STUDIES ON THE USE OF ADSORPTION &

ADVANCED OXIDATION PROCESS FOR the

TREATMENT OF TEXTILE INDUSTRY WASTE
WATER
A thesis submitted towards partial fulfillment of the requirements for the degree of
MASTER OF ENGINEERING IN CHEMICAL ENGINEERING

Submitted by

SAMYA SUBHRA DAS

Class Roll No: 001310302002
Exam Roll No: M4CHE1502
Registration No: 124699 of 2013-14

Under the Guidance of

Dr. Chiranjib Bhattacharjee
Professor & former Head of the Department
Department of Chemical Engineering
Jadavpur University

DEPARTMENT OF CHEMICAL ENGINEERING JADAVPUR UNIVERSITY

Jadavpur, Kolkata-700032
MAY 2015

FACULTY OF ENGINEERING AND TECHNOLOGY

DEPARTMENT OF CHEMICAL ENGINEERING
JADAVPUR UNIVERSITY

CERTIFICATE OF RECOMMENDATION
This is to certify that the thesis entitled STUDIES ON THE USE OF
ADSORPTION & ADVANCED OXIDATION PROCESS FOR THE
TREATMENT OF TEXTILE INDUSTRY WASTE WATER is a bonafide
work carried out by Samya Subhra Das under my supervision and guidance for
partial fulfillment of the requirement of Master of Engineering in Chemical
Engineering, during the academic session 2013-2015

--------------------------------------------

---------------------------------------------

Dr. Chiranjib Bhattacharjee

Dr. Chandan Guha

Project Supervisor

Professor & HOD

Professor & former-HOD

Department of Chemical Engineering

Department of Chemical Engineering

Jadavpur University, Kolkata-32

Jadavpur University, Kolkata-32

--------------------------------------------

DEAN -FET
Jadavpur University,
Kolkata-700 032

FACULTY OF ENGINEERING AND TECHNOLOGY

DEPARTMENT OF CHEMICAL ENGINEERING
JADAVPUR UNIVERSITY

CERTIFICATE OF APPROVAL

This foregoing thesis is hereby approved as a credible study of an engineering

subject carried out and presented in a manner satisfactorily to warranty its
acceptance as a prerequisite to the degree for which it has been submitted. It is
understood that by this approval the undersigned do not endorse or approve any
statement made or opinion expressed or conclusion drawn therein but approve the
thesis only for purpose for which it has been submitted.

-----------------------------------------------

Committee of final examination

-----------------------------------------------

for evaluation of Thesis

-----------------------------------------------

-----------------------------------------------

DECLARATION OF ORIGINALITY AND COMPLIANCE

OF ACADEMIC ETHICS

I hereby declare that this thesis contains literature survey and original research
work by the undersigned candidate, as part of his Master of Engineering in
Chemical Engineering studies during academic session 2013-2015.

All information in this document has been obtained and presented in accordance
with academic rules and ethical conduct.

I also declare that, as required by this rules and conduct, I have fully cited and
referred all material and results that are not original to this work.

Name: SAMYA SUBHRA DAS

Roll Number: 001310302002
Exam Roll No: M4CHE1502
Thesis Title: STUDIES ON THE USE OF ADSORPTION & ADVANCED
OXIDATION PROCESS FOR THE TREATMENT OF TEXTILE INDUSTRY
WASTE WATER

SIGNATURE:

DATE:
(SAMYA SUBHRA DAS)

ACKNOWLEDGEMENT
I consider it as my privilege to express gratitude and respect to all those who
guided and inspired me in the completion of my M.E. project. The undertaking of
this project inculcated a strong sense of research inside me and I also came to
know about many new things.
First of all, I would like to acknowledge and extend my heartfelt gratitude to
Dr. Chiranjib Bhattacharjee (Professor & Former HOD, Department of Chemical
Engineering, Jadavpur University) for his exemplary guidance during the
undertaking of this project entitled, STUDIES ON THE USE OF ADSORPTION
& ADVANCED OXIDATION PROCESS FOR THE TREATMENT OF
TEXTILE INDUSTRY WASTE WATER.
I would like to take this opportunity to thank Mr. Shubhrajit Sarkar (PhD
research scholar, Chemical engg. dept. JU) for his constant encouragement and
helpful advice in completion of this project work. I would also like to extend my
gratitude to my co-researcher Mr. Diptadip Paul (B.E. Chemical engg, JU) & all
the seniors of the Membrane Separation Lab (Chemical engg dept. JU) for
supporting me whenever it was needed.
My very special thanks to my parents & my little brother, whom I owe
everything I am today. Their unwavering faith & confidence in my abilities have
always helped me to overcome all the problems of my life. Thanks to all of my
friends for their constant love & support.
Finally, I would like to take the opportunity to thank all my teachers and
support staff of the Chemical Engineering Department, Jadavpur University,
Kolkata.

CONTENTS
CHAPTER NO & TOPIC/SUB-TOPIC
1. INTRODUCTION
1.1. Waste water: A brief review

PAGE NO
1 - 29
4

1.1.1.

Origin

1.1.2.

Waste water constituents

1.1.3.

Wastewater quality indicators

1.2. Industrial Wastewater

1.2.1.

Types of industrial waste water

7
8

1.3. Textile industry Effluents

10

1.4. Textile dye

11

1.4.1.

Adverse effect of Textile Dye

15

1.5. Different wastewater treatment procedure

15

1.6. Adsorption

18

1.6.1.

Different Popular adsorbents

18

1.6.2.

Advantages & disadvantages of adsorption

22

1.7. Advanced Oxidation Process

23

1.7.1.

Advantages & disadvantages of AOP

25

1.7.2.

Classification

26

2. LITERATURE REVIEW

30 - 36

3. AIMS & OBJECTIVES

37 - 39

4. ADSORPTION

40 - 57

4.1. Materials

41

4.2. Preparation of adsorbents

41

4.3. Equipments

41

4.4. Analytical instrument

41

4.5. Methods

43

4.5.1.

Effect of Adsorbent dosage

43

4.5.2.

Effect of pH

43

4.5.3.

Equilibrium studies

43

4.5.4.

Batch kinetic studies

44

4.5.5.

Analytical method

44

4.6. Results & Discussion: Effect of pH

46

4.7. Results & Discussion: Effect of adsorbent dosage

47

4.8. Results & Discussion: Effect of temperature

48

4.9. Results & Discussion: Effect of stirring speed

49

4.10. Effect of contact time and initial concentration

50

4.11. Equilibrium studies & Isotherm analysis

51

4.12. Results & Discussion: Adsorption kinetics

55

4.13. Characterization study

57

5. SONO FFENTON

60 - 69

5.1. Materials

61

5.2. Equipments

61

5.3. Experimental Methods

62

5.3.1.

Effect of H2O2 dose

62

5.3.2.

Effect of FeSO4 dose

62

5.3.3.

Effect of pH

62

5.4. Results & discussions: Effect of solution pH

64

5.5. Results & discussions: Effect of FeSO4 dose

65

5.6. Results & discussions: Effect of H2O2 dose

66

5.7. Enhancement of dye degradation in Sono Fenton process

67

5.8. Effect of different salts on Sono Fenton

67

6. CONCLUSION

70 - 71

REFERENCES

72 - 74

List of figures
Fig no

Figure details

Page no

Fig I

Different Stages of a textile industry

10

Fig II

Molecular Structure of Reactive green 19

14

Fig III

Different widely popular Adsorbents

21

Fig IV

Outline of the Advanced Oxidation Process

24

Fig V

Oxidation potential of different elements

24

Fig VI

Electron transfer in Advanced Oxidation Process

28

Fig VII

Flow chart of the work to be done

39

Fig VIII

Time & RPM controlled rotary shaker

42

Fig IX

UV Spectrophotometer

42

Fig X

Digital pH meter

42

Fig XI

Cold Centrifuge

42

Fig XII

Vaccum Oven

42

Fig XIII

Decoloration of RG 19 by adsorption at optimum conditions

45

Fig XIV

Effect of pH on decoloration of RG19 on MTW

46

Fig XV

Effect of adsorbent dosage on decoloration of RG19 on MTW

47

Fig XVI

Effect of temperature on decoloration of RG19 on MTW

48

Fig XVII

Effect of stirring speed on decoloration of RG19 on MTW

49

Fig XVIII

Effect of contact time and initial concentration on the adsorption

50

of RG19 on MTW
Fig XIX

Isotherm analysis for Langmuir model

51

Fig XX

Isotherm analysis for Freundlich model

52

Fig XXI

Isotherm analysis for Temkin model

53

Fig XXII

Pseudo second order kinetics

56

Fig XXIII

SEM image of adsorbent (a) Before adsorption (b) After

57

adsorption
Fig XXIV

FTIR spectra of the adsorbent samples: after & before adsorption

57

Fig XXV

Probe Sonicator System

61

Fig XXVI

Decoloration of dye solution at optimum conditions at definite

63

time intervals
Fig XXVII

Effect of solution pH on decoloration of RG 19 by SF

64

Fig XXVIII Effect of solution pH on decoloration of RG 19 by SF

65

Fig XXIX

Effect of H2O2 dose on decoloration of RG 19 by SF

66

Fig XXX

Effect of different process on decoloration of RG 19 by SF

67

Fig XXXI

Effect of different salts on decoloration of RG 19 by SF

68

CHAPTER - 1

IntroductIon

The imbalance between the environment and the existence of life on the earth is due to
rapid and enormous growth of industrial civilization for meeting the needs of the tremendous rise
in human population day by day. Water is available in three different forms on the earth namely:
Ground water, Surface water & Rain water. Rain water, although is extremely pure and safe for
all purposes of our civilization, but harvesting rain water and its storage is inadequate to meet
our demand. Ground water and rain water although are available in plenty, the quality and cost of
these two forms of water have become an alarming threat to our survival. Ground water is
gradually becoming depleted and/or contaminated due to percolation. The surface water is
already contaminated by mercury, chromium, copper, nickel salts & oils & dyes etc. due to
industrial and domestic effluents discharged into the rivers and oceans through the porous bed of
soil and rocks, as also due to sliding in the mineral deposits of arsenic & other detrimental
metals.

Freshwater ecosystems are aquatic systems which contain drinkable water or water of
almost no salt content. Freshwater resources include lakes and ponds, rivers and streams,
reservoirs, wetlands, and groundwater. They provide the majority of our nation's drinking water
resources, water resources for agriculture, industry, sanitation, as well as food including fish and
shellfish. They also provide recreational opportunities and a means of transportation. In addition,
freshwater ecosystems are home to numerous organisms (e.g., fish, amphibians, aquatic plants,
and invertebrates). It has been estimated that 40% of all known fish species on Earth come from
freshwater ecosystems. Human activities are causing species to disappear at an alarming rate. It
has been estimated that between 1975 and 2015, species extinction will occur at a rate of 1 to 11
percent per decade. Aquatic species are at a higher risk of extinction than mammals and birds.
Losses of this magnitude impact the entire ecosystem, depriving valuable resources used to
provide food, medicines, and industrial materials to human beings. While freshwater and marine
ecosystems face similar threats, there are some differences regarding the severity of each threat.
Runoff from agricultural and urban areas, the invasion of exotic species, and the creation of
dams and water diversion have been identified as the greatest challenges to freshwater
environments [1]. Overfishing is the greatest threat to marine environments, thus the need for
sustainable fisheries has been identified by the Environmental Defense Fund as the key priority
in preserving marine biodiversity. Other threats to aquatic biodiversity include urban
development and resource-based industries, such as mining and forestry that destroy or reduce
natural habitats. In addition, air and water pollution, sedimentation and erosion, and climate
change also pose threats to aquatic biodiversity. Pollution has been very damaging to aquatic
2

ecosystems, and may consist of agricultural, urban, and industrial wastes containing
contaminants such as sewage, fertilizer, and heavy metals that have proven to be very damaging
to aquatic habitats and species. Metals, a major category of globally-distributed pollutants, are
natural elements that have been extracted from the earth and harnessed for human industry and
products for modern civilized world. Numerous industrial processes and human & animal
excreting produce aqueous effluents and sewer that contain heavy metals, non-metals and
organic contaminants. People are exposed to organic component through inhalation, water and
food/ ingestion. Textile industries are among those industries that discharge wastewater.
The textile industry uses high volumes of water throughout its operations, from the
washing of fibers to bleaching, dyeing and washing of finished products. On average,
approximately 200 liters of water are required to produce l kg of textiles the large volumes of
wastewater generated also contain a wide variety of chemicals, used throughout processing.
These can cause damage if not properly treated before being discharged into the environment. Of
all the steps involved in textiles processing, wet processing creates the highest volume of
wastewater. The aquatic toxicity of textile industry wastewater varies considerably among
production facilities. The sources of aquatic toxicity can include salt, surfactants, ionic metals
and their metal complexes, toxic organic chemicals, biocides and toxic anions. Most textile dyes
have low aquatic toxicity. On the other hand, surfactants and related compounds, such as
detergents, emulsifiers and dispersants are used in almost each textile process and can be an
important contributor to effluent aquatic toxicity, BOD and foaming. Several methods have been
developed for decontamination of municipal and industrial waters and wastewaters. The most
common methods for removal of contaminants from industrial effluents include chemical
precipitation, solvent extraction, dialysis, electrolytic extraction, electro-dialysis, cementation,
reverse osmosis, membrane filtration, ion exchange, adsorption and co-precipitation.

1.1. Waste Water: a Brief OvervieW

Wastewater, also written as waste water, is any water that has been adversely affected in
quality by anthropogenic influence. Municipal wastewater is usually conveyed in a combined
sewer or sanitary sewer, and treated at a wastewater treatment plant. Treated wastewater is
discharged into receiving water via an effluent sewer. Wastewaters generated in areas without
access to centralized sewer systems rely on on-site wastewater systems. These typically comprise
a septic tank, drain field, and optionally an on-site treatment unit.

Sewage is the subset of wastewater that is contaminated with feces or urine, but is often used to
mean any wastewater. Sewage includes domestic, municipal, or industrial liquid waste products
disposed of, usually via a pipe or sewer (sanitary or combined), sometimes in a cesspool emptier.
Sewerage is the physical infrastructure, including pipes, pumps, and screens, channels etc. used
to convey sewage from its origin to the point of eventual treatment or disposal. It is found in all
types of sewage treatment, with the exception of septic systems, which treat sewage on site.

1.1.1. Origin:
Wastewater or sewage can come from:

Human waste (faces, used toilet paper or wipes, urine, or other bodily fluids), also known
as black water, usually from lavatories;
4

Cesspit leakage;

Septic tank discharge;

Sewage treatment plant discharge;

Washing water (personal, clothes, floors, dishes, etc.), also known as greywater or sullage;

Rainfall collected on roofs, yards, hard-standings, etc. (generally clean with traces
of oils and fuel);

Groundwater infiltrated into sewage;

Surplus

manufactured

liquids

from

domestic

sources

(drinks,

cooking

oil, pesticides, lubricating oil, paint, cleaning liquids, etc.);

Urban rainfall runoff from roads, car parks, roofs, sidewalks / pavements (contains oils,
animal feces, litter, gasoline/petrol, diesel or rubber residues, soap scum, metals from
vehicles exhaust etc.)

Seawater ingress (high volumes of salt and microbes);

Direct ingress of river water (high volumes of micro-biota);

Direct ingress of manmade liquids (illegal disposal of pesticides, used oils, etc.);

Highway drainage (oil, de-icing agents, rubber residues);

Storm drains (almost anything, including cars, shopping trolleys, trees, cattle, etc.);

Blackwater (surface water contaminated by sewage);

Industrial waste

Industrial site drainage (silt, sand, alkali, oil, chemical residues);

Industrial cooling waters (biocides, heat, slimes, silt);
Industrial process waters;
Organic or biodegradable waste, including waste from abattoirs, creameries, and ice

cream manufacture;
Organic or non bio-degradable/difficult-to-treat waste
Extreme pH waste (from acid/alkali manufacturing, metal plating);
Toxic waste (metal plating, cyanide production, pesticide manufacturing, etc.);
Solids and emulsions
Agricultural drainage, direct and diffuse.
Hydraulic fracturing
Produced water from oil & natural gas production

1.1.2. Wastewater constituents:

The composition of wastewater varies widely. This is a partial list of what it may contain:

Water (more than 95 percent), which is often added during flushing to carry waste down a
drain;

Pathogens such as bacteria, viruses, prions and parasitic worms;

Non-pathogenic bacteria;

Organic particles such as feces, hairs, food, vomit, paper fibers, plant material, humus, etc.;

Soluble organic materials such as urea, pharmaceutical wastes, sugars etc.:

Inorganic particles such as sand, grit, metal particles, ceramics, etc.;

Soluble inorganic material such as ammonia, road-salt, sea-salt, cyanide, hydrogen

sulfide, thiocyanates, thiosulfates, etc.;

Animals such as protozoa, insects, arthropods, small fish, etc.;

Macro-solids such as sanitary napkins, nappies/diapers, condoms, needles, children's toys,

dead animals or plants, etc.;

Gases such as hydrogen sulfide, carbon dioxide, methane, etc.;

Emulsions such as paints, adhesives, mayonnaise, hair colorants, emulsified oils, etc.;

Toxins such as pesticides, poisons, herbicides, etc.

1.1.3. Wastewater quality indicators:

Any oxidizable material present in a natural waterway or in an industrial wastewater will
be oxidized both by biochemical (bacterial) or chemical processes. The result is that the oxygen
content of the water will be decreased. Basically, the reaction for biochemical oxidation may be
written as:
Oxidizable material + nutrient + bacteria + O2 CO2 + H2O + Oxidized inorganic species
Oxygen consumption by reducing chemicals such as sulfides and nitrites is typified as follows:
S-- + 2 O2 SO4-NO2- + O2 NO3Since all natural waterways contain bacteria and nutrients, almost any waste compounds
introduced into such waterways will initiate biochemical reactions (such as shown above). Those
6

biochemical reactions create what is measured in the laboratory as the biochemical oxygen
demand (BOD). Such chemicals are also liable to be broken down using strong oxidizing agents
and these chemical reactions create what is measured in the laboratory as the chemical oxygen
demand (COD). Both the BOD and COD tests are a measure of the relative oxygen-depletion
effect of a waste contaminant. Both have been widely adopted as a measure of pollution effect.
The BOD test measures the oxygen demand of biodegradable pollutants whereas the COD test
measures the oxygen demand of oxidizable pollutants. The so-called 5-day BOD measures the
amount of oxygen consumed by biochemical oxidation of waste contaminants in a 5-day period.
The total amount of oxygen consumed when the biochemical reaction is allowed to proceed to
completion is called the Ultimate BOD. Because the Ultimate BOD is so time consuming, the 5day BOD has been almost universally adopted as a measure of relative pollution effect. There are
also many different COD tests of which the 4-hour COD is probably the most common. There is
no generalized correlation between the 5-day BOD and the ultimate BOD. Similarly there is no
generalized correlation between BOD and COD. It is possible to develop such correlations for
specific waste contaminants in a specific wastewater stream but such correlations cannot be
generalized for use with any other waste contaminants or wastewater streams. This is because the
composition of any wastewater stream is different. As an example an effluent consisting of a
solution of simple sugars that might discharge from a confectionery factory is likely to have
organic components that degrade very quickly. In such a case, the 5 day BOD and the ultimate
BOD would be very similar since there would be very little organic material left after 5 days.
However a final effluent of a sewage treatment works serving a large industrialized area might
have a discharge where the ultimate BOD was much greater than the 5 day BOD because much
of the easily degraded material would have been removed in the sewage treatment process and
many industrial processes discharge difficult to degrade organic molecules. The laboratory test
procedures for the determining the above oxygen demands are detailed in many standard texts.
American versions include the "Standard Methods for the Examination of Water and
Wastewater.

1.2. IndustrIal waste water

Now-a-days industrial wastewater is a real threat to the mankind. Industrial bloom has
made the life of ecosystem along with water bodies miserable with their constant emission of
wastewater. Industrial wastewater can be categorized based on different kind of parameters.

1.2.1. Types of industrial waste water:

There are many types of industrial wastewater based on the different industries and the
contaminants; each sector produces its own particular combination of pollutants:

Iron and steel: BOD, COD, oil, metals, acids, phenols, and cyanide
Textiles and leather: BOD, solids, sulfates and chromium
Pulp and paper: BOD, COD, solids, chlorinated organic compounds
Petrochemicals and refineries: BOD, COD, mineral oils, phenols, and chromium
Chemicals: COD, organic chemicals, heavy metals, SS, and cyanide
Non-ferrous metals: Fluorine and SS
Microelectronics: COD and organic chemicals
Mining: SS, metals, acids and salts

Generally, industrial wastewater can be divided into two types: Inorganic industrial wastewater
and Organic industrial wastewater [2].

A. Inorganic industrial wastewater:

Inorganic industrial wastewater is produced mainly in the coal and steel industry, in the
nonmetallic minerals industry, and in commercial enterprises and industries for the surface
processing of metals (iron picking works and electroplating plants). These wastewaters contain a
large proportion of suspended matter, which can be eliminated by sedimentation, often together
with chemical flocculation through the addition of iron or aluminum salts, flocculation agents
and some kinds of organic polymers. The purification of warm and dust-laden waste gases from
blast furnaces, converters, cupola furnaces, refuse and sludge incineration plants, and aluminum
works results in wastewater containing mineral and inorganic substances in dissolved and undissolved form. The pre-cooling and subsequent purification of blast-furnace gases requires up
to 20 m3 water per t of pig iron. On its way into the gas cooler the water absorbs fine particles of
ore, iron and coke, which do not easily settle. Gases dissolve in it, especially carbon dioxide and
compounds of the alkali and alkaline earth metals, if they are water-soluble or if they are
dissolved out of the solid substances by gases washed out along with them. In the separation of
coal from dead rock, the normal means of transport and separation is water, which then contains
large amounts of coal and rock particles and is called coal washing water. Coal-washing water is
8

recycled after removal of the coal and rock particles through flotation and sedimentation
processes. Other wastewater from rolling mills contain mineral oil and require additional
installations, such as scum boards and skim-off apparatus, for the retention and removal of
mineral oils. Residues of emulsified oil remaining in the water also need chemical flocculation.
In many cases, wastewater is produced in addition to solid substances and oils, and also contains
extremely harmful solutes. These include blast-furnace gas-washing wastewater containing
cyanide, wastes from the metal processing industry containing acids or alkaline solutions (mostly
containing non-ferrous metals and often cyanide or chromate), and wastewater from eloxal
works and from the waste gas purification of aluminum works, which in both cases contain
fluoride. Small and medium sized non-metallic-minerals plants and metal processing plants are
so situated that they discharge their wastewater into municipal wastewater systems and have to
treat or purify their effluents before discharge, in compliance with local regulations.

B. Organic industrial wastewater:

Organic industrial wastewater contains organic industrial waste flow from those chemical
industries and large-scale chemical works, which mainly use organic substances for chemical
reactions. The effluents contain organic substances having various origins and properties. These
can only be removed by special pretreatment of the wastewater, followed by biological
treatment. Most organic industrial wastewaters are produced by the following industries and
plants:

The factories manufacturing pharmaceuticals, cosmetics, organic dye-stuffs, glue and

adhesives, soaps, synthetic detergents, pesticides and herbicides;

Tanneries and leather factories;

Textile factories;

Cellulose and paper manufacturing plants;

Factories of the oil refining industry;

Brewery and fermentation factories;

In this report we will basically emphasize on Textile Industry effluents.

Textile dyes and other industrial dyes form one of the crucial organic compounds that
cause an increase in environmental dangers. About 1% to 20% of the overall dye productions of
the world is wasted during the dyeing processes, and is released in textile runoff. Thus, there is
an increasing concern for decolorization of dye containing waste water.
9

1.3. TEXTILE INDUSTRY EFFLUENTS:

The textile industry includes a wide range of activities, from preparation of raw material to
pre-treatment, dyeing and finishing of textile material. All these activities consume large amount
of water and are highly polluting. Textile industry processes are known to be intensive users of
water. In Figure I a process diagram of a textile industry is shown, highlighting the steps where
the water consumption and the generation of aqueous effluents occur

Fig I: Different Stages of a textile industry

10

Due to the wide variety of fibers, dyes, process auxiliaries and final products, these processes
generate waters of great diversity and chemical complexity. This complex composition is
reflected in the color, in a high ratio between chemical oxygen demand and biochemical oxygen
demand (COD/BOD5), in the presence of suspended matter and, possibly, heavy metals, and in
variable pH values, mostly in the alkaline range. However, since the fashions are always varying,
the textile effluents composition is never constant. Environmental problems related to the textile
industry are numerous and well documented. Despite the high volume of waste and its high
organic load, the main problem of textile industry effluents is related to the color generated by
unfixed dyes during textile processing and directly released to the effluent. [3]

1.4. TEXTILE DYES :

Since the beginning of times, people have demonstrated the need to add color to all that
surrounds them & wanted to make the world colourful. They use dyes from natural origins, such
as soot, manganese oxide, hematite and ochre for painting their stories in caves, their skins and
their clothes. The textile natural dyes were mainly obtained from plants, insects, fungi and
lichens [4]. Mauveine, the first synthetic dye, was discovered in 1856 by William Henry Perkin.
Since then, thousands of new synthetic dyes have been produced. Nowadays, the total annual
world textile dye production is estimated at about 7x105 tons, with more than 100,000 dyes
available on the market [5]. The largest consumer of these dyes is the textile industry accounting
for around two thirds of its market. To be colored compounds, dyes have to absorb radiation in
the visible range, i.e., 380 to 780 nm. This property is due to the possession of two different
groups, the chromophores, which is typically an electron withdrawing group and is responsible
for the color of the compound, and the auxochrome, which is an electron donating substituent
that can intensify the color of the chromophores and provides solubility and adherence of the dye
to the fiber [6]. Dyes can be divided in 20-30 different groups regarding their chromophores. The
most important are azo (monoazo, diazo, triazo, polyazo), anthraquinone, phthalocyanine and
triarylmethane dyes. Azo dyes represent about 70 % on weight basis of total annual world
production [7]. These dyes are followed, in terms of prevalence, by the anthraquinone dyes.

11

:Different classes of Textile Dyes:

Application
class

Acid dyes

Characteristics
Highly water soluble;
form ionic
interactions
between the -NH3+
groups of fibers and
the
negative charge of the

Substrates

Wool, polyamide,
silk,
nylon, leather

Common
structures

Azo,
anthraquinone,
triarylmethane

dyes

Reactive dyes

Direct dyes

Basic dyes

Mordant dyes

Disperse dyes

Form covalent bonds

with -OH, -NH or -SH
groups

Cotton, wool, silk,

nylon
Azo, metal

Their flat shape and

length enables them to
maximize van-derWaals, dipole and
hydrogen bonds

Cellulose fibers,
cotton,
viscose, paper,
leather,
nylon

Strong ionic
interaction between
dye
cationic groups and
the negative charges
in the copolymer
Metal salts that act as
fixing agent to
improve the color
fastness
Non-ionic structure,
with polar
functionality,
that improves water
solubility, van-derWaals and dipole
forces and the color.

Synthetic fibers,
paper,
inks

Wool, leather, silk,

modified cellulose
fibers

Polyester, polyamide,
acetate, acrylic,
plastics

Complex azo,
anthraquinone,
phthalocyanine

Sulphonated azo
dyes

Azo,
diarylmethane,
triarylmethane,
anthraquinone

Azo, oxazine,
triarylmethane

Azo, nitro,
anthraquinone,
metal complex
azo

12

Pigment dyes

Vat dyes

Ingrain dyes

Sulphur dyes

Solvent dyes

Other dye classes

Insoluble, non-ionic
compounds or salts
that retain their
crystalline particulate

Paints, inks, plastics,

textiles

Azo, metal
Complex
phthalocyanine

Cellulose fibers,
cotton,
viscose, wool

Anthraquinone,
indigoid

Insoluble products of
a reaction between a
coupling component
and a diazotized
aromatic amine that
occurs in the fiber

Cotton, viscose,
cellulose acetate,
polyester

Tetra-azaporphin

Dyeing with sulphur

dyes involves
reduction and
oxidation processes

Cellulose fibers,
cotton,
viscose

Complex
polymeric
aromatics

Non ionic dyes that

dissolve the substrate
to which they bind

Plastics, varnish, ink,

waxes, fats

Diazo,
triarylmethane,
anthraquinone,
phthalocyanine

Insoluble coloured
dyes which on
reduction
dive soluble
colourless forms
/leuco form
with affinity for the
fiber; can be oxidized
back, with H2O2, to
insoluble form

Food dyes: not used

as textile dyes,
nontoxic;
Natural dyes: use in
textile
processing operations
is very limited;
Fluorescent
brighteners: mask the
yellowish tint of
natural fibers; Metal
complex dyes: strong
complexes of one
metal ion

Food, cotton, wool,

silk,
polyester, polyamide,
soaps and detergents,
paints, plastics

Azo

13

In our study we have used a solution of Reactive Green 19 as industrial wastewater.

Commercial Name: C.I.Reactive Green19
Molecular Structure: Azo Class.
Molecular Formula: C40H23Cl2N15Na6O19S6.
Molecular Weight: 1418.94.
Manufacturing Method: 2,4,6-Trichloro-1,3,5-triazine and 3-Aminobenzenesulfonic acid and
2,5-Diaminobenzenesulfonic acid condensation, Its product (2 moles) and 4-Amino-5
hydroxynaphthalene-2,7-disulfonic acid in acidic and alkaline medium coupling.
Properties and Applications: Blue-green powder, in 20 when solubility of 120 g/L; 50
when solubility of 150 g/L. After dyeing tonal for green, dye bath of copper ions in a red light
and dark (grade 1), encounter iron ion colored light micro to yellow (category 4). The dye sex is
high, the reaction of the medium, and easy to wash the gender is good. For A class of neutral
white, white alkaline for grade C. Apply to cotton, such as glue than small bath dyeing, with high
economic value. Also suitable for polyester/cotton, polyester/stick blended fabric dyeing.

Fig II: Molecular Structure of Reactive green 19

14

1.4.1. ADVERSE EFFECTS OF TEXTILE DYES:

Dyes cause a lot of problems in the environment. The problems which are caused in
environment by dyes are given below:

Depending on exposure time and dye concentration, dyes can have acute and/or chronic
effects on exposed organisms.

The presence of very small quantities of dyes in water (less than 1 mg/L) is highly visible
due to their brilliance.

The greatest environmental concern with dyes is their absorption and reflection of
sunlight entering the water. Light absorption diminishes photosynthetic activity of algae
and seriously influence on the food chain.

Dyes can remain in the environment for an extended period of time, because of high
thermal and photo stability. For instance, the half-life of hydrolyzed Reactive Blue 19 is
about 46 years at pH 7 and 25C.

Many dyes and their breakdown products are carcinogenic, mutagenic and/or toxic to life.
Dyes are mostly introduced into the environment through industrial effluents.

Textile dyes can cause allergies such as contact dermatitis and respiratory diseases,
allergic reaction in eyes, skin irritation, and irritation to mucous membrane and the upper
respiratory tract.

1.5. Different wastewater treatment proceDures

Different treatment processes have been found based on the types of wastewater. The process
description of some of the methods is presented below:

Chemical Precipitation: Precipitation of metals is achieved by the addition of

coagulants such as alum, lime, iron salts and other organic polymers. The large amount of
sludge containing toxic compounds produced during the process is the main
disadvantage.

Microfiltration: Ultrafiltration: They are pressure driven membrane operations that use
porous membranes for the removal of heavy metals. The main disadvantage of this
process is the generation of sludge.

15

Nanofiltration: Osmosis: Reverse Osmosis: It is a process in which heavy metals are

separated by a semi-permeable membrane at a pressure greater than osmotic pressure
caused by the dissolved solids in wastewater. The disadvantage of this method is that it is
expensive.

Electrodialysis: In this process, the ionic components (heavy metals) are separated
through the use of semi-permeable ion-selective membranes. Application of an electrical
potential between the two electrodes causes a migration of cations and anions towards
respective electrodes. Because of the alternate spacing of cation and anion permeable
membranes, cells of concentrated and dilute salts are formed. The disadvantage is the
formation of metal hydroxides, which clog the membrane.

Ion-exchange: In this process, metal ions from dilute solutions are exchanged with ions
held by electrostatic forces on the exchange resin. The disadvantages include: high cost
and partial removal of certain ions.

Phyto-remediation: Phyto-remediation is the use of certain plants to clean up soil,

sediment, and water contaminated with metals. The disadvantages include that it takes a
long time for removal of metals and the regeneration of the plant for further bio-sorption
is difficult.

Sorption: Bio-sorption: The search for new technologies involving the removal of toxic
metals from wastewaters has directed attention to bio-sorption, based on metal binding
capacities of various biological materials. Bio-sorption can be defined as the ability of
biological materials to accumulate heavy metals from wastewater through metabolically
mediated or physico-chemical pathways of uptake. Algae, bacteria and fungi and yeasts
have proved to be potential metal bio-sorbents [8]. The major advantages of bio-sorption
over conventional treatment methods include:
i) Low cost; ii) High efficiency; iii) Minimization of chemical and/or biological sludge;
iv) additional nutrient requirement; v) Regeneration of bio-sorbent; and vi) Possibility
of metal recovery.
The bio-sorption process involves a solid phase (sorbent or bio-sorbent; biological
material) and a liquid phase (solvent, normally water) containing a dissolved species to
be sorbed (sorbate, metal ions). Due to higher affinity of the sorbent for the sorbate
species, the later is attracted and bound there by different mechanisms. The process
continues till equilibrium is established between the amount of solid-bound sorbate
species and its portion remaining in the solution.
16

Hence, at present it is very important to remove the pollutants and pathogens from
wastewater to fulfill the needs for irrigation and industrial and domestic use. In the past years,
conventional biological and physical treatment methods (adsorption, Ultrafiltration, coagulation,
etc.) have been used to remove the organic pollutants. These methods are not efficient and cost
effective for wastewaters containing high concentration of more toxic pollutants. This requires
some novel techniques to transfer the highly toxic pollutants chemically into benign species.
Advanced oxidation processes (AOPs) are more efficient, cheap, and eco-friendly in the
degradation of any kind of toxic pollutants. AOPs generate hydroxyl radical, a strong oxidant,
which can completely degrade or mineralize the pollutants non-selectively into harmless
products.
Here in this study we have tried to compare the effects of Adsorption as a low cost
treatment & advanced oxidation process as a highly efficient process on textile wastewater
containing dye and their respective advantages and disadvantages. Modified Tea waste has been
taken as an adsorbent & Sono-Fenton has been used as an AOP & a comparative study has been
done between these two processes.

17

1.6. Adsorption
Adsorption is the adhesion of atoms, ions, or molecules from a gas, liquid, or dissolved
solid to a surface. This process creates a film of the adsorbate on the surface of the adsorbent.
This process differs from absorption,

in which a fluid (the adsorbate) permeates or is

dissolved by a liquid or solid (the absorbent). Adsorption is a surface-based process while

absorption involves the whole volume of the material. The term sorption encompasses both
processes, while desorption is the reverse of it. Adsorption is a surface phenomenon. Similar
to surface tension, adsorption is a consequence of surface energy. In a bulk material, all the
bonding requirements (be they ionic covalent, or metallic) of the constituent atoms of the
material are filled by other atoms in the material. However, atoms on the surface of the adsorbent
are not wholly surrounded by other adsorbent atoms and therefore can attract adsorbate. The
exact nature of the bonding depends on the details of the species involved, but the adsorption
process is generally classified as physisorption (characteristics of weak van der Waals forces)
or chemisorptions (characteristic of covalent bonding). It may also occur due to electrostatic
attraction. Adsorption is present in many natural, physical, biological, and chemical systems, and
is widely used in industrial applications such as activated charcoal, capturing and using waste
heat to provide cold water for air conditioning and other process requirements (adsorption
chillers), synthetic resins, increase storage capacity of carbide, and water purification.
Adsorption, ion exchange, and chromatography are sorption processes in which certain adsorbate
are selectively transferred from the fluid phase to the surface of insoluble, rigid particles
suspended in a vessel or packed in a column. Lesser known, are the pharmaceutical industry
applications as a means to prolong neurological exposure to specific drugs or parts thereof The
word "adsorption" was coined in 1881 by German physicist Heinrich Kayser (1853-1940).

1.6.1. Different Popular Adsorbents:

A material that has the ability to extract certain substances from gases, liquids,
or solids by causing them to adhere to its surface without changing the physical properties is
called adsorbent. Carbon, silica, and activated alumina are materials frequently used for this
application. The table below gives clear idea about popular adsorbents and their applications.

18

Adsorbent

Applications
Drying of gases, refrigerants, organic solvents, transformer oils

Silica Gel

Desiccant in packing and double glazing

Dew point control of natural gas
Drying of gases, organic solvents, transformer oils

Activated Alumina Removal of Hcl from hydrogen

Removal of fluorine in alkylation process
Nitrogen from air
Hydrogen from syngas
Ethene from methane and hydrogen
Vinyl chloride monomer (VCM) from air
Carbons

Removal of odours from gases

Recovery of solvent vapors
Removal of SOX and NOX
Purification of helium
Clean-up of nuclear off-gases
Water purification
Oxygen from air
Drying of gasses
Removing water from azeotropes
Sweetening sour gases and liquids
Purification of hydrogen
Separation of ammonia and hydrogen
Recovery of carbon dioxide

Zeolites

Separation of oxygen and argon

Removal of acetylene, propane and butane from air
Separation of xylenes and ethyl benzene
Separation of normal from branched paraffin
Separation of olefins and aromatics from paraffin
Recovery of carbon monoxide from methane and hydrogen
Drying of refrigerants and organic liquids
Pollution control, including removal of Hg, NOX and SOX
19

Water purification
Recovery and purification of steroids, amino acids
Separation of fatty acids from water and toluene
Separation of aromatics from aliphatic
Polymers & Resins Recovery of proteins and enzymes
Removal of colors from syrups
Removal of organics from Hydrogen peroxide
Treatment of edible oils
Clay

Removal of organic pigments

Refining of mineral oils
Removal of polychlorinated biphenyls (PCBs)

Selection of an adsorbent basically depends on the following parameters:

Selectivity

Regenerability

Mass transfer kinetics

Compatibility

Cost

In this report we have used Modified Tea waste as a potential, low cost adsorbent for textile
dye removal. It is a natural low cost adsorbent, which is very much effective for textile dye
removal. Many adsorbents are available commercially now-a-days but Tea is basically chosen in
our experiment because it is consumed by most of the people in the world (somewhere between
18 and 20 billion cups of tea are drunk daily on world) and is the second most popular beverage
in the world. So, its very easily available and also it is rich in tannin and polyphenolic
compounds which is very difficult to biodegrade and is an oxygen demanding pollutant. So,
utilization of such waste is very much important

20

Activated Carbon

Silica Gel

Modified Tea Waste (Used in this study)

Fig III: Different widely popular Adsorbents

21

1.6.2. Advantages and disadvantages of Adsorption:

Advantages:

Possibility of product recovery

No chemical pollutant control when pollutant (product) recovered and returned to process

Capability of systems for fully automatic, unattended operation

Excellent control and response to process change

Drawbacks:

Product recovery possibly requiring a special, expensive distillation (or extraction)

Adsorbent progressively deteriorating in capacity as the number of cycles increases

Relatively high capital cost (In some cases).

Spent adsorbent may be considered a hazardous waste

Despite being a very cost effective & easily available process, it has a few drawbacks also.
The main problem with this process is the production of a large number of secondary wastes that
cannot be reused after 2 or 3 cycles. Those wastes are very hard to degrade and cannot be
dumped into the environment directly without further treatment. This process is a little bit
laborious and time consuming also. Hence, adsorption process creates another secondary waste
after removing of materials. So, a newer method is in search which will generate lesser
secondary waste and also cost-effective, efficient and less time consuming. To overcome these
drawbacks and provide the necessities Advanced Oxidation Process (AOP) came to light. We
will now shift our focus towards AOP and find out what are the changes required for this process
and the advancement of it and also how this process operates maintaining all the ecological
balance, following the environmental rules and regulations.

22

1.7. AdvAnced OxidAtiOn PrOcess

Advanced Oxidation Process (AOP) in a broad sense, refers to a set of chemical
treatment procedure designed to remove organic (sometimes inorganic) materials in water &
industrial or agriculture or household waste waters by oxidation through reaction with hydroxide
radicals (OH). In real-world it refers more specially to a subset of such chemical processes that
employ O3, H2O2 or UV light. It is particularly useful for cleaning biologically toxic or non
degradable materials such as aromatics, pesticides, petroleum constituents & volatile organic
matters in waste water. Contaminant materials are converted to a large extent into stable
inorganic compounds such as water, CO2 & salts i.e. they undergo mineralization. A goal of
AOP is the reduction of chemical contaminants & the toxicity to such an extent that the cleaned
waste water may be recycled or at least dumped into a conventional sewage treatment.
The AOP (Advanced Oxidation Processes) is usually used for removing contaminants from
waste water coming out of several types of heavy industries like:

Petrochemical & Plastic Industry

Chemical Industry.

Food Processing Industry.

Pharmaceutical Industry.

Metal and Metal Plating Industry.

Textile and Dying Industry

23

Fig IV: Outline of the Advanced Oxidation Process

Fig V: Oxidation potential of different elements

24

1.7.1. Advantages and disadvantages of Adsorption:

Advantages:

Rapid reaction rates.

Small foot print.

Potential to reduce toxicity and possibly complete mineralization of organics treated.

Does not concentrate waste for further treatment with methods such as membranes.

Does not produce materials that require further treatment such as "spent carbon" from
activated carbon absorption.

Does not create sludge as with physical chemical process or biological processes (wasted
biological sludge).

Due to the remarkable reactivity of OH, it virtually reacts with almost every aqueous
pollutants without much discrimination. AOPs could therefore be applicable in many, if
not all, scenarios where many organic contaminants are expected to be removed at the
same time.

Some heavy metals could also be removed in forms of precipitated M(OH) x.

In some AOPs designs, disinfection could also be achieved, leading AOPs to an

integrated solution to some of the water quality problems.

Since the complete reduction product of OH is H2 O, AOPs theoretically do not introduce

any new hazardous substances into the water.

Drawbacks:

Capital Intensive.

Complex chemistry must be tailored to specific application.

For some applications quenching of excess peroxide is require

Some treatment requires Pre-treatment of waste water. So it should be employed at the

final stage after primary & secondary treatment.

25

1.7.2. Classification of AOPs:

In this study we have used Sono Fenton as a homogeneous process (Using ultra sound) & in
future work, Photocatalysis as a heterogeneous process (Using TiO2 as catalyst) will be used.

1.7.2.1. Homogeneous Process (Sono Fenton):

In homogeneous Process, the reactants and the catalysts exist in the same phase. The
most commonly used homogeneous process includes ozone and Fenton systems (Fe+ and
Fe+/H2O2). The reactive species is the OH which is used for different purposes. The mechanism
of hydroxyl radical production by ozone can follow two paths:

26

O3 + h O2 + O (1D)
O (1D) + H2O OH + OH
O (1D) + H2O H2O2
H2O2 + h OH + OH
Similarly, the Fenton system produces hydroxyl radicals by the following mechanism:
Fe2+ + H2O2 OH + Fe3+ + OH
Fe3+ + H2O2 Fe2+ + 2OH + H+
Fe2+ + OH Fe3+ + OH
In Fenton type processes, additional sources of OH radicals should be considered: through
sonolysis of H2O2, through reduction of Fe3+ ions under UV light etc:
H2O2 + sonication OH + OH
Fe3+ + H2O + sonication Fe2+ + OH + H+
The efficiency of Fenton type processes is influenced by several operating parameters like
concentration of hydrogen peroxide, pH and concentration of catalyst. These reactions have been
proven more efficient than the other processes but the disadvantages of the process are the low
pH values which are required, since iron precipitates at higher pH values and the fact that iron
has to be removed after treatment.

1.7.2.2. Heterogeneous Process (Photocatalysis with TiO2): [Future Scope]

AOPs are based on the generation of very reactive specieshydroxyl radicals (OH) that
could oxidize wide spectra of organic matter in water quickly and non-selectively. In general,
Photocatalysis can be defined as an acceleration of a photo induced reaction by the presence of a
photo catalyst. In case of heterogeneous Photocatalysis such photocatalysts are solid
semiconductors.
Its mechanism follows the following steps:

Mass transfer of the organic contaminant in the liquid phase to the TiO2 surface.

Adsorption of the organic contaminant onto the photon activated TiO2 surface

Photocatalysis reaction on TiO2

Desorption of intermediate from TiO2

Mass transfer of the intermediate from the interface to the bulk.

27

The mechanism of the photocataytic oxidation under UV light can be presented as follows:
TiO2 + h TiO2 (eCB +hVB+)
TiO2 (hVB+) + H2O TiO2 +H+ +OH
TiO2 (hVB+) + OH TiO2 +OH
TiO2 (eCB) + O2 TiO2 +O2
O2 +H+ HO2
HO2 + HO2 H2O2 +O2
TiO2 (eCB) + H2O2 OH + OH
H2O2 +O2 OH + OH +O2
H2O2 + h 2OH
Organic compound + OH degradation products
Organic compound + TiO2 (hVB+) oxidation products
Organic compound + TiO2 (eCB) reduction products

Now to increase the effectiveness hybridization of photo catalysis with membrane process is
used. That is called Photocataytic Membrane Reactor (PMR).
It can be used in two ways:
1. Reactors with catalyst suspended in feed
2. Reactors with catalyst supported in the membrane.

Fig VI: Electron transfer in Advanced Oxidation Process

28

TiO2 over other catalysts:

Attempts have been made to photo catalytically mineralize pollutants (to convert into
CO2 and H2O) in waste water. TiO2 offers great potential as an industrial technology for
detoxification or remediation of wastewater due to several factors:
1. The process uses natural oxygen and sunlight and thus occurs under ambient conditions;
it is wavelength selective and is accelerated by UV light.
2. The photo-catalyst is inexpensive, readily available, non-toxic, chemically and
mechanically stable, and has a high turnover.
3. The formation of photo catalyzed intermediate products; unlike direct photolysis
technique is avoided.
4. Oxidation of the substrates to CO2 is complete.
5. TiO2 can be supported as thin films on suitable reactor substrates.
Thus the study aims to develop an overview of textile wastewater treatment by using a low
cost adsorbent as a conventional treatment procedure and by using Sono Fenton and
Photocatalysis as a newly developed advanced oxidation process.

29

CHAPTER 2

LITERATURE REVIEW

30

Adsorption
V.K. Gupta (2009) studied on the application of three low cost adsorbent for dye removal.
It was found that some Low cost adsorbbents, in addition to having wide availability, have fast
kinetics and appreciable adsorption capacities too. Advantages and disadvantages of adsorbents,
favourable conditions for particular adsorbateadsorbent systems, and adsorption capacities of
various low-cost adsorbents and commercial activated carbons as available in this study were
shown. [9]
B.H. Hameed (2009) used spent tea leaves (STL) as a new non-conventional and low-cost
adsorbent for the removal of cationic dye (methylene blue). Batch adsorption experiments were
carried out at 30C. Equilibrium sorption isotherms and kinetics were investigated. The
monolayer adsorption capacity was found to be 300.052 mg/g at 30 C. [10]
N. Nasuha.et.al (2011) showed removal of a basic dye, methylene blue (MB) from
aqueous solution using NaOH-modified rejected tea (N-RT). The results confirmed that the
adsorption isotherm data fitted well by Langmuir isotherm with monolayer adsorption capacity
of 242.11 mg/g. [11]

J. Raffiea Baseri (2012) Activated Carbon (TPAC) of high adsorption capacities and
highly active surface properties were prepared from Thevetia peruviana by physical and
chemical processes such as direct pyrolysis, dolomite process, Chemical activation with H2SO4 +
H2O2, impregnation of raw material with Conc. H2SO4, KOH, ZnCl2 and H3PO4 solution
respectively followed by activation at 800C. Based on the results of the characterization studies,
the activated carbon prepared by impregnation of TPAC with H3PO4 (30%) solution followed by
activation at 800C was selected as a best quality adsorbent due to highest surface area with large
number of pores and low ash content for the removal of dyes from textile industry effluent. [12]

Emine Yagmur.et.al (2012) presents the production of activated carbon from waste tea.
Activated carbons were prepared by phosphoric acid activation with and without microwave
treatment and carbonization of the waste tea under nitrogen atmosphere at various temperatures
and different phosphoric acid/precursor impregnation ratios. The surface properties were
analyzed by SEM, FTIR & BET. The maximum BET surface area was 1157m2/g for the sample
treated with microwave energy and then carbonized at 350 C. In case of application of
31

conventional method, the BET surface area of the resultant material was 928.8 m2/g using the
same precursor and conditions. [13]

Tayyebeh Madrakian.et.al. (2012) adsorption of seven different organic dyes from

aqueous solutions onto magnetite nanoparticles loaded tea waste (MNLTW) was studied.
MNLTW was prepared via a simple method and was fully characterized. The properties of this
magnetic adsorbent were characterized by scanning electron microscopy and X-ray diffraction.
Adsorption characteristics of the MNLTW adsorbent was examined using Janus green,
methylene blue, thionine, crystal violet, Congo red, neutral red and reactive blue 19 as adsorbate.
[14]

Lei Gong.et.al. (2013) showed NaOH-modified dead leaves of plane trees were used as
bio adsorbent to remove methylene blue (MB) from aqueous solution. Variable influencing
factors, including contact time, temperature, initial MB concentration and pH were studied
through single-factor experiments. The results showed that the initial concentration 100 mg/L,
bioadsorbent of 2.5 g/L, pH of 7, room temperature were the best adsorption conditions. The
NaOH-modified bio adsorbent had a high ad-sorption capacity for MB, and its saturated extent
of adsorption was 203.28 mg/g, which was higher than the un-modified dead leaves (145.62
mg/g) and some other bio adsorbents. [15]

Md. Tamez Uddin.et.al (2013) studied the potentiality of tea waste for the adsorptive
removal of methylene blue, a cationic dye, from aqueous solution. Batch kinetics and isotherm
studies were carried out under varying experimental conditions of contact time, initial methylene
blue concentration, adsorbent dosage and pH. The adsorption capacity of methylene blue onto
teawaste was found to be as high as 85.16 mg/g, which were several folds higher than the
adsorption capacity of a number of recently studied in the literature potential adsorbents. [16]

Antonio Zuorro.et.al. (2013) Spent tea leaves (STL), a solid waste that is available in
large amounts worldwide, was investigated as a potential low-cost adsorbent for the removal of
two azo dyes, Reactive Green 19 (RG19) and Reactive Violet 5 (RV5), from contaminated
waters. Preliminary experiments conducted on untreated STL showed that this material exhibited
very low removal efficiencies (<10 %). By contrast, thermal activation of STL (200 to 400 C
for up to 2 h) resulted in a significant increase in dye adsorption. After thermal exposure of STL

32

to 300 C for 1 hour, removal efficiencies of 98.8 % and 72.8 % were observed, respectively, for
RG19 and RV5. [17]
Ekta Khosla.et.al.(2014) described that the objective of the study was to examine the
potential use of Tea waste and anionic surfactant modified house hold tea waste as a low cost
sorbent for a basic dye removal from simulated textile effluent. The adsorbents were
characterized by XRD, SEM and FTIR techniques. Batch adsorption experiments were carried
out for the removal of Basic Red 12 from aqueous solution using tea waste and surfactant
modified tea waste. [18]

Jian-Zhong Guo.et.al. (2014) utilized Chemically modified bamboo (CMB) was utilized
for removing methylene blue (MB) from aqueous media The adsorbent was characterized by
Fourier transform infrared (FTIR) spectra and elemental analysis, which confirms that carboxyl
groups and diethylenetriamine were successfully introduced into the surface of bamboo. By
variation of the parameters like Temperature, Adsorbent dose, pH etc it was found that the
adsorption of MB in CMB fits Langmuir mode well, and the maximum adsorption capacity of
CMB achieved 606 mg g-1 at 298 K, which is much higher than those obtained from previously
investigated bio adsorbents. [19]

Mohammad Foroughi-Dahr.et.al.(2015) investigated the feasibility of using tea waste as

a low cost adsorbent for the adsorption of an anionic dye ( congo red). They made variation in
pH, adsorbent dosage, dye concentration, temperature etc. They also used vibratory mill treated
tea waste that leads to an increase in the adsorption capacity of tea waste from 32.6 mg/g to
43.48 mg/g. [20]

33

ADVANCED OXIDATION PROCESS

A.H. Mahvi et al (2009) assessed the photocataytic oxidation of reactive orange-16

aqueous solution by UV radiation in presence of TiO2. They investigated the effects of dye initial
concentration, pH, TiO2 loading & effect of anion present on dye degradation. The
mineralization was reported by measuring initial & final COD of the solution. He performed the
photocataytic oxidation using a 2.3-L solution containing a specific concentration of selected
dye. Samples were withdrawn from sample points at certain time intervals & analyzed for
decolorization & degradation. It showed a pseudo-first order decolorization rate of RO-16. He
then determined the pH, TiO2 loading & optimized condition for maximum degradation was
found. [21]

M. Y. Multani.et.al (2010) used ozonization process on reactive green-19. They kept

varying the operating parameters like dye concentration, pH & the time of ozone passing. He
found out that by this process [22]:
Decolorization of RG-19

99.68%

COD removed

82%

Maximum removal efficiency

Between pH 10-14

M. T. Sulak.et.al (2010) used cheap and eco-friendly bio adsorbent wheat bran. It was
very much effective for textile dyes like Reactive red 180, reactive blue 5, RO-16, direct red 80
& acid red. The % removal increased with the increased amount of dye & adsorbent. They then
studied the process kinetics and effects of parameters to found out the optimum condition [23].

N. Sharma.et.al (2010) showed that low cost adsorbent obtained from agricultural waste
products was found to be having outstanding removal capabilities. The feasibility of various nonconventional low cost adsorbents prepared from agricultural waste has been focused in this paper
[24].

34

S. Mozia (2011) presented an overview of the hybrid Photocatalysis membrane process &
their possible application. Now to increase the effectiveness hybridization of photo catalysis with
membrane process is used. That is called Photo-catalytic Membrane Reactor (PMR).
It can be used in two ways:
1. Reactors with catalyst suspended in mode.
2. Reactors with catalyst supported on the surface.
Membrane plays role of a simple barrier for photo-catalyst & of a selective barrier for molecules.
An advantage of PMRs with catalyst in suspension from the discussion was concluded that all
the PMRs with catalyst in suspension allow effective retention of photocatalyst particles [25].

M. N. Chong.et.al (2011) studied the recent R&D progresses of engineeredphotocatalysts, photo reactor systems, and the process optimizations and modeling of the photo
oxidation processes for water treatment. They described how to utilize a multi-variables
optimization approach to determine the optimum operation parameters so as to enhance process
performance and photo oxidation efficiency. They also discussed the effects of different
parameters [26].

S. Ahmed.et.al (2011) also described the influence of parameters on the heterogeneous

photocataytic degradation of pesticides and phenolic contaminants in wastewater. They
described about the different parameters that affect the degradation like [27].
1. Type and composition of the photo catalyst
2. Light intensity
3. Initial substrate concentration
4. Amount of catalyst
5. pH of the reaction medium
6. Ionic compounds in water
7. Solvent types
8. Oxidizing agents
9. Catalyst application mode
10. Calcination temperature

35

D. H. Tseng.et.al (2012) studied the influences of oxygen and hydrogen peroxide (H2O2) on
the degradation and mineralization of monochlorobenzene (MCB) in the UV/TiO2 process. Their
studies provided very useful information that the oxygen was a determining parameter for
promoting the photocataytic degradation [28].

Chih-Huang Weng.et.al. (2013) described decolorization of direct azo dye, direct blue 15
(DB15), by an advanced Fenton process coupled with ultrasonic irradiation (Fenton/US) was
investigated. Zero-valent iron (ZVI) aggregates were used as the catalyst. A positive synergistic
effect occurred when Fentons reagent was combined with ultrasonic irradiation. Experimental
results showed that the optimum conditions for decolorization were pH 3.0, Fe(0) 1 g/L, H2O2
5.15*10-3 mol/L with ultrasound density of 120 W/L at 60 kHz. These conditions yielded 99%
decolorization of DB15 solution within 10 min. [29]

Bing Chen.et.al (2013) investigated the degradation of azo dye direct sky blue 5B by
sonication combined with zero-valent iron (US-FeO) and an evident synergistic effect was
observed. The degradation of direct sky blue 5B followed a pseudo-first-order kinetics &
pseudo-second order kinetics. The degradation rate constants were found to be 0.0206 and 0.169
min_1 respectively. [30]

Hui Zhang (2014) investigated the combination of ultrasound and the advanced Fenton
process (AFP, zero-valent iron and hydrogen peroxide) for the degradation of C.I. Acid Orange
7. The effect of hydrogen peroxide concentration, initial pH, ultrasonic power density, dissolved
gas, and iron powder addition on the decolorization of C.I. Acid Orange 7 was investigated. [31]

Katie Baransi.et.al (2015) investigated the photo catalytic degradation of two phenolic
compounds, p-coumaric acid and caffeic acid, with a suspended mixture of TiO2 and powdered
activated carbon (PAC) (at pH 3.4 and 8). Adsorption, direct photolysis and photocataytic
degradation were studied under different pH and UV light sources (sunlight vs. 365 nm UV
lamps). Photo degradation of anaerobically treated and diluted (1:10) OMW by the combined
TiO2 ePAC sorbent was observed to be higher in terms of the efficiency of polyphenol removal
in comparison to COD removal. A removal of 87% of total polyphenols, compared to 58%
removal of COD, was determined after 24 h exposure to 365 nm UV light (at 7.6Wm-2). [32]

36

CHAPTER 3

AIMS & OBJECTIVES

37

We have found from the forgoing discussions that textile waste water especially
wastewater containing dye is very harmful to the environment. So lots of studies have been done
on degradation and decolorization of textile dye from waste water. It has been found from
literatures that maximum dye concentration that can be emitted is 30 40 ppm. Hence, we have
to degrade the dye to a level that is not harmful to the environment. For that here we have studied
the effects of Adsorption & Advanced Oxidation Process for the decolourization of on textile
wastewater.
Firstly, textile wastewater was simulated. (RG 19 has been treated as textile dye)
Secondly, Modified tea waste was used as adsorbent

Modified Tea Waste was used as a low cost adsorbent. Different experimental runs were
taken by changing various parameters (pH, Adsorbent Dosage, Temperature, RPM etc.).

Then kinetic studies were done. Different adsorption isotherms were taken into account
(Langmuir, Freundlich etc.)

Characteristics studies like SEM, FTIR were done.

Advantages & disadvantages of using adsorbent were discussed.

Thirdly, two kind of Advanced Oxidation Process were taken into account. Homogeneous &
heterogeneous process. Sono fenton was used as a homogeneous AOP in this study &
Photocatalysis using TiO2 will be used as heterogeneous process in future works.
Fourthly, Sono fenton process was used for dye degradation.

Different experimental runs were done varying different parameters e.g. pH, Fe2+ dosage,
H2O2 dosage etc. and optimizing them.

Studies were done based on those data.

Finally, Photo-catalytic oxidation process is done taking TiO2 as catalyst (Future scope of
work)

Different experimental runs will be done in the same process as stated above.

Studies will be done based on those data.

Thus a conclusion was drawn based on the advantages and disadvantages of different processes.

38

Simulated Textile Dye

Adsorption with
Modified Tea Waste

Advanced
Oxidation Process

Optimization of different
process parameters

Different kinetic studies

Different characterization
studies

Homogeneous Process

Heterogeneous Process

Sono - Fenton

Photocatalysis [Future Work]

Optimization of different
process parameters

Optimization of different
process parameters

Different kinetic studies

Different kinetic studies

Fig VII: Flow chart of the work to be done

39

CHAPTER 4

Adsorption

40

MATERIALS & METHODS

4.1. Materials:
Reactive

Green

19

(molecular

weight

1418.94),

molecular

formula

C40H23Cl2N15Na6O19S6, was procured from Sigma-Aldrich Chemicals. A stock solution of 300

ppm was prepared by mixing with distilled water and was diluted as per requirement. H3PO4,
NaOH and Hcl are of analytical grade, purchased from Mark India Ltd., Mumbai, India and were
used without further purification. Laboratory grade water was prepared with a Sartorious arium
pro VF pure water system. Tea waste was collected from university hostel canteen.

4.2. Preparation of adsorbent:

The tea leaves used in this work were collected from hostel canteen of Jadavpur
University. After that it was washed with boiling water for several times to remove the dirt and
dye particles of tea. Then it was boiled with a 30% H3PO4 solution for modification and the TW
along with the acid solution was kept in a closed place for 24 hours. Then it was washed with
boiling water for several times and was continued till the filtered water was dirt free and
completely color free and till the acid is removed. Treated tea wastes were repeatedly washed with
water until its pH became neutral. It was then oven dried for 48 hours at 80 C. The dried tea waste

was crushed in a mixer grinder & sieved in a screen of mesh 100 micron The prepared sample
was then stored in a plastic container for further use.

4.3. Equipments:
The batch process was conducted in a rotating & time controlling shaker (Sartorius
Certomat). The pH of the different samples was checked by using microprocessor based pH
meter by Hanna Instruments. The samples were centrifuged by a cold centrifuge (Superspin RV/F m Plasto crafts). The wet tea waste was dried in a Vacuum oven.

4.4. Analytical Instruments:

The dye concentration was determined by finding out the absorbance at max= 630 nm by
using UV-Vis spectrophotometer (Varian Cary 50).

41

Fig VIII: Time & RPM controlled rotary shaker

Fig IX: UV Spectrophotometer

Fig X: Digital pH meter

Fig XI: Cold Centrifuge

Fig XII: Vaccum Oven

42

4.5. Methods:
The batch experiments were done taking 100 ml of the dye solution of desired ppm in an
Erlenmeyer flask. pH of the solution was adjusted using NaOH or Hcl. Then requisite amount of
Modified Tea Waste (MTW) was added to the solution and was mixed by the help of vortex.
Then it was placed in a time controlled rotary shaker for 2 hrs. After that the samples were
centrifuged for 10 minutes in a cold centrifuge & then the supernatant fluid was analyzed with
the help of a UV vis Spectrophotometer. The removal of dye was measured by the following
equation:

% =

100. (1)

Where, Co = Initial dye concentration

Ct = Final dye concentration

4.5.1. Effect of Adsorbent dosage:

To study the effect of adsorbent dosage on removal of RG-19, different amounts of MTW
(0.1 1.2 g) were taken and agitated with 100 ml of RG-19 solution of 100ppm. Then the
samples were placed in different Erlenmeyer flasks and were kept in a shaker at 150 rpm for 2 hr
at 30 C without changing the pH. Samples were collected at definite time intervals.

4.5.2. Effect of pH:

pH of the dye solution has a tremendous effect on the dye removal. The effect of pH on
the dye removal was investigated in the range from 2-10. In this study, 100 ml of dye solution of
fixed initial concentration of 100 ppm at varying pH (with the help of acid or base) value was
agitated with 0.8gm of MTW in a thermostatic rotary shaker at a constant speed of 150 rpm for
2hrs at 30 C. The pH was adjusted by adding a few drops of 0.1N of NaOH & 0.1N of Hcl
solutions & was measured using a digital pH meter.

4.5.3. Equilibrium Studies:

Adsorption experiments were carried out by adding a fixed amount of sorbent (0.80 g)
into a number of 250mL stoppered glass Erlenmeyer flasks containing a definite volume (100mL
in each flask) of different initial concentrations (50300 mg/L) of dye solution without changing
the solution pH at temperature of 30 C. The flasks were placed in a time controlled rotary
43

shaker and agitation was provided at 150 rpm for 120 min to ensure equilibrium was reached. At
time t = 0 and equilibrium, the dye concentrations were measured using a double beam UVvis
spectrophotometer at 630 nm wavelength. The amount of adsorption at equilibrium, qe (mg/g),
was calculated by:

=(

) ( / ) (2)

where Co and Ce (mg/L) are the liquid-phase concentrations of dye at initial and equilibrium,
respectively. V (L) is the volume of the solution and W (g) is the mass of dry sorbent used. The
dye removal percentage can be calculated as follows:
Removal percentage =

100.. (3)

where Co and Ce (mg/L) are the liquid-phase concentrations of dye at initial and equilibrium,
respectively.

4.5.4. Batch Kinetic Studies:

The procedures of kinetic experiments were basically identical to those of equilibrium
tests. The aqueous samples were taken at preset time intervals, and the concentrations of dye
were similarly measured. All the kinetic experiments were carried out without pH adjustment.
The amount of sorption at time t, qt (mg/g), was calculated by:

=(

) ( / ) (4)

where Ct (mg/L) is the liquid-phase concentration of dye at any time.

4.5.5. Analytical Methods:

The obtained dye solution along with MTW was centrifuged for 10 minutes. The dye
concentrations were measured by measuring absorbance at 630 nm using a double beam UV
spectrophotometer. Prior to the measurement, a calibration curve was obtained by using the
standard RG solution with known concentrations.

44

Results & Discussions

Fig XIII: Decoloration of RG 19 by adsorption at optimum conditions

45

4.6. Effect of pH:

The effect of solution pH on RG19 adsorption was studied using 0.80 g of MTW, 100
mg/L dye initial concentration, pH 210 at 30 C, and the results are shown in Fig. XIV. The dye
adsorption was slightly changed over the pH value from 2 to 8. The dye adsorption was almost
constant at pH 47. The lowest dye adsorption was recorded at pH 3 (15 mg/g). The equilibrium
adsorption (qe) was found to increase with increasing solution pH. The removal % decreased
from 92 to 42% for an increase in pH from 2 to 10. The maximum removal of about 98% was
observed at pH 3. It was observed that, at lower pH (pH<3), the adsorption of RG 19 slightly
decreased despite our supposition that the positive charge of the adsorbent at lower pH values
would be in favor of the adsorption of anionic dye. Therefore, other adsorption mechanisms such
as hydrogen bonding, ion exchange, chelation, or - stacking interaction can be taken into
account for lower pH values. At higher pH (pH>3) the adsorption of the dye decreases due to
increase in concentration of OH- ions which bind with the dye, preferably in bulk solution. So the
optimum pH taken is 3.

Fig XIV: Effect of pH on decoloration of RG19 on MTW (Adsorbent

dose=0.8g/100mL; temperature = 30C; C0 =100mg/L; stirring rate = 150
rpm)

46

4.7. Effect of Adsorbent dosage:

To investigate the effect of adsorbent dose (g) on dye adsorption, the experiments were
conducted at initial dye concentration of 100 mg/L. Fig XV shows the effect of MTW dose on
the removal of RG 19. It was observed that the removal percentage increased with increase in
adsorbent dose. At equilibrium time, the % removal increased from 42% to 96% for an increase
in MTW dose from 0.1 to 0.8 g. After that, with increment of adsorbent dosage from 0.9 to 1.2g
the % removal remained constant. The increase in % color removal was due to the increase of the
available sorption surface and availability of more adsorption sites. But after 0.8g the solution
had more active sorption surface but no adsorbate was available to be adsorbed. So, optimum
MTW dose was found to be 0.8 g of adsorbent per 100mL of dye solution.

Fig XV: Effect of adsorbent dosage on decoloration of RG19 on MTW (pH=

3; temperature = 30C; C0 =100mg/L; stirring rate = 150 rpm)

47

4.8. Effect of Temperature:

Experiments at different temperatures (25 C, 30 C, 35 C, 40 C) were carried out to study
the effect of temperature on adsorption of RG 19 dye on MTW (fig XVI). It can be seen that the
adsorption capacity increased with the increment of temperature, which indicates that it is an
endothermic process. With increase in temperature the % removal increased at from 92 98%.
But in this study we have taken all the data at room temperature that is 30 C.

Fig XVI: Effect of temperature on decoloration of RG19 on MTW (pH= 3;

Adsorbent dose=0.8g/100mL; temperature = 30C; C0 =100mg/L; stirring rate
= 150 rpm)

48

4.9. Effect of stirring speed:

Experiments at different rpm (100 200rpm) were conducted to study the effect of
stirring speed on decoloration of reactive green 19 by MTW adsorbent at optimum conditions. It
is evident from the fig XVII that % removal increases as the stirring speed increases from 100
rpm to 150 rpm, as higher rpm helps more dye to come in contact of the adsorbent. But, as the
rpm increases to more than 150, % removal decreases. Increasing the speed of agitation causes
the thickness of the adsorbent boundary layer to decrease, which lowers the resistance for
transfer of dyes to the surface of the adsorbent owing to the turbulence that would be produced
by high speed. On account of this, the adsorbent molecules are forced towards the surface of the
adsorbent, facilitating the adsorption process. So the optimum stirring speed is taken as 150rpm.

Fig XVII: Effect of stirring speed on decoloration of RG19 on MTW (pH= 3;

Adsorbent dose=0.8g/100mL; temperature = 30C; C0 =100mg/L)

49

4.10. Effect of contact time and initial concentration on dye adsorption:

The effect of initial concentration & contact time on the adsorption of RG19 is shown in
Fig XVIII. It can be seen that the amount of dye adsorbed per unit mass of adsorbent increased
with the increase in initial concentration, although % removal decreased with the increase in
initial concentration. The amount of dye adsorbed at equilibrium (qe) increased from 6 to 27.3
mg/g as the initial concentration was increased from 50 to 300 mg/L. The initial concentration
provides an important driving force to overcome all mass transfer resistances of the dye between
the aqueous and solid phases. Hence, a higher initial concentration of dye will enhance the
adsorption process. However, the RG 19 % removals decreased from 98.71% to 72.89% as the
dye concentration was increased from 50 to 300 mg/L. It also shows rapid adsorption of RG 19
in the first 20 min for all initial concentrations, and thereafter, the adsorption rate decreases
gradually till it reaches equilibrium. The equilibrium conditions were reached within 6090 min
for initial concentrations less than 150mg/L while 30 min was needed for concentrations from
200 to 300 mg/L.

Fig XVIII: Effect of contact time and initial concentration on the adsorption
of RG19 on MTW (pH= 3; Adsorbent dose = 0.8g/l; temperature = 30C;
stirring rate = 150 rpm)

50

4.11. Equilibrium studies & Isotherm analysis:

Equilibrium isotherms were used to develop a relation between the equilibrium RG 19
concentration on the adsorbent & in the solution. The equilibrium isotherms in this study were
analyzed using the Langmuir, Freundlich and Temkin isotherms at 30 C.

4.11.1. Langmuir Isotherm:

The Langmuir isotherm model considers a monolayer adsorption, and the adsorbent surface is
considered to be homogeneous. This means that by the adsorption of the 1st molecules of the
adsorbate, the adsorption is restricted on those sites of the adsorbents.
The Langmuir isotherm is represented by the following equation:

(5)

Where qm (mg/g) and KL (L/mg) are the Langmuir isotherm constants. The equilibrium data were
fitted to Langmuir isotherm and the constants together with the R2 value are listed in Table 1.

Fig XIX: Isotherm analysis for Langmuir model

51

4.11.2. Freundlich Isotherm:

The Freundlich isotherm is an empirical equation assuming that the adsorption process takes
place on heterogeneous surfaces and adsorption capacity is related to the concentration of RG 19
dye at equilibrium:

ln

= ln

+ (ln

Where kf (mg/g (L/mg)

)(1/ ) ... (6)

1/n

) is roughly an indicator of the adsorption capacity and 1/n is the

adsorption intensity. The magnitude of the exponent, 1/n, gives an indication of the favorability
of adsorption. Values of n > 1 represent favorable adsorption condition. The values of kf, n and
the linear regression correlation (R2) for Freundlich model are given in Table 1.

Fig XX: Isotherm analysis for Freundlich model

52

4.11.3. Temkin Isotherm:

Temkin considered the effects of some indirect adsorbate/adsorbate interactions on adsorption
isotherms and suggested that because of these interactions the heat of adsorption of all the
molecules in the layer would decrease linearly with coverage.
The Temkin isotherm has been used in the following form:

( ) +

( ) (7)

where, B = RT/b
The constant B is related to the heat of adsorption. The constants A and B together with the R2
values are shown in Table 1.

Fig XXI: Isotherm analysis for Temkin model

53

Isotherm Parameters: (Table 1)

Langmuir
qm (mg/g)

26.3158

Ka (L/mg)

7.1316

R2

0.988

Freundlich
KF ((mg/g)(L/g)1/n

6.398

R2

0.971

3.1645

Temkin
A (L/g)

3.132

4.302

R2

0.961

Diagrams show the experimental equilibrium data and the predicted theoretical isotherms
for the adsorption of RG 19 onto MTW. The calculated isotherm constants by non-linear method
are listed in Table 1. It can be seen from Figures that Langmuir isotherm fits the data better than
Freundlich and Temkin isotherms. This is also confirmed by the high value of R2 in case of
Langmuir (0.988) compared to Freundlich (0.971) and Temkin (0.961). This indicates that the
adsorption of RG 19 on MTW takes place as monolayer adsorption on a surface that is
homogenous in adsorption affinity. Table 1 indicates that the computed maximum monolayer
adsorption capacity (qm) of MTW for RG 19 was relatively large, which was 26.31mg/g.

54

4.12. Adsorption kinetics:

The modeling of the kinetics of adsorption of RG 19 on MTW was investigated by two
common models, namely, the Lagergren pseudo-first-order model and pseudo-second-order
model.
The pseudo-first-order model was described by Lagergren as:

log(

) = log

.. (8)

where qe (mg/g) is the amount of RG 19 adsorbed at equilibrium, qt (mg/g) is the amount of RG

19 adsorbed at time t and k1 (1/min) is the rate constant of pseudo-first-order adsorption. A linear
plot of log (qeqt) against time allows one to obtain the rate constant (fig. not shown). If the plot
was found to be linear with good correlation coefficient, it indicates that Lagergrens equation is
appropriate to RG 19 sorption on MTW. So, the adsorption process is a pseudo-first-order
process. The Lagergrens first-order rate constant (k1) and qe determined from the model are
presented in Table 2, along with the corresponding correlation coefficients. It was observed that
the pseudo-first-order model did not fit well. It was found that the calculated qe values did not
agree with the experimental qe values (Table 2). This suggests that the adsorption of RG 19 did
not follow first-order kinetics.
The pseudo-second-order kinetics may be expressed as:

+ (9)

Where the equilibrium adsorption capacity (qe) and the second order constant k2(g/mg min) can
be determined experimentally from the slope and intercept of plot t/qt versus t (Fig. XXII). The
k2 and qe determined from the model are presented in Table 2 along with the corresponding
correlation coefficients. The values of the calculated and experimental qe are presented in Table
2. It can be seen from Table 2 that the pseudo-second-order model better represented the
adsorption kinetics, suggesting that the adsorption process was controlled by chemisorption.

55

Fig XXII: Pseudo-second-order kinetics

Comparison of the pseudo-first-order, pseudo-second-order adsorption rate
constants and calculated qe (qe, cal) and experimental qe (qe, exp) values
obtained at different initial RG 19 concentrations: (Table 2)

Initial
concentration
(mg/L)

Pseudo-first-order kinetic

Pseudo-second-order kinetic

model

model

qe, exp
(mg/g)

k1

qe, cal

(1/min)

(mg/g)

k2
R2

(g/mg
min)

qe, cal
(mg/g)

R2

50

5.923

0.049

0.419

0.540

0.487

5.93

0.999

100

11.57

0.064

1.267

0.712

0.207

11.61

0.999

150

16.357

0.052

2.262

0.707

0.108

16.42

0.999

200

20.5

0.041

3.670

0.645

0.052

20.57

0.998

250

23.26

0.078

5.642

0.904

0.055

23.41

0.999

300

26.24

0.064

3.805

0.744

0.065

26.38

0.999

56

CharaCterization study
SEM image:

Fig XXIII: SEM image of adsorbent (a) Before adsorption (b) After
adsorption
Fig XXIII shows the SEM micrographs of the samples before and after adsorptions.
According to these figures, highly heterogeneous pores within the MTW molecules can be
observed. It is also obvious that the pores of the adsorbent particles were packed with dye
molecules after adsorption.

FTIR image:

Fig XXIV: FTIR spectra of the adsorbent samples: after & before adsorption
57

Fig XXIV shows the FTIR spectra of MTW before and after RG 19 adsorption.It was
studied in the range of 400 to 4000cm-1 to characterize the probable reaction mechanism. It was
studied using a FTIR spectrophotometer (Perkinelmer, USA). IR adsorption bands and
corresponding possible functional groups for MTW are presented in Table 3 [33]

FT-IR of MTW after and before adsorption: (Table 3)

Before

After

Adsorption

Adsorption

3417.68

IR peak

Differences

Assignment

3402.32

15.36

Bonded OH group

2926.07

2922.41

3.66

Aliphatic C H group

2853.65

2849.99

3.66

Aliphatic C H group

2365.7

2358.38

7.32

C=N stretching

1638.53

1634.14

4.39

C=O stretching

1531.72

1518.55

13.17

Secondary amine group

1453.44

1447.59

5.85

Symmetric bending of CH3

1373.7

1370.05

3.65

Symmetric bending of CH3

1239.83

1230.32

9.51

SO3 stretching

10

1040.11

1042.31

2.2

C=O stretching

11

670.67

615.07

55.60

CC group

12

468.76

472.42

3.65

Amine group

58

OUTCOME Of ThE sTUdy

The results obtained from the study shows that acid treated modified tea waste can be
used as a very efficient adsorbent for removal of textile dye RG 19. At optimum conditions it
could absorb more than 95% of RG 19 from the dye solution. After fitting the experimental data
to different isotherm it was found that it was best described by Langmuir isotherm model at 30
C. Kinetic data were tested using the pseudo-first-order and pseudo-second-order kinetic
models. The kinetics of the adsorption process was found to follow the pseudo-second-order
kinetic model, suggesting that the adsorption process was controlled by chemisorptions. This
process is a very cost efficient process which is the main advantage of this process. But on the
other hand it contains some drawbacks like excess manual labor, production of secondary wastes
etc. So to overcome these problems we will shift our attentions to a very effective process, which
is being developed in the recent days and being used by the industries, namely Advanced
Oxidation Process.

59

CHAPTER 5

SONO-FENTON
Process
(A HOMOGENEOUS AOP)

60

MATERIALS & METHODS

5.1. Materials:
Reactive

Green

19

(molecular

weight

1418.94),

molecular

formula

C40H23Cl2N15Na6O19S6, was procured from Sigma-Aldrich Chemicals. A stock solution of 300

ppm was prepared by mixing with distilled water and was diluted as per requirement. Iron
powder (200 mesh), H2O2, NaOH and Hcl are of analytical grade, purchased from Mark India
Ltd., Mumbai, India and were used without further purification. Laboratory grade water was
prepared with a Sartorious arium pro VF pure water system.

5.2. Equipments:
The dye solution along with H2O2 & Fe-salt at a pre determined pH was placed in an
ultrasound sonicator (Sartorius, Labsonic M) system. The pH of the different samples was
checked by using microprocessor based pH meter by Hanna Instruments. The samples were
centrifuged by a cold centrifuge (Superspin R-V/F m Plasto crafts). The dye concentration was
determined by finding out the absorbance at max= 630 nm by using UV-Vis spectrophotometer
(Varian Cary 50).

Fig XXV: Probe Sonicator System

61

5.3. Experimental Methods:

Sonication of the dye solution was performed in air atmosphere with a fixed frequency of
60 kHz generated by an ultrasonic generator equipped with a titanium probe transducer. The tip
of the probe was 1.2 cm in diameter; 6 cm of the tips total length was submersed in the dye
solution. The sonication was operated in pulse mode with a 60% duty cycle. Fenton/US
experiments were conducted for a 100mL RG19 dye of desired concentrations. The pH was
adjusted to a predetermined value using a solution of either H3PO4 or NaOH. The experimental
solution was placed in a beaker and irradiated with an ultrasonic sound and appropriate amounts
of Zero Valent Ion and H2O2 were added. At desired time intervals, 10mL samples were
withdrawn from the beaker and immediately centrifuged to collect the supernatant, which was
then analyzed by UV spectrophotometer to determine the residual concentration. From the
absorbance data % of removal of dye was determined using Eq. (8)

% =

100.. (8)

Where, Co = Initial dye concentration

Ct = Final dye concentration

5.3.1. Effect of H2O2 dosage:

To study the effect of H2O2 dosage on removal of RG-19, different amounts of H2O2
(310-2 to 710-2M) were added to 1000 ml of RG-19 solution of 100ppm. Then the sample was
placed in a sonicator for sonication for 30 minutes without changing the pH & FeSO4
concentration. 10ml sample at a definite time interval was collected and analyzed.

5.3.2. Effect of FeSO4 dosage:

To study the effect of FeSO4 dosage on removal of RG-19, different amounts of FeSO4
(0.08 0.75g/L) were added to 1000 ml of RG-19 solution of 100ppm Then the sample was
placed in a sonicator for sonication for 30 minutes without changing the pH & H2O2
concentration. 10ml sample at a definite time interval was collected and analyzed.

5.3.3. Effect of pH:

To study the effect of pH on removal of RG-19, different amounts of H3PO4 or NaOH
were added to 100mL of RG-19 solution of 100ppm to adjust the pH (pH 3-6). Then the sample
was placed in a sonicator for sonication for 30 minutes without changing the FeSO4 & H2O2
concentration. 10mL sample at a definite time interval was collected and analyzed.
62

Results & discussions

Fig XXVI: Decoloration of dye solution at optimum conditions at definite time

intervals

63

5.4. Effect of Solution pH:

The pH value of the solution plays a significant role in the decoloration of RG 19,
because it governs the solubility of Fe2+ and Fe3+, and ultimately affects the production of OH
radicals. Fig XXVII shows that the decoloration of RG 19 was pH-dependent. Within 20 min
treatment, the decoloration efficiency markedly increased from 55% to 93% as a consequence of
the solution pH lowering from 6.0 to 4.0 while keeping the remaining variables constant at
suitable decoloration conditions (FeSO4 0.25 g/L; H2O2 510-2 M). This can be explained that
due to the corrosion of FeSO4 more Fe2+ was released in acid condition. The oxidation decreased
substantially at pH > 4 because of the formation of Fe precipitates Fe(OH)2(s) and Fe(OH)3(s),
which suppressed the regeneration of OH radicals and lowered catalytic activity during the
decomposition of H2O2. This implies that pH value below 4.0 should have promoted RG 19
oxidation, but studies have shown that the rate of oxidation decreased at pH less than 4.0 because
the production of OH radicals was inhibited by the formation of the complex species
[Fe(II)(H2O)6]2+, which reacted with H2O2 to form [Fe(II)(OH)(H2O)5]+. Results demonstrated
that the oxidation reaction retarded at pH 2.0 & 3.0. Since 93% decoloration can be achieved
within 20 min at pH 4.0, in terms of cost-effectiveness for practical applications, the optimum
operational condition is pH 4.0.

120
pH
pH
pH
pH

Concentration

100

=
=
=
=

3
4
5
6

80

60

40

20

0
0

10

15

20

25

30

35

Time

Fig XXVII: Effect of solution pH on decoloration (FeSO4 = 0.25 g/L; H2O2 =

510-2 M; Co = 100ppm)
64

5.5. Effect of FeSO4 dose:

FeSO4 plays an important role as a source of Fe2+ in Fenton/US reaction. The effects of
FeSO4 dose on the RG 19 decoloration was examined by varying FeSO4 dose from 0.08 g/L to
0.75 g/L while keeping the remaining variables constant at suitable decoloration conditions (pH
4.0, H2O2 510-2 M) based on aforementioned results. The experimental results are shown in Fig
XXVIII. The decoloration of RG 19 was markedly influenced by the dosage of FeSO4 in the
Fenton/US system. It was evident that a decoloration efficiency of 93% was achieved within 20
min by increasing FeSO4 dose from 0.08 to 0.25g/L to treat 100 ppm RG 19. In this study, since
FeSO4 was used, the corrosion of its surfaces in aqueous solution was the only source of Fe2+.
Under the influence of ultrasound, higher doses of FeSO4 lead to the release of greater amounts
of Fe2+. In the Fenton process, Fe2+ acts as a catalyst, which initiates the decomposition of H2O2
to produce the reactive OH radical. More OH radicals were produced from the Fentons
reaction when the dosage of FeSO4 was increased, thereby increasing the decoloration efficiency.
But when FeSO4 dose greater than 0.25g/L was used a decrease in oxidation was found. It can be
explained by at higher FeSO4 concentration more Fe2+ and Fe3+ produced causing the super
saturation of Fe hydroxide precipitation and therefore decreasing the availability of soluble Fe2+
ions in the process. Moreover, excess Fe2+ also competes for hydroxyl radicals. So the optimum
FeSO4 dose for this study is 0.25g/L.

120
FeSO4= 0.08 gm/l
FeSO4=0.16 gm/l

100

FeSO4=0.25 gm/l

Concentration

FeSO4=0.5 gm/l
80

FeSO4=0.75 gm/l

60

40

20

0
0

10

15

20

25

30

35

Time

Fig XXVIII: Effect of FeSO4 dose on decoloration (pH = 4; H2O2 = 510-2 M;

Co = 100ppm)

65

5.6. Effect of H2O2 dose:

Fig XXIX presents decoloration of RG 19 at various H2O2 concentrations and the
corresponding rate constants. The results indicate that the decoloration of RG 19 was affected by
the H2O2 dose. In the Fenton/US system, the main sources of OH radicals are majorly produced
via two reactions: (1) H2O2 under the influence of ultrasound and (2) H2O2 reacting with Fe2+.
Theoretically larger amount of H2O2 should result in the generation of more active OH radicals
if Fe2+ is not a limiting factor in the system. As expected, within 20 min treatment, the
decoloration efficiency increased from 60% to 94% as a consequence of increasing the H2O2
dosage from 310-2M to 510-2M, respectively. However, further increase in H2O2 concentration
from 510-2M to 710-2M had an adverse effect on decoloration. In the Fenton system, when the
available H2O2 exceeds a critical concentration, OH could be depleted through the scavenging
of OH by excessive H2O2 and the recombination of OH the hydroperoxy radicals (HO2)
generated from the scavenging effect are less active than the hydroxyl radicals. Therefore, an
overdose of H2O2 will decrease the decoloration rate. Therefore, the optimum dose of H2O2 was
510-2M for the decoloration of RG 19 by Fenton/US.

120
H2O2= 310-2 M
-2

-2

-2

-2

H2O2= 410

100

Concentration

H2O2= 510
H2O2= 610

80

H2O2= 710

60

40

20

0
0

10

15

20

25

30

35

Time

Fig XXIX: Effect of H2O2 dose on decoloration (pH = 4; FeSO4 = 0.25 g/L; Co
= 100ppm)

66

5.7. Enhancement of dye degradation in the Sono Fenton process:

To study the effect of different process on dye degradation, a study was done taking all
the parameters optimum (i.e. H2O2 = 510-2M; FeSO4 = 0.25 g/L & pH = 4). A 100 ppm sample
of RG 19 went through different processes like only Fenton, only sonication, Fe2+ + sonication,
H2O2 + sonication & lastly Sono Fenton. But the maximum dye degradation was found in case of
the Sono Fenton process. In this process maximum number of OH was produced from H2O2 &
water by the presence of Fe2+ along with sonication.

120

Concentration

100

80

FeSO4 + H2O2
US
H2O2 + US

60

US + FeSO4 + H2O2
FeSO4 + US
40

20

0
0

10

15

20

25

30

35

Time

Fig XXX: Effect of different process on decoloration (pH = 4; FeSO4 = 0.25

g/L; H2O2 = 510-2 M; Co = 100ppm)

5.8. Effect of different salts on Sono Fenton:

Effluent streams from dying process are typically heavily colored with high loading of
inorganic salts of great environmental importance. Because of the presence of high concentration
salt, activity of oxidation reaction will be decreased. The impacts of inorganic anions on the RG
19 decoloration by Fenton/US process were investigated. The experiments were carried out by
adding different types of salts (NaCl, NaNO3, Na2SO4, Na2CO3 & Na2HPO4) to the RG 19
solution while keeping the remaining variables constant at the conditions of H2O2 = 510-2M;
FeSO4 = 0.25 g/L & pH = 4. These salts were selected because they are likely to be present in
67

wastewater from textile and printing industries. Since the pH of the water has a significant effect
on the chemical species in the solution, at pH 4.0 and in an air atmosphere, the dominant ion
species would be Cl-, NO3- and SO42-. In the case of Na2HPO4 and Na2CO3 salt additions, the
dominant species would be H2PO4- and CO3 -, respectively. The results (Fig. XXXI) reveal that
the decoloration of RG 19 was not suppressed by the presence of Cl-, NO3- and SO42- species.
However, the extent of decoloration was not favorable in the presence of H2PO4-. A possible
reason for the retardation of RG 19 oxidation is that H2PO4- formed complexes with Fe(III) ion,
such as ferric dihydrophosphate (Fe(H2PO4)3), which are more stable than the complexes formed
by other ions (Cl-, NO3- and SO42-). Such complicated formation greatly affects the distribution
and reactivity of Fe species with H2O2. Because of the precipitation of (Fe(H2PO4)3)(s) that
occurs in the Fenton/US process with the addition of Na2HPO4, the concentration of Fe(II) and
Fe(III) is expected to be much lower than the process without Na2HPO4. The H2PO4- ion could
accept an OH radical to form the less reactive (H2PO4) radical thereby leading to the shortage
of oxidants in the system. Same thing happens in case of Na2CO3. Presence of these two salts in
wastewater streams affects the decoloration adversely.

120

Concentration

100
Nacl
NaNO3

80

Na2SO4
Na2CO3
60

Na2HPO4
Without salt

40

20

0
0

10

15

20

25

30

35

Time

Fig XXXI: Effect of different salts on decoloration (pH = 4; FeSO4 = 0.25 g/L;
H2O2 = 510-2 M; Co = 100ppm; salt conc. = 110-2 M)

68

OutcOme Of the study

The Fenton process with ultrasound irradiation using FeSO4 as the catalyst is a more
effective process for the decoloration of Reactive green 19 in aqueous solution compared with
the use of either processes alone. The use of ultrasound can enhance the corrosion of FeSO4
resulting in the continuous release of large quantities o Fe(II), which in turn triggers a more
effective Fentons reaction. Compared to the use of the Fenton reagent alone, ultrasonic
irradiation enhanced Fentons reaction significantly increased the production of OH radicals.
The decoloration was obviously affected by pH, FeSO4 dose, H2O2 dose, ultrasound power
density and addition of salts. The optimum conditions for decoloration were: H2O2 = 510-2M;
FeSO4 = 0.25 g/L & pH = 4. Under these optimum conditions, a decoloration efficiency of 95%
was achieved within 20 minutes, which is not harmful to the environment. The decoloration was
inhibited by the presence of H2PO4 in the solution, but it was not affected significantly by the
presence of Cl-, ClO4-, NO3- or SO42-. FeSO4 can be reused; however, the rate of decolouration
decreased with repeated use of FeSO4. The operating cost is not very high for this process. This
study shows that oxidation power is remarkably enhanced by ultrasonic irradiation. Overall, it
can be concluded that the Fenton/US process using FeSO4 aggregates as the catalyst is a costeffective and secondary waste free technology for treating RG 19 if the operational conditions
are properly controlled.

69

CHAPTER 6

CONCLUSIONS

70

In this study we have tried some advance processes to treat textile waste water containing
dye Reactive Green 19. Firstly, we have tried a very popular process of dye removal i.e.
adsorption. Tea waste that is basically abandoned after use has been used as a very effective
adsorbent. We have acid treated the tea waste & have used the modified tea waste for dye
removal. At optimum conditions i.e. pH= 2; Adsorbent dose=0.8g/100ml; temperature = 30C;
stirring rate = 150 rpm, it could absorb more than 95% of RG 19 from the dye solution. After
fitting the experimental data to different isotherms, it was found that it was best described by
Langmuir isotherm model at 30 C. Kinetic data were tested using the pseudo-first-order and
pseudo-second-order kinetic models. The kinetics of the adsorption process was found to follow
the pseudo-second-order kinetic model, suggesting that the adsorption process was controlled by
chemisorptions. So this study leads us to a very cost effective process. In case of adsorption
complete degradation of dye cannot be possible, which creates secondary wastes. For complete
removal of dye advanced oxidation process is being used. Advanced oxidation processes, which
are basically governed by the production of OH radicals are very efficient regarding dye
degradation. For that we have selected Sono Fenton process as a homogeneous advanced
oxidation process for dye removal. The Fenton process with ultrasound effect using FeSO4 as the
catalyst is a more effective process for the decoloration of Reactive green 19 in aqueous solution
compared with the use of either processes alone. Compared to the use of the Fenton reagent
alone, ultrasonic irradiation enhanced Fentons reaction significantly increased the production of
OH radicals. The decoloration was obviously affected by pH, FeSO4 dose, H2O2 dose,
ultrasound power density and addition of salts. The optimum conditions for decoloration were:
H2O2 = 510-2M; FeSO4 = 0.25 g/L & pH = 4. Under these optimum conditions, a decoloration
efficiency of more than 95% was achieved within 20 minutes, which is not harmful to the
environment. The decoloration was inhibited by the presence of H2PO4 in the solution, but it was
not affected significantly by the presence of Cl-, ClO4-, NO3- or SO42-. Hence, we could develop a
more effective secondary waste free technique for dye removal.
FUTURE SCOPE: In the future work we will emphasize more on the development of
different AOP techniques, as this process is very efficient to treat textile industry effluents as
well as a cost effective, secondary waste free treatment which is very much applicable in
industries now-a-days. In future we will work on photo catalysis, which is a heterogeneous AOP,
using TiO2 as a photo catalyst. The process parameters will be optimized and advantages &
disadvantages of the process will be discussed.

71

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