is no previous literature centered on the use of pumpkin seed extract to decolorize
textile dye effluent. The active component from pumpkin seed will be extracted using
soxhlet equipment by solvent extraction process and the de-oiling seed (defatted seed) used
as a coagulant. The research will investigate the effect of operating parameters like, pH,
mixing time, and coagulant dose for optimum condition of coagulation and will evaluate
color removal efficiency, turbidity reduction as well as COD removal.

1.2. Problem Statement

In Ethiopia, the textile industry is the largest manufacturing industry which is given more
attention and further expansion. In almost all cases, the Ethiopian industries (textile, paper,
plastic, leather, food, cosmetic, etc.) release their untreated or partially treated wastewaters
into municipal sewers or directly into nearby drains, rivers, stagnant, ponds, lagoons, or
lakes. Such wastewater disposal may cause damage to the quality of the receiving water
bodies, the aquatic ecosystem, animal health, human health and the environment at large.
Among the different kinds of textile waste water effluents, reactive dyes are widely used
in the dyeing of cotton and other cellulosic fibers since they offer high washing fastness
and brilliant colors. Reactive dyes represent 25% of the total world market [6]. About 50–
80 g/L−1 of salt is added during the reactive dyeing which is almost completely discharged
into the wastewater after the dyeing process. The presence of high concentration of salts is
very harmful for aquatic ecosystems.

Several methods are used to treat textile waste water to achieve decolorization. These
include physicochemical methods such as filtration, coagulation, use of activated carbon
and chemical flocculation [9]. These methods are effective but they are expensive and

3
involve the formation of a concentrated sludge that creates a secondary disposal problem
which requires safe disposal. The utilization of bio-coagulants for textile waste water
treatment is perhaps one of its most interesting usages. Although there are many previous
papers investigating its utilization as a natural adsorbent for special pollutant removal. The
waste of these natural seeds of these local plants have a high amount of proteins that act
like cationic polyelectrolytes once they are added to raw water [7]. The interest in this
aspect of bio-coagulants has been pointed out by institutions such as the Food and
Agricultural Organization of the United Nations (FAO).

All previous investigations pointed out the advantages of bio-coagulants as a treatment

agent versus synthetic coagulant combinations (FeCl3 and Al2 (SO4)3) with synthetic
polyelectrolytes. The main benefits can be divided into three big groups:
Technologically, using bio-coagulants are much easier than the traditional
coagulation/flocculation process, due to the fact that modifying the pH level is not
mandatory and concentrations of species such as Cl− and SO4= are not significantively
increased in the treated water. The process is not complex and it does not require special
maintenance;
Environmentally, the origin of bio-coagulant extract is completely natural, so several
disadvantages linked to the usage of alum are avoided, particularly those that have to do
with aluminum intake;
Abundance, Bio-coagulants is widely available and easy to store, especially in developing
countries. It can be a social-change factor, since it allows waste water treatment without
dependence (importing synthetic coagulants.)

1.3. Objective of the study

General objective:

The general objective of this study is to extract coagulant from pumpkin seed and
investigate the effect of this bio-coagulant on decolourization of textile waste water
through coagulation.

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Specific objectives:

1. To investigate the ingredients available in pumpkin seed.

2. To extract the coagulant from pumpkin seed.

3. Study the coagulant capacity of pumpkin seed extract for decolourization of textile waste
water.

4. Examine the effects of parameters (pH, coagulant dosage and mixing time) on the color
removal efficiency.

5. Determine the optimum value of these operating parameters.

1.4. Scope of the study

This thesis work includes the collection of bio-coagulants from South Wollo Zone and
around Kombolcha areas, Characterization of functional groups present in bio-coagulant,
investigation of coagulation of textile effluent using the extract seed powder and study the
removal efficiency of coagulant at different concentration, optimize the optimum coagulant
dose, pH, and mixing time using Jar-test apparatus. This study generally objected at
assessing the effectiveness of bio-coagulant in decolourization of textile effluents. Thus,
this study does not concern methods and processes which may be applicable for textile
wastewater treatment other than coagulation. Besides, this research does not attempt to
examine every parameters of textile wastewater. Instead it is delaminated on the basic
parameters that measures the pollution strength of the textile effluent namely color,
turbidity, COD and pH.

Furthermore, although there are different factors which can be studied in relation to
coagulation process, this study pays attention on the major factors like coagulant dose, pH
and mixing time. Finally, the paper summarizes the results and experimental investigations.

5
 1.5. Significance of the study

The significance of the study is fully recognized in solving the environmental problems of
the textile sector by suggesting a coagulation process using natural coagulant. Bio-
coagulants contribute in minimizing contaminant found in the textile waste water
discharged into inland surface water which is important to protect the biodiversity found
in the surface water, safe for human health, environmental friendly behavior, locally
availability as well as cost effective, produce lesser volume and biodegradable sludge, and
to keep the sustainability of the environment. Therefore, this research is beneficial in
Ethiopia to have effective textile wastewater treatment method, by using bio-coagulants,
which has fundamental importance for maintaining people’s health, protecting the quality
of the environment and ultimately to reduce the costs of wastewater treatment chemicals.

These are the most important benefits:

1. Farmers who grow pumpkin can generate income through selling its seed.
2. Using naturally occurring coagulants are biodegradable, locally available and are
presumed safe for human health this also makes the study significant.
3. The use of the natural coagulant saves the cost spends to buy chemicals using foreign
currency which in turn contributes role for the development the country.

4. Easy preparation of coagulant and easy technology

5. Might be low cost compare to conventional methods (but economic analysis has to be
evaluated.
This study contribute in minimizing contaminant found in the textile waste water
discharged into inland surface water which is important to protect the biodiversity found
in the surface water, ground water and to keep the sustainability of the environment.

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 2. LITERATURE REVIEW
2.1. Introduction

In this chapter an attempt was made by the researcher to review literatures which are
expected to provide theoretical supporting for the problem sought to be achieved under this
thesis. Eventually, issues like the strength, limitation and gaps of previous studies about
the use of bio-coagulants for waste water treatment, review of available decolorization
methods, wastewater disposal standards, coagulation flocculation process, Mechanism of
coagulation flocculation process, synthetic coagulants, bio-coagulants and their
coagulation mechanism, factors affecting coagulation and flocculation process, limitations,
challenges and perspective in the use of plant based natural coagulants were discussed.
Also, the strength, limitation and gaps of all previous studies are included in this chapter.
Lastly, special attention has been given to coagulation process using pumpkin seed as a
coagulant for decolorization of textile waste water. In dyeing and printing stage of textile
industry various types of dyes are used to color their products. The dye containing
wastewater is usually released directly into the nearby drains, rivers, stagnant, ponds or
lagoons. Such wastewater disposal may cause damage to the quality of the receiving water
bodies, the aquatic eco-system and the biodiversity of environment. The dyeing industry
effluents contain high BOD and COD value, suspended solids, toxic compounds and the
color that is perceived by human eyes at very low concentration. Moreover, dyes may
adversely affect the aquatic life because of the presence of aromatic materials, metals and
chlorides highly colored and saline as well as contain non-biodegradable compounds etc.
Therefore, the problem associated with textile wastewater discharge in Ethiopia need
immediate solution.

2.2. Textile waste water

The textile industry is one of the most important manufacturing sectors and produces large
volumes of highly toxic wastewater due to the use of high quantities of water, dyes and
chemicals in its processes. The World Bank estimates that 17–20% of industrial water
pollution is contributed by the textile industry [36]. Scouring, dyeing, printing, finishing

7
and washing processes contribute the highest volumes of wastewater. The dyeing industry
consumes about 30–50 L of water per 1 kg of cloth depending on the type of dye used. The
overall water consumption of yarn dyeing is about 60 L per 1 kg of yarn [37]. In general,
textile industries typically generate 200–350 L of wastewater per 1 kg of finished product
resulting in an average pollution of 100 kg chemical oxygen demand (COD) per ton of
fabric. For a textile unit processing 400,000 lb. of cotton per week, more than 50,000 lb.
of salts are released. The usual salt concentration in wastewater is 2000–3000 ppm [36].
The salts in the effluent can lead to the soil infertility and aquatic life damage. Not to
mention that about 2 to 50% of the total dyes that have not been fixed to the fiber are lost
during dyeing and washing process, leading to severe contamination of surface and ground
water.

The Environmental Protection Agency (EPA) has classified textile wastes into four
principal groups, namely dispersible, hard-to-treat, high-volume, and hazardous and toxic
wastes [38]. The composition and volume of wastewater from textile industries exhibit
wide heterogeneity, depending on many different factors, including the type of fibers,
chemicals and dyes, machines, techniques, the season of the year, the characteristic quality
imparted to processed fabric, the nature of the special finishing if any, the specificity of the
process and the principles on which the water use has been modeled. In general, textile
wastewater is quite a complex mixture and is highly variable, comprising many polluting
substances. It is a mixture of different types of dyes and auxiliary products such as
surfactants, fixing agents, oxidizing agents, recalcitrant chlorinated compounds, salts,
heavy metals, dispersing agents and smoothing agents (compounds that may be both
persistent and toxic). Wastewaters are highly colored due to the presence of dyes that have
not been fixed to the fiber during the dyeing process. They are usually also characterized
by high levels of chemical oxygen demand (COD), biochemical oxygen demand (BOD),
pH, salinity, temperature, turbidity, toxic chemical compounds, total dissolved solids
(TDS) and total suspended solids (TSS).

2.2.1. Characteristics of Textile Waste water

The characteristics of textile effluents vary and depend on the type of raw materials,
chemicals used, and the type of textile manufactured [16] . The textile wastewater

8
contains high amounts of agents causing damage to the environment and human health
including suspended and dissolved solids, biological oxygen demand, chemical oxygen
demand, heavy metal, odor and color [15] . Most of the BOD/COD ratios are found to
be around 1:4, indicating the presence of non-biodegradable substances. Generally, the
effluent from a textile industry is characterized by extreme fluctuations in many
parameter s such as COD, BOD, pH, strong color and salinity [6 ]. The composition
of the wastewater will depend on the different organic - based compounds, chemicals
and dyes used in the dry and wet-processing steps [5]. Recalcitrant organic, colored,
toxicant, surfactant, chlorinated compounds and salts are the main pollutants in textile
effluents. This research also, characterize textile waste water sample taken from
Kombolcha textile industry of Ethiopia and the typical characteristics of textile waste water
described in result.

2.3. Effect of textile waste water

Depending on the concentration and exposure time, dyes can have acute and/or chronic
effects on exposed organisms [37]. Today, two classes of dyes, azo and disperse, are
recognized worldwide as having the potential to cause allergic contact dermatitis and
possibly cancer. They can be cleaved by skin bacteria, or by dermal or systemic metabolism
into aromatic amines which might have undesired toxicological properties, particularly due
to their carcinogenic or allergenic potential. Textile dyes also affect human metabolism
through the food chain, causing kidney and respiratory problems, and hypertension, among
others. Studies carried out with workers in the textile industry indicated that these
professionals are more prone to pancreatic cancer, bladder cancer and cancer of the
digestive system because they are exposed to dyes on a daily basis. Azo and nitro dyes are
reduced in the intestinal environment, resulting in the formation of toxic amines in both
cases. Other studies also found an association between esophageal cancer and workers in
the textile industry. Wastewaters from the textile industry are usually polluted with
recalcitrant or hazardous organics, such as dyes, surfactants, metals, salts, and persistent
organic pollutants (POPs) [36]. These industries discharge large volumes of wastewaters
into aquatic environments, which may affect aquatic organisms both directly and indirectly,

9
through the trophic chain or by re suspension, which may make pollutants bioavailable and
enable them to reach human beings.

2.3.1. Effects of textile on environmental and human health

Depending on the concentration and exposure time, dyes can have acute and/or chronic
effects on exposed organism [39]. Today, two classes of dyes, azo and disperse, are
recognized worldwide as having the potential to cause allergic contact dermatitis and
possibly cancer. They can be cleaved by skin bacteria, or by dermal or systemic metabolism
into aromatic amines which might have undesired toxicological properties, particularly due
to their carcinogenic or allergenic potential. Textile dyes also affect human metabolism
through the food chain, causing kidney and respiratory problems, and hypertension, among
others. Studies carried out with workers in the textile industry indicated that these
professionals are more prone to pancreatic cancer, bladder cancer and cancer of the
digestive system because they are exposed to dyes on a daily basis. Azo and nitro dyes are
reduced in the intestinal environment, resulting in the formation of toxic amines in both
cases. Although textile wastewaters are variable mixtures of many pollutants, their major
characteristic is high coloration due to the presence of dyes. This high coloration coupled
with high organic load induces perturbation to aquatic life and causes dramatic aesthetic
pollution, which cannot be tolerated by local populations [39].

The greatest environmental concern about dissolved dyes in water bodies is not only their
visibility, but also because they absorb sunlight and can hinder light penetration in the
water (rivers, lakes, lagoon, etc.) and, hence reduce the photosynthetic activity of aquatic
flora. As a result, there is a significant reduction in the oxygenation capacity of the water,
disturbing the whole aquatic ecosystem and the food chain. Dissolved dyes can also cause
an increase in air pollution in terms of stringent foul odors, inorganic carbon deposits,
changes of the soil matrix and ground water systems are affected due to leaching through
the soil. In addition, dyes accumulate in sediments at many sites, especially at location
of wastewater discharge , which has an impact on the ecological balance in the aquatic
system. These pollutants because of leaching from soil also affect ground water system.
Therefore, color is the first contaminant to be recognized in the dyeing effluents and
has to be removed before discharging into the receiving environment. Verma, summarized

10
the harmful direct and indirect effects of textile wastewaters in the environment as shown
in Fig. 2.1.

Textile wastewater discharge of the

Environment

Indirect Effects
Direct Effects
• Killing of aquatic life such as
• Aesthetic problems
fishes, plants, mammals.
• Poor sunlight penetration in the
• Eutrophication.
receiving water, damage flora & fauna.
• Coloured allergen accelerates
• Ground water pollution due to
genotoxicity and microtoxicity.
leaching of contaminant through soil.
• Suppression of immune system
• DO depletion of receiving water.
of human beings.

Figure 2. 1 Effects of textile wastewater into the environment

2.4. Coagulation/flocculation processes

Currently, there is an increased interest in the decolorization and decontamination of

industrial textile wastewater. Different treatment technologies have been studied in order
to solve the problems caused by the toxic substances contained in industrial textile
wastewater, such as electrocoagulation, adsorption, photo catalytic process, ozonation,
membrane bioreactor and anaerobic/aerobic biological treatment. However, these methods
are neither economically nor technologically suitable for large scale use and normally
require the combination of two or three methods to achieve an appropriate level of color
remove. Coagulation/flocculation (CF) is the most widely used technique in industrial
wastewater treatment worldwide because it is relatively simple and inexpensive to operate.

11
It has been reported that the Egyptians were using aluminum sulfate (alum) to cause
suspended particles to settle in water as early as 1500 BC. Although the early Romans were
also familiar with alum, it was not until 77 AD that its utilization as a coagulant in water
treatment was firs recorded. Today, the coagulation-flocculation process is a vital step in
removal of colloidal particles, natural organic matter, microorganisms and inorganic ions
present in untreated water [25].

Figure 2. 2 Coagulation, sedimentation and filtration steps

The first step in the coagulation process is destabilizing the particle charges in the water.
Coagulant of opposite charges added to neutralize the negative charge on the dispersed non
settable solids. Once the charge is neutralizes, the smaller particles are capable of sticking
together to form a slightly larger particles. Rapid and slow mixing after coagulant dosing
is a design parameter. Rapid mixing ensures the coagulant is properly dispersed in the
water and promotes particle collision that is needed to achieve good coagulation.
Slower mixing helped in promoting floc formation by enhancing particle collisions which
led to larger flocs.

The inherent disadvantage to this process is its generation of large quantities of chemical
sludge that is classified as hazardous waste that must be disposed of in secure landfills. The
process also increases the total dissolved salt content in the treated wastewater, increasing
desalination costs by a substantial margin. On the other hand, coagulant aids are inorganic
12
materials that, when used alongside a main coagulant improve or accelerate the process of
coagulation and flocculation by producing quick forming, dense and rapidly settling flocs.
Coagulant aids increase the density of slow settling flocs and add toughness to the flocs so
that they do not break up during the mixing and settling processes [25]. Selecting a
coagulant for treatment of water and wastewaters is a function of several factors
which include the nature of the suspended particles, raw water and wastewater condition,
design of treatment facility, cost of coagulant chemicals, zeta potential (the amount of
repulsive forces which ensure that particles stay in water environment), and Van der Waal’s
forces (weak inter-molecular forces that influence particle formation). Plant scale
evaluation analysis or ‘jar testing’ is performed to select appropriate coagulants for the
treatment process. For any treatment process to be effective, attention must be paid
to required effluent quality, sludge handling disposal cost (most coagulants generate
sludge), and overall dosage cost of coagulant.

The efficiency of CF its operational costs depend on several factors, including the
coagulant type and dosage, mixing conditions, pH, temperature, ionic strength, as well as
the nature and concentration of the organic matter, the total dissolved solids, the size and
distribution of the colloidal particles in suspension among others [9]. There are two main
types of coagulant chemicals. These include; primary coagulants and coagulant aids.
Primary coagulants are involved in neutralizing electrical charges of suspended solids
in water, while coagulant aids increases the density of slow-settling flocs by impacting
toughness to the flocs to avoid shearing during mixing and settling processes. Coagulant
chemicals are either inorganic metallic salts or polymers. Polymers are of three types
namely; cationic polymers (positively charged), anionic polymers (negatively
charged), and non-ionic (neutrally charged).

13
Table 2. 1 Principal existing and emerging processes for textile waste water treatment

Dye removal method Advantages Disadvantages

Conventional Coagulant Simple, economically High sludge production,

handling and
treatment Flocculant Feasible
disposal problems
process
Biodegradation Economically attractive, Slow process, necessary
publicly to create an

acceptable treatment optimal favorable

environment,

maintenance and
nutrition requirement
Adsorption on The most effective Ineffective against
adsorbent, great, disperse and vat
activated
capacity, produce a
carbon dye, the regeneration is
high-quality treated
effluent
expensive and result in
loss of the

adsorbent, non-
destructive process
Establish Membrane Remove all dye types, High pressure,
expensive, incapable of
recovery separation produce a high-quality
treating large volumes
process treated effluent
Ion-exchange No loss of sorbent on Economic constraints,
not effective for
regeneration, effective

14
 disperse dye

Oxidation Rapid and efficient High energy cost,

chemical required
Process
Emerging Advanced No sludge production, Economically
unfeasible, formation of
removal oxidation little or no consumption
process of by-products, technical
processes
constraints
chemicals, efficiency

for recalcitrant dyes

Reverse Removal of all mineral

Osmosis salts
High pressure
hydrol yzes reactive
dyes, and

chemical auxiliaries.
Electrochemical Capacity of adaptation Iron hydroxide sludge
processes to different

volumes and pollution

loads.
Selective Economically attractive, Requires chemical
modification,
Bio adsorbents Regeneration is not
necessary, nondestructive process

high selectivity

15
 2.5. Coagulation mechanisms

The process of coagulation or destabilization of colloidal particles may occur through four
types of mechanisms: adsorption and bridging; double-layer compression; charge
neutralization; and sweep coagulation. Each of the mechanism explained in detail below:

2.5.1. Adsorption and Bridging

Bridging between particles occurs with the introduction of long-chain polymers or
polyelectrolytes, as these coagulants are capable of extending into the solution to capture
and bind multiple colloids together. The bridging efficiency is further improved when
coagulants with larger molecular weights are used, due to their extended polymeric chains.
Natural polymers such as polysaccharides and proteins can also induce coagulation via
bridging. Such a mechanism has been recognized since the 1950s and is extremely
important in practice. An essential requirement for bridging flocculation is that there should
be sufficient unoccupied surface on the particles for attachment of segments of polymer
chains adsorbed on other particles. It follows that the adsorbed amount should not be too
high, otherwise the particle surfaces will become so highly covered that there are
insufficient adsorption sites available [25]. In general, if the molecular weight is high and
the charge density is low, the polymer adsorbs on the particle surface in such a way that
tails and loops extend far beyond the surface and can interact with other particles. The
consequence of bridging flocculation is that the flocs produced can be much stronger than
those formed when particles are destabilized by simple salts.

2.5.2. Double-Layer Compression

This mechanism involves the reduction of the double layer around the colloidal particle by
a change in ionic strength induced by the addition of a different electrolyte, which results
in the destabilization of colloid [10]. Under stable conditions in which the concentration of
counter-ions is low, colloidal particles are unable to get close to each other because of their
thick double electrical layer. However, as the concentration of counter-ions increases via
the addition of salts, the diffuse layer becomes thinner and particles can approach more
closely before experiencing repulsion. It has been speculated that compression of the

16
electrical double layer is the dominant coagulation mechanism for divalent ions, principally
Ca2+ and Mg2+, in the normal pH range of water treatments.

2.5.3. Charge Neutralization

Charge neutralization is the process of adding cationic metals or polymers to neutralize the
negative charges of the particles. This coagulation mechanism involves the adsorption of
an oppositely charged coagulant on the colloidal surface. It is well known that electrostatic
interactions give strong adsorption in these systems and that neutralization of the particle
surface and even charge reversal can occur. There is thus the possibility that flocculation
could occur simply as a result of the reduced surface charge of the particles and hence a
decreased electrical repulsion between them [7].

2.5.4. Sweep Coagulation

Sweep coagulation is a mechanism related to metal coagulants like Al3+ and Fe3+. If a high
concentration of these metals is added to water, a large quantity of metal hydroxide will be
produced. This amorphous hydroxide will settle, and sweep colloidal particles in its way
downward. Sweep flocculation generally gives considerably better particle removal than
destabilization by charge neutralization alone. At least part of the reason is the greatly
improved rate of aggregation, because of the increased solid concentration. Hydroxide
precipitates tend to have a rather open structure, so that even a small mass can give a large
effective volume concentration and, hence, a high probability of capturing other particles
[8].

The addition of certain chemicals into the raw water causes particle s to destabilize
and allows agglomeration and floc formation to occur. The general terms used for this
purpose are: Coagulants, which assist the destabilization of particles (particularly colloidal
sizes). Flocculants (also known as flocculent aids or coagulant aids), which assist in the
joining and enmeshing of the particle s together. In textile wastewater treatment
coagulation -flocculation are a commonly treatment methods that can be employed to
decolorize effluent and also to reduce the total lo ad of pollutants. The main advantage
of these methods is cost effective, simple to operate and energy saving treatment
alternative. The inherent dis advantage to this process is the generation of large quantities
of chemical sludge and its classification as hazardous waste, necessitating the need for

17
secured land filling of hazardous solid wastes. For this reason, alternative natural
materials have been considered for environmental applications. In this stud y the
researcher used the term coagulation, in line with the common trend, to represent the
whole process starting from adding of coagulant in wastewater up to their settlement.

2.6. Natural coagulants

In view of the need to overcome the drawbacks of inorganic coagulants and synthetic
polymers associated with growing environmental concerns worldwide, there is a need to
consider other potential alternatives for textile wastewater treatment in order to minimize
environmental damage and improve the wellbeing of human populations. Therefore,
researchers have shown significantly more interest in the development of natural polymers
as coagulants in recent years [14]. The use of natural coagulants for the clarification of

18
water and wastewater has been recorded throughout human history since ancient times and
it is still current today. Natural organic polymers have been used for more than 2000 years
in India, Africa, and China as effective coagulants and coagulant aids at high water
turbidities

Figure 2. 3 Coagulation/flocculation mechanism of bio-coagulant extract

Natural coagulants can be divided into cationic, anionic or nonionic, and hence are also
termed as polyelectrolytes. Examples of natural cationic polymers are chitosan and cationic
starches, while some examples of anionic polymers are sulfated polysaccharides and
modified lignin sulfonate. Starch and cellulose derivatives are examples of non-ionic
natural polymers [12]. Particles can aggregate and settle out of solution through four basic
mechanisms: double layer compression; sweep flocculation; adsorption and charge
neutralization; and adsorption and inter particle bridging. Natural coagulants generally
exhibit two types of mechanism: adsorption and charge neutralization; and adsorption and
inter particle bridging. Adsorption and charge neutralization can occur when suspended
particles in solution sorb to oppositely charged ions, while inter particle bridging occurs
when polysaccharide chains of coagulants can attach to multiple particles so that particles
are bound to the coagulant and need not contact one another. Based on their origin of
production, natural coagulants can be divided into three categories; plant, microorganism
or animal-based as shown in Figure 2.5.

19
 Tree

Figure 2. 4 Schematic categorization of natural coagulants

Natural coagulants are mostly either polysaccharides or proteins. In many cases, even
though polymers labeled as non-ionic are not necessarily absent of charged inter-actions,
as there may be interactions between the polymer and a solvent within a solution
environment as the polymer may contain partially charged groups including –OH along its
chain. Although many plant-based coagulants have been reported, only four types are
generally well-known within the scientific community, namely, nirmali seeds (Strychnos
potatorum), Moringa Oleifera, tannin and cactus are some of them.

2.6.1. Nirmali seeds

Most studies concerning its use as coagulant seem to be limited within the Indian
subcontinent [14]. Nirmali seed extracts are anionic polyelectrolytes that destabilize
particles in water by means of inter particle bridging [15]. Previous studies [15] have
established that the seed extracts also contain lipids, carbohydrates and alkaloids

20
containing the –COOH and free –OH surface groups which enhance the extracts’
coagulation capability. [16] Report that a mixture of polysaccharide fraction extracted from
S. potatorum seeds contained galactomannan and galactan capable of reducing up to 80%
turbidity of kaolin solution. Although the specific coagulation mechanism associated with
nirmali seed extracts has not been extensively investigated, one can surmise that the
presence of copious amount of –OH groups along chains of galactomannan and galactan
provides weakly but abundant adsorption sites that ultimately lead to the aforesaid
coagulant interparticle bridging effect [16]. Since both ionic ( –COO−H+) and
comparatively non -ionic (galactomannan ) groups or substances are suggested to be
present in the extract, the author deems that its designation as ‘anionic polyelectrolytes’ is
premature, as there are no identified studies that provide detailed elucidation of its
coagulation mechanisms and percentage composition of the extract.

2.6.2. Moringa oleifera

M. oleifera (horseradish or drumstick tree), a non-toxic (at low concentrations) tropical
plant found throughout India, Asia, sub -Saharan Africa and Latin America [17] whose
seeds contain an edible oil and water soluble substance [18], is arguably the most studied
natural coagulant within the environmental scientific community. It is widely
acknowledged as a plant with numerous uses with almost every part of its plant system can
be utilized for beneficial purposes. Moringa is most frequently used as food and medicinal
sources within less -developed communities. A succinct summary of its various uses
afforded by its different plant parts such as leaves, flowers, seeds, roots and bark. It has
been reported that rural communities in African countries utilize its crude seed extracts to
clear turbid river water. The seminal paper by [18] published in year 1995 is the first
literature that comprehensively elucidates the basic coagulation mechanisms inherent in
M. oleifera has applied for turbid water treatment and it essentially sparked widespread
interests among environmental scientific community from then onwards. It is suggested
that its active coagulating agents are dimeric cationic proteins with molecular mass of 12–
14 kDa and isoelectric point (pI) between 10 and 11 and its main coagulation mechanism
is adsorption and charge neutralization.

21
Since then, however, there have been conflicting reports on the exact nature of the active
coagulating agent present in Moringa. In many cases, impurity particles are negatively
charged and cationic polyelectrolytes are the most efficient coagulants, which bodes well
for usage of Moringa as coagulation agent. It is well-established that electrostatic
interaction provides strong adsorption in these systems and that neutralization of the
particle surface and even charge reversal can occur [13]. All these technical factors
ultimately attract the interest of the scientific community to continue on research of using
Moringa to treat a wide spectrum of turbid waters or even industrial wastewaters. Its
coagulating capability can be further enhanced by addition of cations. In a study conducted
by [19], it is established that bivalent cations (e.g. Ca2+ and Mg2+) significantly enhance
the coagulating effect of M.oleifera extracts in which the cations may have adsorbed to the
active components to form insoluble net-like structure to capture suspended kaolin
particles.

2.6.3. Tannin

Tannin is a general name given to large polyphenol compounds obtained from natural
materials, for example, the organic extract from bark and wood [20] of trees such as Acacia,
Castanea, or Schinopsis [21]. It is a polymer with molecular weights ranging from hundreds
to tens of thousands and traditionally used as a tanning agent in the leather industry. There
have been conflicting reports on the effect of tannin on human health and its portrayal in
this negative light may have limited its application as natural coagulant for water treatment.
Nonetheless, such application is still a preferred research area for many researchers. The
tannin used in their study is extracted from valonia, which is obtained from the corn cup of
the oak that grows in Asia Minor [21]. They conclude that tannin is an excellent substitute
to chemical coagulants. The effectiveness of tannin as a natural coagulant for water
treatment is influenced by the chemical structure of tannins that have been extracted from
plant and degree of tannin modification [20]. The presence of phenolic groups in tannin
clearly indicates its anionic nature since it is a good hydrogen donor. Fig. 2.5 illustrates the
schematic representation of basic tannin structure in aqueous solution and possible
molecular interactions that induce coagulation.

22
 Figure 2. 5 Schematic representation of basic tannin structure in aqueous solution and possible
molecular interactions

It is common knowledge that phenolic groups can easily deprotonate to form phenoxide
which is stabilized via resonance. This de protonation is attributed to delocalization of
electrons within the aromatic ring which increases the electron density of the oxygen atom.
This provides an indication that the more phenolic groups are available in a tannin
structure, the more effective its coagulation capability. [20] Suggests that their tannin is
cationic in nature since there is a single tertiary amine group per monomer, giving a charge
density of approximately 3 meq/g. This tannin also exhibits amphoteric nature as a
consequence of presence of phenolic groups.

2.6.4. Cactus
Application of cacti species for water treatment is rather recent compared to other natural
coagulants such as nirmali or M. oleifera. The most commonly studied cactus genus for
water treatment is Opuntia which is colloquially known as ‘nopal’ in Mexico or ‘prickly
pear’ in North America. This cactus type has long been associated with its medicinal
properties and dietary food sources. Besides Opuntia, other cactus species including Cactus
latifaria have also been successfully used as natural coagulants. The high coagulation
capability of Opuntia is most likely attributed to the presence of mucilage which is a
viscous and complex carbohydrate stored in cactus inner and outer pads that has great water
retention capacity [22]. Previous studies have established that mucilage in cactus Opuntia
contains carbohydrates such as l-arabinose, d -galactose, l -rhamnose, d-xylose, and
galacturonic acid [22]. Recently report that galacturonic acid is possibly the active

23
ingredient that affords the coagulation capability of Opuntia spp. though it should be noted
that it only accounts for only 50% of turbidity removal. Nonetheless, this is still a
significant quantum and therefore, this compound deserves further evaluation on its
contribution to the overall coagulation capability of cactus [20]. They suggest that Opuntia
spp. operates predominantly through a bridging -coagulation mechanism where solution
particulates do not directly contact one another but are bound to a polymer-like material
that originates from the cactus species. Relevant dominant molecular interactions
associated with adsorption and bridging in coagulation are shown in Fig. 2.2.

Figure 2. 6 Schematic representation of polygalacturonic acid in aqueous solution and possible

dominant molecular interactions associated with adsorption and bridging

All these studies point to the importance of galacturonic acid which possibly acts as one of
the major active coagulating agents in plants and therefore, deserves further technical
assessment. Though not extensively reported in open literatures, it is highly possible that
galacturonic acid [a major constituent of pectin in plants] exists predominantly in
polymeric form [polygalacturonic acid] [23] that provides a ‘bridge’ for particles to adsorb
on. The polygalacturonic acid structure evidently indicates that it is anionic due to partial
deprotonation of carboxylic functional group in aqueous solution. The existence of such
functional groups along the chain of polygalacturonic acid implies that chemisorption
between charged particles and –COO− may occur although this requires further empirical
substantiation. The presence of –OH groups along its polymeric chain also infers possible
intramolecular interactions which may distort the relative linearity of the chain [23].

24
 2.7. Fruit wastes for coagulation

An overview of different research reports showed that extracts of an array of fruit wastes
had been studied as coagulants in the treatment of turbid synthetic water, raw surface water
and wastewater [24]. These fruit wastes include the seeds of Carica papaya, pumpkin
(cucurbita maxima), Mangifera indica, Tamar indus indica, Moringa oleifera. The
coagulating actions of these fruit wastes were ascribed mainly to the presence of proteins
and polysaccharides, which are among the natural polymers present in fruit waste. The
nomenclature of the particular polysaccharide that is responsible for the coagulating proper
ties of the fruit waste is often not identified or pinpointed. The usually large molecular
weights and longer polymeric chain of polysaccharides are typically regarded as the
impetus for coagulation efficiency since the number of active sites that are available for
particle adsorption, and subsequent flocculation abounds in such skeletal frameworks.

2.7.1. Preparation steps of bio-coagulants

The general processing steps involved in production of plant-based coagulants can be
divided into three major stages, namely, primary, secondary and tertiary (Fig. 3). The
primary processing step is very straightforward and most research studies and domestic
applications utilize only this processing step to simulate the traditional method of drying
and subsequent pulverizing of plant parts into fine powder generally used by local
communities in the absence of sophisticated processing equipment. Nonetheless, an
obvious setback emerges since the prepared powder contains not just the coagulating active
agents, but also plant tissues. The latter is rich in organic constituents and increases organic
loadings in the treated water which may exacerbate the situation further, rather than
improving the treatment efficiency [22].

25
 Figure 2. 7 General processing steps in preparation of plant-based coagulants

This problem can be addressed by processing the powder through secondary (extraction)
and tertiary (purification) stages. This works by extracting their active coagulating agents
and subsequently purifying them to eliminate undesired organics. This may increase their
processing costs and may not be practical as POU water treatment technology.
Nonetheless, extraction of active coagulating agents is still a noteworthy aspect which may
prove useful should they be commercialized or applied in concentrated form for industrial
wastewater treatment. In the secondary processing stage, extraction of the active agents
can be performed via different solvents (organic, water or salt solution), which at first
glance, are rather surprising as they are somewhat dissimilar given their distinct chemical
structures and electrostatic properties. In most cases, different solvents are jointly used at
this stage to extract useful and edible oil [22] and active coagulants in separate sub-steps.
Extraction using water is evidently the most accepted choice due to its abundance and cost
-effectiveness, especially for M. oleifera as its active coagulating agent is water-soluble
protein.

However, extraction using salt solution (NaCl) has been reported by [21] to be superior to
water. They found that by using NaCl solution extraction, the extracted components

26
showed better coagulation activity with dosages 7.4 times lower than components extracted
by distilled water for the removal of kaolinite turbidity. They attributed this enhanced effect
to the salting -in mechanism in proteins wherein a salt increases protein –protein
dissociations and protein solubility as the salt ionic strength increases. Tertiary processing
is rarely done in the case of plant-based coagulants and is presently restricted to academic
research on purification of M. oleifera extracts [20] since it apparently increases the overall
processing cost. Preliminary studies suggest that lyophilization, ion-exchange and dialysis
[18] are feasible purification methods for M. oleifera extracts which can be incorporated
into a scaled-up setup for treatment of higher throughput of turbid water. Such methods
have not been extensively applied to other plant-based coagulants and this presents
opportunities for other research.

2.8. Factors affecting coagulation processes

The effectiveness of the coagulation is influence by factors such as wastewater type,

initial turbidity, temperature, physical and chemical characteristics of coagulant, pH of
the solution, the type and dosage of coagulants/flocculent, mixing speed and time,
settling time and etc. The review of literatures is limited on coagulant dose, pH and
mixing time since these are variables on coagulation experiment in this study. The
coagulant dose is one of the most important parameter that has been considered to
determine the optimum condition for the performance of coagulants in coagulation -
flocculation process [27]. Essentially, insufficient dosage or overdosing would result in the
poor performance in process. There is a range of optimum doses for a coagulant at
which maximum settling and removal of pollutants is most effectively achieved. Below
this range, the amount of coagulant added is inadequately to destabilize the particles.
Above this range, the coagulant essentially serves as a chemical coating which re -stabilizes
the particle [28]. Therefore, it is significant to determine the optimum dose in order to
minimize the dosing cost and sludge formation and also to obtain the optimum
performance in treatment process. Since the range coagulant dose varies with the type
of coagulant, the dose pumpkin seed extract was studied under this research. The pH is
also the second important parameter that has been considered to determine the optimum
condition for the performance of treatment [29]. In coagulation process pH could not

27
only affect the surface charge of coagulants, but also the degree of stabilization of the
suspension. Besides, pH seems an interesting variable which has a greater influence
on the pollutants removal efficiency . Therefore, effect of pH was one of the parameters
was crucial to determine the optimum level in order to minimize the sludge formation
and obtain the optimum performance in treatment. Thus, pH must be controlled, by
adding either strong acid or base, to establish optimum condition for coagulation process.

In addition to coagulant dose and pH, the effect of mixing time also play an important
role on flocs formation and growth in coagulation-flocculation process [30]. The time
of macro floc formation (flocculation time) is one of the operating parameters that is
given great consideration in any water and wastewater treatment plant that involves
coagulation [31]. Therefore, it is important to determine the optimum mixing time for the
treatment system. There are typically three phases of mixing in a coagulation process:
rapid mix, slow mix , and no mix . The rapid mixing phase is a short period of extremely
turbulent mixing that allows coagulants contact with suspended particles [32]. The next
phase is flocculation time. It is characterized by slow mixing and allows destabilized
particles to agglomerate together into larger particles. This mixing period is important for
floc formation. Flocs are highly fragile, so sudden movements lead to floc breakage and
therefore to a loss of effectiveness. The final phase consists of no mixing. It allows
flocculated particles to settle out of the system. Insufficient periods of slow mixing result
in poor agglomeration of particles. Prolonged agitation periods, however, lead to
ruptures in floc fragments and dis agglomeration of particles.

In general, optimization of coagulant dose, mixing time and pH is significantly

increases the effectiveness and efficiency of coagulation so that it is recommended to
take in to consideration. Actually, in this study these three determinant factors are
examined.

2.9. Treatment of textile waste water using bio-coagulants

Many natural coagulants may be inappropriate for treatment of industrial wastewaters due
to their low availability for large-scale treatment and the extreme conditions (pH and
concentration) of the wastewaters but usage of natural polymeric coagulants may afford

28
benefits that can somewhat offset its disadvantages. Other than the evident sustainable and
environmental -friendly aspects, natural polymeric coagulants also form stronger flocs via
bridging effect with higher resistance to shear forces in a turbulent flow compared to non-
polymeric coagulants such as alum [13]. This implies that natural coagulants can be utilized
within a batch stirred tank setup to treat contaminated industrial wastewaters, at least in a
mechanical sense, since bridging linkages are more resistant to breakage at high shear
levels. An underlying observation regarding these studies is that the stronger the flocs, the
larger they can grow under given shear conditions. So far, identified usage of natural
coagulants for industrial wastewater has been limited to academic research.

Many findings from these academic studies, however, indicate their good potential for
industrial wastewater treatment [13] and [21]. In many cases, the natural coagulants can
perform at their best when used for treatment of wastewaters with less variety of
contaminants. Besides dyeing effluent, there are several studies conducted to evaluate the
technical viability of using plant based coagulants for other types of industrial wastewater,
though their research aims are rather divergent. It appears that many of these coagulants
are quite uncommon and represent new varieties of plant-based active coagulant extract
besides the afforested established plant coagulants. It should be noted that there is scarcity
of comprehensive studies that compare the effectiveness of these natural coagulants with
that of chemical coagulants and this may be one of the factors that inhibit their potential
for industrial wastewater application.

2.9.1. Advantages of natural coagulants

Organic polymeric compounds have advantages over inorganic materials, as they possess
several novel characteristics such as their ability to produce large, dense, compact flocs
that are stronger and have good settling characteristics. Natural polymers may potentially
be applied not only in food and fermentation processes, and in downstream processing, and
they can be applied in textile wastewater treatment [26]. The advantages of using plant-
based coagulants in place of inorganic coagulants and/or organic polymers include lower
coagulant dose requirements, smaller increases in the ionic load of the treated wastewater,
and reduced levels of metals in the treated wastewater. Due to their low toxicological risk
(generally free of toxicity) and high biodegradability, they are safe to human health and

29
aquatic life, consequently having a smaller environmental impact. One obvious advantage
of using renewable materials is their minimal net effect on global warming. Figure 2.5
summarizes the benefits of using natural coagulants as an alternative to chemical
coagulants.

Figure 2. 8 Advantages of natural coagulants over chemical coagulants

2.9.2. Pumpkin seed

Pumpkin is an important horticultural crop that belongs to the family Cucurbitaceae. It is

comprised of five domesti-cated species: Cucurbita moschata Duchesne ex Poiret, C. pepo
L., C. maxima Duchesne, C. mixta pangalo, and C. micifolia. Three of these, C. moschata
C. pepo and C. ma-xima represent economically important varieties cultivated worldwide
and with high production. In Ethiopia C. ma-xima cultivated almost every part of the
country with high production. The proximate analyses of precursors were summarized in
Table 2.1. The moisture contents show the ability of coagulants to absorb water and
consequently, enhance surface adsorption of the particles. The high crude protein value of

30
55.09 % indicates the presence of protein, which is in agreement with the literature that
the protein contents of the coagulant are cationic polypeptides (long chains of amino
acids held together by peptide bonds) [35]. Fibre contents present established that the
precursors were of an organic polymer with repeating small molecules that could
extend as tails and loops when dispersed in water. The particle attachment on the
extended tails enhances particle adsorption because there are more surface sites available.
The proximate results justify the use of these seed powders as a potential source of
coagulant in this work.

Table 2. 2 Proximate composition determination of the coagulant [35]

No. Parameters Values

pumpkin seed
1 Yield 38.4
2 Bulk density (g/ml) 0.354
3 Moisture Content (%) 12.58
4 Ash content (%) 1.52
5 Protein content (%) 55.09
6 Fat content (%) 17.17
7 Fibre content (%) 0.87
8 Carbohydrate (%) 12.77

2.10. Textile waste water disposal standards

While there are many technologies available in treating the textile wastewater, a majority
of them are relatively expensive to be applied by the small and mid-size industries.
Furthermore, many of the physico-chemical technologies only transform the pollutants
from one form or one phase to another and therefore do not provide any ultimate solution
to the problem. Several environment protection agencies worldwide have imposed rules
entrusted with the protection of human health and guarding the environment from pollution
caused by the textile industry. These agencies imposed certain limits on the disposal of

31
effluents into the environment. The disposal limits are found to differ from country to
country. However, a constant check is to be kept on these discharge limits every now and
then to maintain a safe and a healthy environment. It is urgently required that industries
should continuously monitor textile effluents and take necessary actions to properly treat
the wastewater prior their disposal to water bodies and save already depleting natural water
resources. The EPA emission limits for textile industry describe in appendix 1.

2.10.1. Environmental legislation

With respect to legislation, there is as yet no international consensus concerning
discharging textile effluent, including Azo dyes, and there is no official document listing
the different effluent limit values applied in different countries. Many developed countries,
such as the United States of America, Canada, Australia and the nations of the EU enforce
environmental legislation, which establishes limits. Countries, such as Thailand, have
copied the US system, whereas others, such as Turkey and Morocco, have copied the EU
model. In other nations, including India, Pakistan and Malaysia, the effluent contamination
limits are recommended, not mandatory. In the majority of cases, Azo dye limitations are
not specified as separate from that of groupings such as „total dissolved solid‟
concentration.

In nations such as China, with environmental management enhanced, pollution has been
controlled to some degree. 90% of wastewater from state-owned Chinese dyeing
enterprises is treated, 70% of which reaching national discharge standards, while 50% from
private enterprises is treated, only a small proportion of it reaching national discharge
standards because of inadequate management. Moreover, with the growth of the global
textile market, the volumes of water that need management have seen dramatic increases,
most significantly by 87.74% between 1985 and 1995 , and so the release of Azo dye into
the environment in real terms cannot be said to be improving. In Ethiopia there is
governmental environmental watching dog known as Ethiopian environmental, Forest and
climate change commission.

32
 2.11. Literature summary

The knowledge and scientific research in pollutants removal of wastewater are of utmost
importance in order to respond to environmental needs. To meet the increased more and
more stringent environmental laws, many different technologies of wastewater treatment
have been developed for removal of suspended and dissolved organic matter from textile
wastewater. It is evident from a review of current literature that coagulation/flocculation
process has been widely used to remove organic matter and color from textile wastewater.
The usage of natural coagulants derived from plant-based sources as an alternative to usage
of chemical coagulants represents a great development in sustainable environmental
technology since it focuses on the improvement of quality of environmental and human
health without losing industrial process efficiency. In technical terms, these natural
coagulants are highly efficient for reduction of physical-chemical parameters of the
wastewater such as color, turbidity, COD, TOC, BOD, TSS and others.

Planted-based coagulants also have several reasons to become effective coagulant; high
cationic charge density, long polymer chains, bridging of aggregates and precipitation,
safe, eco-friendly, non-toxic, non-corrosive, high biodegradability, reducing sludge
volume, increasing floc size, allowing the reduction of production costs since using raw
material from renewable resources. Many researchers have tried to focus on the efficiency
of bio-coagulants extract as a coagulant powder on physical factors and quality of water to
the reduction of water turbidity, color, total dissolved solids and organic matters. Several
studies were concentrated on the development and improvement of the characteristics of
the bio-coagulants like Moringa, cactus, chitosan, and tannin to enhance the coagulant
ability to removal water and waste water effluents. However, lack of studies has been
directed towards the characterization of the active component in pumpkin seeds extracted
with solvent using soxhlet. Moreover, in this paper the extracted seed cake were used as a
coagulant for textile waste water treatment.

33
 3. MATERIALS AND METHODS
3.1. Materials and chemicals

3.1.1. Materials
The materials used throughout the experiments to achieve the objective of the study
were: Jar test apparatus (VELP ) to determine optimum dose of coagulant,
Spectrophotometer (Jenway 6300 England) for measuring decolorization, soxhlet
equipment for de- oiling of the seed, COD analyzer, S.D. oven (model : memmer ) for
drying, disk Milling machine to make seeds in to powder, measuring cylinder, beakers,
magnetic stirrer, electronic weighing balance, Sieves (250-500 micron size), filter
paper, pH meter (Janway, model 3510), and HACH turbid meter were used during the
experiment work. All of these materials were obtained from KTSC and BiT Environmental
engineering laboratory.

3.1.2. Chemicals
The chemicals used during experimental work were commercially available laboratory
graded chemicals (H2SO4 and NaOH solution) stock solution concentration are used to
adjust pH during the experiment, Solvent (ethanol) for extraction, dried and crushed
pumpkin seed, NANO COLOR C SB 1500 as COD reagent. All of these chemicals has
been obtained from KIoT and KTSC laboratory.

3.2. Methods

The general experimental methodology to carry out this investigation are described as in
the following sub -titles.

3.2.1. Pumpkin seed collection and preparation

Pumpkin fruit was purchased from Kombolcha market and undergo various processing
in the course of its preparation for extraction. Pumpkin fruit shells were carefully cut
open to expose the seeds which were embedded in an orange–yellow fibrous material.
Figure 3.1 shows Maturity level of pumpkin seed(A), hulled pumpkin seed(B),

34
grinding(C), sieve analysis 2mm(D), sieved pumpkin seed before oil extraction(E) and
Pumpkin seed cake after oil extraction(F) respectively.

A) B)

C) D)
35
The seeds were removed from the fruit and thoroughly washed with distilled water to
remove other component of pumpkin and impurities. After that Pumpkin seeds was cleaned
manually in order to remove foreign material and impurities and then dulled manually to
remove the outer seed coat and subsequently dried in an electric oven at 500C until a
constant weight was obtained.

E) F)

Figure 3. 1 Coagulant preparation processes

3.2.2. Textile wastewater collection

In this study the sample of wastewater were collected from KTSC textile industry.
Wastewater samples were collected, by using Grab sampling technique, from the inlet
of the treatment plant. Plastic containers were used for sample collection after cleaned with
detergent, and rinsed with deionised water. After sample collection and it was transported
in to KIoT laboratory and preserved in a refrigerator at 4°C in order to minimize the
chance of their characteristics changes until used for experiment. Then, some
physiochemical characteristics of the waste water before treatment like total dissolved
solid, COD, BOD, suspended solid, turbidity and initial colour was studied. These are
measured according standard methods for the examination of water and wastewater.
Methods - 2130 -B, 2540-C, 2540-D, 5210-B, 5220-D, 2120-B were used for the
measurement of turbidity, TSS, TDS, COD, BOD and colour. PH was measured using
digital pH meter (Janway, model 3510)

36
 3.2.3. Characterization of the coagulant and waste water

Yield, bulk density, moisture content, ash content, protein content, fat content,
carbohydrate content and fibre content of the seed powders were determined by the
standard official methods of analysis of the A.O.A.C [33]. Wastewater sample was
taken corresponding to the washing process that is performed after textile dyeing. The
wastewater sample was collected directly from the discharge pipe with the sampler. Thus,
an initial experiment were carried out to determine the Physico-chemical parameters of
Kombolcha textile wastewater in term of parameters namely COD, TSS, TDS, Color, TS,
turbidity and pH; then, the samples were stored in plastic bottles. This experiment was
conducted based on procedures which are provided under standard methods for the
examination of water and wastewater.

3.3. Coagulant extraction

3.3.1. Soxhlet extraction

Experimental works were conducted using soxhlet equipment by solvent extraction
process. The solvent used during extraction was ethanol. The result from soxhlet extraction
like extraction time, particle size and pumpkin seed meal to solvent ratio was used as the
starting parameter: Initially the raw material pumpkin seed was prepared and cleaned well
and then dried in order to remove the moisture contents. After the moisture is removed the
pumpkin seeds were grinded and sieve in order to get good surface area or particle size and
dried well again in order to get high yield. The grounded pumpkin seed samples were
placed in a filter paper. The filter paper was placed in an extraction chamber which is
being suspended above a flask containing the solvent and below a condenser.

Heat is being applied to the flask and the solvent evaporates and moves to the condenser
where it is converted into liquid that trickles in to the extraction chamber containing the
sample. The extraction chamber was made in such a way that when the solvent
surrounding the sample exceeds a certain level it overflows and trickles back down
in to the boiling flask. Finally, the oil and solvent were separated through rotary
evaporator (simple distillation) at the end of the extraction process. Finally, the defatted

37
seed (oil removed seed) were used as a coagulant. Figure: 3.2 shows soxhlet extraction set
up.

Tumble Pumpkin seed

Soxhlet
Condenser extractor

Round
bottom flask Ethanol

Simple
distillation

Stove (80oc)
Oil

Figure 3. 2 Soxhlet extraction set up and ethanol and oil from soxhlet respectively

3.3.2. Experimental studies

The experimental design follows One-factor-at-a-time (OFAT) approach. OFAT is a

prevalent type of experimentation commonly used by many engineers and scientists in both
industry and academia. Tests are conducted by systematically changing the levels of one
factor while holding the levels of all other factors fixed. The “optimal” level of the first
factor is then selected. Subsequently, each factor in turn is varied and its “optimal” level
selected while the other factors are held fixed. The experiments are regarded as easier to
implement, more easily understood, and more economical than factorial experiments.

38
Better than trial and error. OFAT experiments are believed to provide the optimum
combinations of the factor levels.

3.4. Jar test

The jar test – a laboratory procedure to determine the optimum pH, mixing time and the
optimum coagulant dose.

Figure 3. 3 Jar test apparatus set up

A jar test simulates the coagulation and flocculation processes. It is the most widely used
experimental method for evaluating and optimizing coagulation-flocculation processes
based on standard methods. Similarly this research has used the jar test apparatus consists
of the batch test, accommodating a series of six beakers together with six-spindle steel
paddles. Before operating the jar test the wastewater samples were mixed homogenously.
The jar test experimental studies were carried out in three steps. In each of the steps, 500
ml of textile wastewater was poured into each beaker labelled from 1-6.

The first run, in which the coagulant dose varies while the mixing time was kept
constant to determine the optimum coagulant dose. Here the experimental factor was

39
coagulant dose ranging between 4 -12 g/l. The removal efficiency of coagulate dose
was determined based on removed amount of color, turbidity and COD.

In the second run, Optimum mixing time was investigated by providing optimum dose
determined from the first phase. In this case the experimental factor was mixing time
which ranges from 30-60 minutes and evaluated based on the removal efficiency of color,
turbidity and COD. Then, Plot residual (turbidity, colour and COD) against mixing time.
Hence, the time with the lowest residual (turbidity, colour and COD) will be the optimum
mixing time.

In the thrid run, optimum pH for the treatment was determined using the optimum dose
and mixing time taken from the previous phases. This study was carried out using pH
value range of 5 – 9. In each case, the desired pH value of the wastewater was adjusted by
using 1 M H2SO4 and NaOH. Then added coagulant (pumpkin seed cake) to each jar
(Coagulant dose obtained from first phase). Then mix (at optimum mixing time obtained
from seconed phase) each jar to disperse the coagulant throughout each container. Then
reduce the stirring speed and continue mixing to promote floc formation by enhancing
particle collisions, which lead to larger flocs. Finally, turn off the mixers and allows flocs
to settle. Finally, measure the final residual turbidity in each jar. Then, Plot residual
(turbidity, colour and COD) against pH. Hence, the pH with the lowest residual (turbidity,
colour and COD) will be the optimum PH.

In the last step, The coagulant dose vary between 4-12g/L while the pH and mixing
time maintained constant at the optimum value which were taken from second and
third phase was used to determine the optimum dose. For all phases the optimum value
was picking depending on the highest removal efficiency of color, turbidity and COD.
Then measure the final residual turbidity in each jar. Finally, Plot residual turbidity against
coagulant dose. The coagulant dose with the lowest residual turbidity, colour and COD will
be the optimum coagulant dose.

40
 3.5. Data analysis

The data collected from the above experiment are analysis using Microsoft Excel
program. The results are presented using tables and graphs. The percentage removal
efficiency of the parameters was calculated using following formula calculated using the
following formula:

(Co−C)
Colour removal Efficiency: (% Removal) = ∗ 100………….1
Co

Where, Co = initial concentrations (before treatment) and

C = final concentrations (after treatment)

𝑇2−𝑇1
Turbidity Removal Efficiency: (% Reduction) = ∗ 100……….…2
𝑇2

Where, T1 = final turbidity

T2 = initial turbidity

41
 4. RESULTS AND DISCUSSION
4.1. Characterization of coagulant and waste water
4.1.1. FTIR analysis of coagulant

FTIR analysis was made in order to determine the functional groups involved in the
coagulation process. The spectra of pumpkin seed extract were shown in figure 4.1. One
could find that the most significant peaks were in the regions of, 2922.90, 2853, 1743.90,
1641, 1460 and 1158 cm-1 for the seed powder. The spectrum show the peaks typical
for hydroxyl groups at the range 2850-2930cm-1, confirming the presence of the free
hydroxyl groups of carboxylic acids, alcohols and phenols on the coagulant surface.

Figure 4. 1 FTIR analysis of Pumpkin seed before extract

42
FT-IR spectra for pumpkin seeds which verify the presence of many functional groups,
indicating the complex nature of this material. The peaks present at 2922.90 cm-1 and
2853.40 cm-1, respectively, correspond to asymmetric and symmetric stretching of the C-
H bond of the CH2 group. Due to the high intensity of these bands, high content of protein
and the predominantly lipid component of the seed, which is present in stretching of OH
bonds present in: proteins, fatty acids, carbohydrates and lignin units and N-H stretching
of the amide bond. Due to the heterogeneous nature of the seed, the carbonyl group may
be bonded to different neighborhoods as part of the fatty acids of the lipid portion or amides
of the protein portion. The carbonyl component that appears due to the presence of lipids
can be seen at 1743.90 and 1641.79 cm-1. In the region of 1743.90-1168.04 cm-1 a number
of overlapping peaks are observed and between 1743.90 and 1641.79 cm-1 this can be
attributed to C=O stretching. As can be observed in the infrared spectra as small peaks, and
the shoulders forming part of the main band that appears at 1641.79 cm-1 are attributed to
the carbonyl amides present in the protein portion. The peak observed at 1460.05 cm-1
may be attributed to stretching connecting CN and also the deformation of the N-H bond
present in the proteins of seeds.

Figure 4. 2 FTIR analysis of Pumpkin seed after extract

43
FT-IR spectra analysis of pumpkin seed extract verify that the dominant peak at 2922.90
cm-1 attributed to O-H stretching vibrations in hydroxyl groups. A shift in hydroxide group
from 2922.90 cm-1 to 2923.58 cm-1 ( 68%T to 92.67%T), alcohol group from 1743.90
cm-1 to 1742.69 cm-1 ( 67.69%T to 94.70%T), while a shift in carbonate group from
1480.06 cm-1to 1464.2 cm-1 ( 84.87%T to 96.69%T), shifting in peaks was observed after
extraction and this shows that all dominant functional groups were completely involved in
coagulation process and many least dominant bands, natural organic matters , oils, fats,
residuals and over lapping peaks were removed during extraction of seed through solvent
extraction.

Therefore, from FTIR spectra result, we can conclude that pumpkin seed extract contains
many complex protein, amine, phenolic groups and possible molecular interactions that
elucidate coagulation potential. It is well known that solubility of proteins increase with oil
and in active components (natural organic matter) removed while extraction of the
coagulant using solvent. Since the active component for coagulation in pumpkin seed is
protein, it is probable to increase its solubility by increasing its ionic strength. The increase
in solubility of the active component will improve coagulation efficiency. Hence, hydroxyl
and amino groups present in the functional group of the seed enhance decolourization.

Figure 4. 3 FTIR analysis of Pumpkin seed before and after extract

44
 4.2. Characteristics of textile waste water

The experiment undertaken to examine the initial character of the textile wastewater
sample demonstrate the following result. Accordingly, the collected samples had a red
and dark blue color and the measurement result was 2300 Pt -Co. The pH of the effluent
was found pH 11.2. This indicated that the effluent from the textile industry is more
alkaline due to the use of high amount of salt as exhaustion agent in dyeing. The
measurement as to total dissolved solids and total suspended solids were 3200 mg/l and
1700 mg/l, respectively. Besides, the experiment was confirmed that the particles of
TDS are higher than TSS in the textile waste water sample. Furthermore, the
experimental result of wastewater sample show 7500 mg/l of total solids. Finally, COD
and BOD values were 1200 mg/l and 240 mg/l respectively. In other words textile
wastewater contain high amount of non-biodegradable, 3 to 4 times, than degradable
organic matters. The preliminary characters of textile wastewater sample were summarized
in table 4.1.

Table 4. 1 The physicochemical characteristics of collected raw waste water from Kombolcha
textile industry.

No. Parameters measured Unit Textile waste water value

1 pH - 11.2
2 Turbidity NTU 210
3 Suspended solid mg/l 1700
4 Total dissolved solid mg/l 3200
5 Chemical oxygen demand (COD) mg/l 1200

6 Biological oxygen demand (BOD) mg/l 240mg/l

7 Color Pt -Co 2300

This implies that the waste water is highly polluted and needs treatment. These values are
above Textile wastewater limit Values for discharges to Water bodies according to EPA
2003, so such high concentration of pollutant of the textile waste water will have great
environmental impact.

45
 4.3. Factors affecting coagulation process

The effects of coagulant dose, pH, and mixing time are important factors in order to
investigate the performance of pumpkin seed extract on coagulation process. The color,
COD and turbidity level in textile wastewater are considered as the most important
parameter to measure the pollution strength of textile wastewater, which can be used as
the indicator on the coagulant capacity of pumpkin seed in these experiments.

4.3.1. Effect of coagulant dose

The dosage of the coagulant used on a coagulation process has been established to be one
of the most important factors having influence on the mechanism of coagulation. The
observations were made experimentally and the result was as follows:

Table 4. 2 Percentage removal of color, COD and turbidity at various coagulant doses.

Coagulant Color Color Turbidity Turbidity COD COD

dose (g/l) concentration removal concentra removal concentr remo
(pt-co) (%) tion (%) ation val
(NTU) (%) (%)
Initial 2300 - 210 - 1200 -
value
4 506 78 53.34 74.6 592 50.67
8 184 92 21 90 210 82.5
12 239.2 89.6 28.35 86.5 372 69

The results were presented in the above Figure shows the effects of the coagulant dose on
percentage reduction of color, COD and turbidity by using pumpkin seed extract as
coagulant for textile wastewater treatment. In addition to discussing the optimum value
and the percentage performance of treatment is important to explain other results
which were observed during the experiment.

46
The result illustrated above indicates that with an increase of coagulant dosages, the
removal efficiencies increased and maximum colour removal efficiency was achieved at
coagulant dosages of 8 (g/l) with color removal efficiency of 92% followed by turbidity
reduction with efficiency of 90% and COD removal efficiency 82.5%. Here, we can
understand from the table with an increase of coagulant dosages, the removal efficiency
steadily reaches maximum and decreased after optimum coagulant dose. Essentially,
insufficient dosage or overdosing would result in the poor performance. Thus, optimum
doses for coagulation at which maximum settling and removal of pollutants is most
effectively achieved. Below this range, the amount of coagulant added is inadequately
to destabilize the particles and above this range, the coagulant essentially serves as a
chemical coating which re -stabilizes the particle [28].

Therefore, it is significant to determine the optimum dose in order to minimize the dosing
cost and sludge formation and also to obtain the optimum performance in treatment
process. The higher removal could be due to the charge neutralization coagulation
mechanism, which is inclined to occur at high dosages. The coagulant apparently served
as condensation nuclei and the dye particles were neutralized as the precipitate was settled.
The high dosages up to optimum dose of the organic polymer could also give rise to chain
bridging and adsorption mechanism. Furthermore it was found that by increasing the
amount of the coagulant dose the adsorption increases. The increase in the dye adsorption
was due to the increased in availability of dye binding sites resulting from an increase in
coagulant dosage. Higher dose of the media (greater than 8 g/L) would increase the amount
of sludge and decrease color, turbidity and COD removal. The decrease in residual dye
concentration was most significant when the amount of media is increased from dose of
8g/l to 12 g/l, accordingly, the initial colored textile wastewater sample was changed in to
colorless after adding different doses of the coagulant.

47
 100
90
80
70
% Removal

60
50
40
30
20
10
0
4 8 12
Cagulant dose (g/l)

% Color reduction % Turbidity reduction % COD reduction

Figure 4. 4 Effect of coagulant dose on % removal of color, COD and turbidity

This confirms that pumpkin seed extract have coagulant properties and effective for
removal of color. With regard to turbidity, initially it was 210 NTU and after the
coagulation experiment it becomes 21 NTU and initial COD were 1200 g/l and after
coagulation it becomes 210 which is greater than 80% removal efficiency as per the limit
of EPA, 2003. This is good evidence on the effectiveness of pumpkin seed extract for
decreasing COD of textile wastewater effluent. This result is also match with reports made
by other researchers [25] and [31] proved that the potential of pumpkin seed extract to
remove 80 - 93% turbidity. In general, the overall results of the coagulation experiment
under this research proved that the seed extract have an effective coagulant to remove
the turbidity, COD and color from textile wastewater.

4.3.2. Effect of pH

Jar tests were carried out in order to establish a practical understanding of the coagulation
performance and to find optimum pH, time and coagulant dosage. In coagulation process,
pH has been found to be very important since it (coagulation) occurs within a specific pH

48
range for each coagulant, and the influence of pH on the removal of suspended solids,
turbidity and colour is important in coagulation process [18]. In considering the influence
of pH, a range between 5 and 9 was selected, and the results obtained from the experiments
carried out on the effect of pH on turbidity, color and COD removal efficiency when
pumpkin seed extract were used as the coagulant presented in Table 4.5. As can be seen
from the table, to determine the optimum pH value for the process, it was varied while all
the other parameters were held constant. According to the results given in the table below
when pH was increased from 5 to 9, color, turbidity and COD removal efficiency was
found to decrease from approximately 85.2% to 45.9%, 84.76% to 40.52% and 82.1% to
54% respectively. As can be observed from the results given in Table 4.5, the higher the
pH value, the lower the color, turbidity and COD removal efficiency of the coagulant. It
was found clearly from the results that the optimum pH for the process was established to
be 5. The information obtained from a previous research showed that the optimum pH of
turbidity removal was at acidic pH range [21].

Table 4. 3 Percentage removal of color, COD and turbidity at different pH

PH Color Color Turbidity Turbidity COD COD

Concentra removal concentrat removal concent removal
tion (%) ion (%) ration (%)
(pt-co) (NTU) (g/l)
Initial 2300 - 210 - 1200 -
value
5 340.5 85.2 32 84.76 215 82.1
7 890.5 61.3 76.5 63.57 437.6 63.5
9 1252.5 45.5 124.9 40.52 552 54

In acidic medium, the oxide surface of coagulant develops a net positive charge. This in
turn renders a strong electrostatic attraction towards anionic dyes ( reactive dyes
currently used in KTSC) than in basic medium. At lower pH, the –NH– groups of the
dye are protonated and the positive charge develops on the dye molecule. However,

49
reactive dye is an ionic dye with NaSO3- - groups that contribute for its solubility in aqueous
solution. The pH value of the solution would determine the surface charge of the
coagulant which affects the interaction between the dye and coagulant. The pH of the
system exerts profound influence on the adsorptive uptake of dye molecules most probably
due to its influence on the surface properties of the coagulant and ionization or dissociation
of the dye molecule.

Fig. 4.5, shows the variations in the percentage removal of the color from textile
wastewater at different pH using pumpkin seed extract. From the Figure, it is evident
that, percentage removal of color significantly decreased from 85.2% to 45.5 % as the
pH increases from 5 to 9. This indicates that acidic pH is favorable for the dye adsorption
by the coagulant. This is due to the fact that low pH value leads to an increase in H+ ion
concentration in the system and the surface of coagulant may acquires positive charge by
absorbing H+ ions. As the seed extract is positively charged at low pH value, a strong
electrostatic attraction appears between the negatively charged anionic dye and the
pumpkin seed extract leads to maximum coagulation by charge neutralization. On the other
hand, increase in pH value led to increase in the number of negatively charged sites on the
coagulant. The negatively charged surface on seed extract doesn’t favor the coagulation of
anionic dyes due to electrostatic repulsion appears between the negatively charged
anionic dye molecules and the coagulant surface leads to minimum adsorption of the
dye. Based on the result high dye removal efficiency of 85.2% was achieved at pH 5. Thus,
PH plays an important role in the coagulation-flocculation process because it must be
controlled in order to establish optimum conditions for coagulation-flocculation. It was
observed that colour removal efficiency increased in acidic pH. Charge on the hydrolysis
products and precipitation of coagulant hydroxides are both controlled by pH variations.
As the functional groups of the reactive dyes are anionic, hydrolyses products of the
organic biopolymer can neutralize the negative charges on dye molecules in wastewater

50
followed by pumpkin seed extract coagulation. The effectiveness of the coagulant in colour
removal from textile wastewater is highly dependent on pH as shown in figure 4.5.

90
80
70
60
50
% Removal

40
30
20
10
0
5 7 9
PH
% Color reduction % Turbidity reduction % COD reduction

Figure 4. 5 Effect of pH on color, COD and turbidity percentage removal

At high pH values which yielded low efficiencies for the colour, turbidty and COD
removal. There is a competition between OH- and organic anions contaminants for
polymer hydrolysis products. Coagulation of the natural organic contaminants (NOC)
or NOC-polymer contaminant complexes onto polymer hydroxide precipitate forming
at high pH is also limited. As pH increases, natural organic compounds become
more negatively charged and polymer hydrolysis species become less positively
charged, resulting in less coagulation tendency. For these reasons, coagulation-
flocculation of NOC in wastewater is mainly performed under low pH conditions
along with the presence of soluble cationic polymer hydrolysis species.

51
 4.3.3. Effect of mixing time

The mixing time used on a coagulation process is as important as other parameters (pH and
coagulant dose) considered because it has been established to be one of the most important
factors having influence on the mechanism of coagulation. The effect of mixing time on
removal of color, COD and turbidity was tested at 8 g/l coagulant dose and at pH 5. The
following table and figure summarized the experimental results of mixing time. The
experimental result shows that there was a continuous removal of color, turbidity and
COD while increasing the mixing time from 30 to 45 minutes. When the mixing time is
low (30 min.), the collisions between the coagulants and colloids are not efficient to
precipitate suspended solids in wastewater. On the other hand, if mixing time longer
(60 min.) it would lead to an increase in flocs break age & limit the size of the floc
formed. As a result, small size flocs which are not dense to settle down & finally
cause the sample to be turbid again.

Table 4. 4 Percentage removal of color and turbidity at different mixing time

Mixing Color Color Turbidity Turbidity COD COD

time concentra removal concentrat removal concentrati removal
(min) tion (%) ion (%) on (g/l) (%)
(pt-co) (NTU)
Initial 2300 - 210 - 1200 -
value
30 894 61.1 89.25 57.5 617.6 48.5
45 276.5 87.9 37.8 82 223.5 81.37
60 579.6 74.8 69.3 67 472 60.67

Flocs formation involve both interactions of coagulant hydroxide precipitate following

hydrolyses reaction and contact with particles. Coagulation-flocculation performance is
usually evaluated through time-dependent decrease in particle concentration. This decrease
in the concentration of particles coincides with the growth of aggregates. The longer
coagulation-flocculation time (30-60min.) in this process is also a confirmation of
presence of coagulation mechanism. The reduction in concentration did not vary

52
significantly after 45min. from the initial stage. This shows that equilibrium can be
assumed to have been achieved after 45min. Destabilization of the aggregate flocs could
set in after this time. This was basically due to saturation of the active sites which does
not allow further polymer adsorption and also prolonged settling time. In sum, it was
also found that the longer or shorter mixing time would result in the poor performance
of the coagulant for binding and bridging. There were similar results in experiments
made by the researchers [12].

100
90
80
70
% Removal

60
50
40
30
20
10
0
30 45 60
Mixing time (min.)
% Color reduction % Turbidity reduction % COD reduction

Figure 4. 6 Effect of mixing time on color and turbidity percentage removal

There is consistent percentage increment of removal was revealed with increasing mixing
time up to 45 minutes, and it decreases after 45. The results obtained indicated that,
decolourization efficiency of textile wastewater reaches maximum at 45 min. Therefore,
the optimum flocculation time is attained at 45 minute. This result also proximately
matched with other study conducted to treat textile wastewater using natural coagulant
[31]. There is highest removal percentage of color, turbidity and COD, 87.9 %, 82% and
81.37% respectively, at the optimum mixing time. Thus, the removal percentage of
pumpkin seed extract to remove color, turbidity and COD form textile wastewater was
influence by mixing time. And it is a great importance to optimize the mixing time so as
to increase removal performance of the coagulation.

53
 4.4. Optimization Analysis

The optimum condition for removal of colour, turbidity, and COD using pumpkin seed
extract as a coagulant in coagulation process were at 5, 8g/l, and 45 minute for pH,
coagulant dose, and mixing time, respectively. The results of these are summarized under
the following figure below.

8
7
6
5
4
PH

3
2
1
0
4 8 12
Coagulant dose (g/l)
pH

Figure 4. 7 The response pH at different coagulant doses

It was also found important to examine the relationship between coagulant dose and
pH from the coagulation experiment. And consequently the result of the experiment
observed that unlike chemical coagulants pumpkin seed extract did not have significant
effect on the pH of treated textile wastewater. Besides, pH scale of the treated
wastewater has fulfilled the permissive limit standard which set by EPA of Ethiopia.
Thus, there is no need of pH adjustment for treated textile wastewater after coagulation
using pumpkin seed extract. This in turn avoids additional cost which is commonly
incurred to adjust pH while using the chemical coagulant. The relationship between pH

54
and coagulant doses were presented above in Fig. 4.8. Besides, textile wastewater emission
limit standard of Ethiopia Therefore, these optimum experimental conditions are needed to
achieve the best performance of the pumpkin seed. Since there is no clear standard which
are set for color and turbidity it made difficult to compare the result of the experiment. The
following pictures shows different stages and results of the decoloration of textile waste
water before and after treatment.

a) Waste water sample before treatment

b) Waste water samples after decolorization through coagulation

Figure 4. 8 Wastewater samples & results of coagulation at optimum factors

55
Table 4. 5 Comparisons between treatment result with national discharge standard

No. Parameters Before After (%) removal at Ethiopian

treatment treatment optimum values discharge
standard
Optimum dose (8 g/l)
1 Color (Pt -Co) 2300 184 92 -
2 TURBIDITY 210 21 90 -
(NTU)
3 PH 11.2 6.8 - 6-9
4 COD 1200 210 82.5 >80%
Optimum PH
1 Color (Pt -Co) 2300 340.5 85.2 -
2 Turbidity (NTU) 210 32 84.76 -
3 PH 11.2 6.4 - 6-9
4 COD 1200 215 82.1 >80%
Optimum mixing time
1 Color (Pt -Co) 2300 276.5 87.9 -
2 Turbidity (NTU) 210 37.8 82 -
3 PH 11.2 6.5 - 6-9
4 COD 1200 223.5 81.37 >80%

56
 5. CONCLUSION AND RECOMMENDATIONS
5.1. Conclusion

In general, it can be concluded that the use of pumpkin seed extract as natural coagulant
for the treatment of textile wastewater is technical, economic and environmentally viable.
The methodology for the elaboration of coagulants extracts is very simple and economical;
it does not imply the use of reagents or complex equipment. The process is highly efficient
for reactive dyes because it can remove up to 92% of the visible color in a period of time
that varies between 30 to 45 minutes. According with studies performed for textile dye
effluent, the optimum coagulant dosage ranges is between 4 and 12 g/L. The flocculant
capacity of the proteins contained in the seed could be comparable with a synthetic cationic
polymer coagulant and its activity is based on the selective coagulation of suspended
material on the surface of the molecule, due to its high density of positive charge. The
results allow us to infer that the coagulation with the seed extracts are not controlled by
electrostatic forces, but by adsorption and formation of inter particle bridges. This enables
to suggest their direct application in a textile dye effluent treatment, without the need to
adjust the pH of the water during the process.

This study concluded that the treatment of textile dye effluent before disposal is important
to ensure the safety of our environment. To this end, there has been different textile
wastewater treatment methods are studied and applied. Coagulation, which was applied in
the present study, represents a powerful treatment method for toxic pollutants of textile
wastewater. Thus, different type of experiments were undertaken to address each of the
specific objectives of the study. The initial character of the textile wastewater sample
showed pH (11.2), Color (2300 Pt –Co), COD (1200 g/l) and Turbidity was 210 NTU.

The coagulation experiment proved coagulant dose, pH, and mixing time for being
important operating parameters for the removal of color and turbidity from textile dye
effluent using pumpkin seed extract as a coagulant. And their optimum conditions were
at 8g/l of coagulant dose, pH 5, & 45 minutes of mixing time. The final character of the
textile wastewater after treated with coagulant showed pH (6.8), Color (184 Pt –Co), COD

57
(210 g/l) and Turbidity were 21 NTU. Hence, at these optimal conditions the removal
efficiency of color, COD and turbidity was 92 %, 82.5% and 90 % respectively.

In general, it can be concluded that pumpkin seed extract is an effective coagulant;

that has significant potential to remove the level of color, COD and turbidity from
textile wastewater. Therefore, cultivation, promotion and development of pumpkin seed
which offers many diverse advantages for developing countries like Ethiopia; cost effective
and environmental eco -friendly.

5.2. Recommendations

Based on the above findings, the researcher recommends the wide use of pumpkin seed
extract as a coagulant for the treatment of textile industry wastewater which operate in
Ethiopia. Because, for one thing it is possible to cultivate pumpkin locally, and for
another thing its application as coagulant should be encouraged since it is
environmental friendly coagulant. To this end, the following points need attention:

1. Considering the settling time and temperature as factors in the coagulation-

flocculation treatment process is recommendable.

2. It is also better to study the health impact of the textile dye effluent on the workers found
in the textile industry in special and the society near by the textile industry in diverse.

3. It is recommendable to study the Environmental and economic feasibility of using

pumpkin seed as a coagulant.

4. Apply pumpkin seed as coagulant in Textile dyeing industries wastewater treatment

plant at industrial scale in Ethiopia, since it has significant potential to remove color and
turbidity.

5. Future research should be done using this technology in combinational with other cost
effective treatment methods for further treatment to improve the removal efficiency of the
system.

58
6. Additional studies should be conducted to identify other operational variables that may
affect the effectiveness of pumpkin seed as a coagulant in treating textile dye effluent
treatment.

7. Further research should be also undertaken on the use of pumpkin seed at industrial
scale for textile wastewater treatment.

8. It is essential to create awareness to farmers to cultivate and engage on pumpkin

tree development all over the countries and creating market to local people to sell the
seeds.

9. Policy makers of Ethiopia should pay attention and exert pressure on wider application
of pumpkin seed as a coagulant in textile industries wastewater treatment system.

10. Further research should be conducted on the use of treated water for re-dyeing,
irrigation, agricultural use and for watering city sanitary area and beautification purpose.

59
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 APPENDIX

Appendix 1: Textile wastewater discharges to water bodies according

to EPA, 2003

Parameter limit values

PH 6–9
BOD5 50 mg/ l>90% removal
Turbidity -
COD (mg /l) 150 mg/l >80% removal
Suspended solid 30mg/l
Color -
Total dissolved solid 80mg/l

Appendix 2: Experimental runs and results to optimize operational

parameter

A. Determination of optimum coagulant dose without pH adjustment

R Variables and Parameters

u levels
n dose pH Time Color (pt-co) COD (mg/l) Turbidity (NTU)
(g/l)
S1 S2 S3 Avera S 1 S 2 S 3 Avera S 1 S2 S3 Avera
(min) ge ge ge
1 4 11.2 30 49 512 50 506 48. 58 53. 53.34 581 60 591 592
9 6.3 6 5 2.5 .5
3
2 8 11.2 30 17 185 18 184 19 20. 22. 21 198 20 222 210
9 7.5 8 5 9.5 .5
3 12 11.2 30 23 248. 23 239.2 19. 28. 37 28.35 371. 35 386 372
0 5 9 5 38 5 7

63
 B. Determination of optimum mixing time

8 11.2 30 88 895 90 894 83 94. 90. 89.25 608 63 614 617.6

4 2 6 2 3 0 .9
4 8 11.2 45 26 290 27 276.5 31 47 35. 37.8 216 22 225 223.5
1 5.8 5 9.5
5 8 11.2 60 57 583 57 579.6 61 76. 70 69.3 459 48 476 472
5 9.6 8 0
C. Determination of optimum Ph

6 8 5 45 32 341 35 340.5 27 39 30 32 201 22 214 215

8 2.5 8 .6
7 8 7 45 87 902. 89 890.5 69. 81 79 76.5 423 45 437 437.6
8.5 25 1 5 1 .5
8 8 9 45 12 1264 12 1252.5 11 13 12 124.9 539. 56 550 552
40 53. 7 2 5.6 5 6
8
D. Determination of optimum dose at optimum pH and mixing time

9 4 5 45 49 512 50 506 48. 58 53. 53.34 581 60 591 592

9 6.3 6 5 2.5 .5
3
1 8 5 45 17 185 18 184 19 20. 22. 21 198 20 222 210
0 9 7.5 8 5 9.5 .5
1 12 5 45 23 248. 23 239.2 19. 28. 37 28.35 371. 35 386 372
1 0 5 9 5 38 5 7

64
 Appendix 3: The overall treatment stages of these experimental work with
images

a) Matured pumpkin b) Seeds

c) Grinding using disc milling machine d) Sieve analysis at 2mm size

65
e) Pumpkin seed powder f) Pumpkin seed extract (oil removed)

g) Jar test apparatus for optimization of coagulation

66
 Waste water sample before treatment

Waste water samples after decolorization through coagulation

67