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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

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Dr. Chiranjib Bhattacharjee Project Supervisor Professor & former-HOD Department of Chemical Engineering Jadavpur University, Kolkata-32

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Dr. Chandan Guha Professor & HOD Department of Chemical Engineering Jadavpur University, Kolkata-32

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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

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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:

(SAMYA SUBHRA DAS)

DATE:

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

PAGE NO

1 - 29

1.1.

Waste water: A brief review

4

1.1.1. Origin

5

1.1.2. Waste water constituents

6

1.1.3. Wastewater quality indicators

6

1.2.

Industrial Wastewater

7

1.2.1.

Types of industrial waste water

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

3. AIMS & OBJECTIVES

4. ADSORPTION

30 - 36 37 - 39 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 H 2 O 2 dose

62

5.3.2. Effect

of

FeSO 4 dose

62

5.3.3. Effect of pH

62

5.4. Results & discussions: Effect of solution pH

64

5.5. Results & discussions: Effect of FeSO 4 dose

65

5.6. Results & discussions: Effect of H 2 O 2 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

REFERENCES

70 - 71 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 of RG19 on MTW

50

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 adsorption

57

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 time intervals

63

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 H 2 O 2 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

1

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.

3

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.

tank, drain field, and optionally an on-site treatment unit. Sewage is the subset of wastewater that

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

cream manufacture;

from abattoirs, creameries,

and ice

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

5

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 + O 2 → CO 2 + H 2 O + Oxidized inorganic species

Oxygen consumption by reducing chemicals such as sulfides and nitrites is typified as follows:

S -- + 2 O 2 → SO 4

NO 2 - + ½ O 2 → NO 3

--

-

Since 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 5- day 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.

7

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 un- dissolved form. The pre-cooling and subsequent purification of blast-furnace gases requires up to 20 m 3 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

where the water consumption and the generation of aqueous effluents occur Fig I: Different Stages of

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/BOD 5 ), 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 7x10 5 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.

basis of total annual world production [7]. These dyes are followed, in terms of prevalence, by

11

 

:Different classes of Textile Dyes:

 

Application

Characteristics

Substrates

Common

class

structures

 

Highly water soluble; form ionic interactions between the -NH 3 groups of fibers and the negative charge of the

+

   

Wool, polyamide, silk, nylon, leather

Azo,

Acid dyes

anthraquinone,

triarylmethane

dyes

 

Reactive dyes

Form covalent bonds with -OH, -NH or -SH groups

Cotton, wool, silk, nylon Azo, metal

Complex azo,

anthraquinone,

phthalocyanine

 

Their flat shape and length enables them to maximize van-der- Waals, dipole and hydrogen bonds

Cellulose fibers,

 

Direct dyes

cotton,

viscose, paper,

Sulphonated azo

 

leather,

dyes

nylon

 

Strong ionic interaction between dye cationic groups and the negative charges in the copolymer

 

Azo,

Basic dyes

Synthetic fibers,

paper,

inks

diarylmethane,

triarylmethane,

anthraquinone

 

Metal salts that act as “fixing agent” to improve the color fastness

 

Azo, oxazine,

Mordant dyes

Wool, leather, silk, modified cellulose fibers

triarylmethane

 

Non-ionic structure, with polar functionality, that improves water solubility, van-der- Waals and dipole forces and the color.

 

Azo, nitro,

Disperse dyes

Polyester, polyamide,

anthraquinone,

metal complex

acetate, acrylic, plastics

azo

12

Pigment dyes

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

 

Azo, metal

Paints, inks, plastics, textiles

Complex

phthalocyanine

Vat dyes

Insoluble coloured dyes which on reduction dive soluble colourless forms /leuco form with affinity for the fiber; can be oxidized back, with H 2 O 2 , to insoluble form

Cellulose fibers,

 

cotton,

viscose, wool

Anthraquinone,

indigoid

Ingrain dyes

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,

Complex

Sulphur dyes

cotton,

polymeric

viscose

aromatics

 

Non ionic dyes that dissolve the substrate to which they bind

 

Diazo,

Solvent dyes

Plastics, varnish, ink, waxes, fats

triarylmethane,

anthraquinone,

   

phthalocyanine

Other dye classes

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: C 40 H 23 C l2 N 15 Na 6 O 19 S 6 .

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.

suitable for polyester/cotton, polyester/stick blended fabric dyeing. Fig II: Molecular Structure of Reactive green 19 14

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 25°C.

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

Silica Gel

Activated Alumina

Carbons

Zeolites

Applications

Drying of gases, refrigerants, organic solvents, transformer oils Desiccant in packing and double glazing Dew point control of natural gas

Drying of gases, organic solvents, transformer oils 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 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 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

Polymers & Resins

Clay

Water purification Recovery and purification of steroids, amino acids Separation of fatty acids from water and toluene Separation of aromatics from aliphatic Recovery of proteins and enzymes Removal of colors from syrups Removal of organics from Hydrogen peroxide

Treatment of edible oils 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, it’s 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

Activated Carbon

Activated Carbon Silica Gel Modified Tea Waste (Used in this study) Fig III: Different widely popular

Silica Gel

Activated Carbon Silica Gel Modified Tea Waste (Used in this study) Fig III: Different widely popular

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 O 3 , H 2 O 2 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, CO 2 & 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

Fig IV: Outline of the Advanced Oxidation Process

Fig IV: Outline of the Advanced Oxidation Process Fig V: Oxidation potential of different elements 24

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 H 2 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:

1.7.2. Classification of AOPs : In this study we have used Sono Fenton as a homogeneous

In this study we have used Sono Fenton as a homogeneous process (Using ultra sound) & in future work, Photocatalysis as a heterogeneous process (Using TiO 2 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 + /H 2 O 2 ). 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

O 3 + hγ → O 2 + O (1D)

O

(1D) + H 2 O → OH• + OH•

O

(1D) + H 2 O → H 2 O 2

H 2 O 2 + hγ → OH• + OH•

Similarly, the Fenton system produces hydroxyl radicals by the following mechanism:

Fe

2+ + H 2 O 2 → OH• + Fe 3+ + OH

Fe

3+ + H 2 O 2 → Fe 2+ + 2OH• + H +

Fe

2+ + OH•→ Fe 3+ + OH

In Fenton type processes, additional sources of OH radicals should be considered: through sonolysis of H 2 O 2 , through reduction of Fe 3+ ions under UV light etc:

H 2 O 2 + sonication→ OH• + OH•

Fe 3+ + H 2 O + sonication → Fe 2+ + 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 TiO 2 ): [Future Scope]

AOPs are based on the generation of very reactive species–hydroxyl 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 TiO 2 surface.

Adsorption of the organic contaminant onto the photon activated TiO 2 surface

Photocatalysis reaction on TiO 2

Desorption of intermediate from TiO 2

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:

TiO 2 + hγ→ TiO 2 (e CB +h VB + ) TiO 2 (h VB + ) + H 2 O TiO 2 +H + +OH• TiO 2 (h VB + ) + OH TiO 2 +OH• TiO 2 (e CB ) + O 2 TiO 2 +O 2

O 2 +H + HO 2

HO 2 • + HO 2 H 2 O 2 +O 2 TiO 2 (e CB ) + H 2 O 2 OH• + OH

H

2 O 2 +O 2 OH• + OH +O 2

H

2 O 2 + hγ→ 2OH•

Organic compound + OH• degradation products Organic compound + TiO 2 (h VB + ) oxidation products Organic compound + TiO 2 (e CB ) 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.

in feed 2. Reactors with catalyst supported in the membrane. Fig VI: Electron transfer in Advanced

Fig VI: Electron transfer in Advanced Oxidation Process

28

TiO 2 over other catalysts: Attempts have been made to photo catalytically mineralize pollutants (to
TiO 2 over other catalysts:
Attempts have been made to photo catalytically mineralize pollutants (to convert into
CO 2 and H 2 O) in waste water. TiO 2 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 CO 2 is complete.
5. TiO 2 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 adsorbate–adsorbent 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 30°C. 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 H 2 SO 4 + H 2 O 2 , impregnation of raw material with Conc. H 2 SO 4 , KOH, ZnCl 2 and H 3 PO 4 solution respectively followed by activation at 800ºC. Based on the results of the characterization studies, the activated carbon prepared by impregnation of TPAC with H 3 PO 4 (30%) solution followed by activation at 800ºC 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 1157m 2 /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 m 2 /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 TiO 2 . They investigated the effects of dye initial concentration, pH, TiO 2 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, TiO 2 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 non- conventional 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 engineered- photocatalysts, 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

and phenolic contaminants in wastewater. They

photocataytic

degradation

of

pesticides

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 (H 2 O 2 ) on the degradation and mineralization of monochlorobenzene (MCB) in the UV/TiO 2 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 Fenton’s reagent was combined with ultrasonic irradiation. Experimental results showed that the optimum conditions for decolorization were pH 3.0, Fe(0) 1 g/L, H 2 O 2 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 TiO 2 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 TiO 2 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 TiO 2 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, Fe 2+ dosage, H 2 O 2 dosage etc. and optimizing them.

Studies were done based on those data.

Finally, Photo-catalytic oxidation process is done taking TiO 2 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
Adsorption with
Modified Tea Waste
Advanced
Oxidation Process
Optimization of different
process parameters
Different kinetic studies
Different characterization
studies

Homogeneous Process

Sono - Fenton

Heterogeneous Process Photocatalysis [Future Work] Optimization of different process parameters Different kinetic
Heterogeneous Process
Photocatalysis [Future Work]
Optimization of different
process parameters
Different kinetic studies

Optimization of different

Different kinetic studies Optimization of different process parameters Different kinetic studies Fig VII: Flow

process parametersDifferent kinetic studies Optimization of different Different kinetic studies Fig VII: Flow chart of the work

Different kinetic studiesDifferent kinetic studies Optimization of different process parameters Fig VII: Flow chart of the work to

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 C 40 H 23 C l2 N 15 Na 6 O 19 S 6 , 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. H 3 PO 4 , 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% H 3 PO 4 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 R- V/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 λ max = 630 nm by using UV-Vis spectrophotometer (Varian Cary 50).

41

Fig VIII: Time & RPM controlled rotary shaker Fig IX: UV Spectrophotometer Fig XI: Cold

Fig VIII: Time & RPM controlled rotary shaker

Fig VIII: Time & RPM controlled rotary shaker Fig IX: UV Spectrophotometer Fig XI: Cold Centrifuge

Fig IX: UV Spectrophotometer

RPM controlled rotary shaker Fig IX: UV Spectrophotometer Fig XI: Cold Centrifuge Fig X: Digital pH

Fig XI: Cold Centrifuge

rotary shaker Fig IX: UV Spectrophotometer Fig XI: Cold Centrifuge Fig X: Digital pH meter Fig

Fig X: Digital pH meter

rotary shaker Fig IX: UV Spectrophotometer Fig XI: Cold Centrifuge Fig X: Digital pH meter Fig

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, C o = Initial dye concentration C t = 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 (50–300 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 UV–vis spectrophotometer at 630 nm wavelength. The amount of adsorption at equilibrium, q e (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 C o and C e (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, q t (mg/g), was calculated by:

= ( ) × ( / ) ………………………………… (4)

where C t (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

Results & Discussions Fig XIII: Decoloration of RG 19 by adsorption at optimum conditions 45

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 2–10 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 4–7. The lowest dye adsorption was recorded at pH 3 (15 mg/g). The equilibrium adsorption (q e ) 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 π-π 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.

preferably in bulk solution. So the optimum pH taken is 3. Fig XIV: Effect of pH

Fig XIV: Effect of pH on decoloration of RG19 on MTW (Adsorbent dose=0.8g/100mL; temperature = 30C; C 0 =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.

found to be 0.8 g of adsorbent per 100mL of dye solution. Fig XV: Effect of

Fig XV: Effect of adsorbent dosage on decoloration of RG19 on MTW (pH= 3; temperature = 30C; C 0 =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. ͦ

taken all the data at room temperature that is 30 C. ͦ Fig XVI: Effect of

Fig XVI: Effect of temperature on decoloration of RG19 on MTW (pH= 3; Adsorbent dose=0.8g/100mL; temperature = 30C; C 0 =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.

process. So the optimum stirring speed is taken as 150rpm. Fig XVII: Effect of stirring speed

Fig XVII: Effect of stirring speed on decoloration of RG19 on MTW (pH= 3; Adsorbent dose=0.8g/100mL; temperature = 30C; C 0 =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 (q e ) 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 60–90 min for initial concentrations less than 150mg/L while 30 min was needed for concentrations from 200 to 300 mg/L.

30 min was needed for concentrations from 200 to 300 mg/L. Fig XVIII: Effect of contact

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 q m (mg/g) and K L (L/mg) are the Langmuir isotherm constants. The equilibrium data were fitted to Langmuir isotherm and the constants together with the R 2 value are listed in Table 1.

and the constants together with the R 2 value are listed in Table 1. Fig XIX:

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 )(1/ ) ………………

….

(6)

Where k f (mg/g (L/mg) 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 k f , n and the linear regression correlation (R 2 ) for Freundlich model are given in Table 1.

correlation (R 2 ) for Freundlich model are given in Table 1. Fig XX: Isotherm analysis

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 R 2 values are shown in Table 1.

constants A and B together with the R 2 values are shown in Table 1. Fig

Fig XXI: Isotherm analysis for Temkin model

53

Isotherm Parameters: (Table 1) Langmuir 26.3158 q m (mg/g) 7.1316 K a (L/mg) 0.988 R
Isotherm Parameters: (Table 1)
Langmuir
26.3158
q m (mg/g)
7.1316
K a (L/mg)
0.988
R 2
Freundlich
6.398
K F ((mg/g)(L/g) 1/n
0.971
R 2
3.1645
n
Temkin
3.132
A (L/g)
4.302
B
R 2
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 R 2 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 (q m ) 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 q e (mg/g) is the amount of RG 19 adsorbed at equilibrium, q t (mg/g) is the amount of RG 19 adsorbed at time t and k 1 (1/min) is the rate constant of pseudo-first-order adsorption. A linear plot of log (q e q t ) 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 Lagergren’s equation is appropriate to RG 19 sorption on MTW. So, the adsorption process is a pseudo-first-order process. The Lagergren’s first-order rate constant (k 1 ) and q e 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 q e values did not agree with the experimental q e 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 (q e ) and the second order constant k 2 (g/mg min) can be determined experimentally from the slope and intercept of plot t/q t versus t (Fig. XXII). The k 2 and q e determined from the model are presented in Table 2 along with the corresponding correlation coefficients. The values of the calculated and experimental q e 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

Fig XXII: Pseudo-second-order kinetics

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

Initial

 

Pseudo-first-order kinetic model

Pseudo-second-order kinetic model

concentration

q e , exp (mg/g)

     

k

2

   

(mg/L)

k

1

q e , cal (mg/g)

R

2

(g/mg

q e , cal (mg/g)

R

2

 

(1/min)

 

min)

 

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:

CharaCterization study SEM image: Fig XXIII: SEM image of adsorbent (a) Before adsorption (b) After adsorption

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:

were packed with dye molecules after adsorption. FTIR image: Fig XXIV: FTIR spectra of the adsorbent

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)

IR peak

Before

Adsorption

After

Adsorption

Differences

1 3417.68

3402.32

15.36

2 2926.07

2922.41

3.66

3 2853.65

2849.99

3.66

4 2365.7

2358.38

7.32

5 1638.53

1634.14

4.39

6 1531.72

1518.55

13.17

7 1453.44

1447.59

5.85

8 1373.7

1370.05

3.65

9 1239.83

1230.32

9.51

10 1040.11

1042.31

2.2

11 670.67

615.07

55.60

12 468.76

472.42

3.65

Assignment

Bonded –OH group

Aliphatic –C –H group

Aliphatic –C –H group

–C=N stretching

–C=O stretching

Secondary amine group

Symmetric bending of CH 3

Symmetric bending of CH 3

–SO 3 stretching

C=O stretching

–C–C– group

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 C 40 H 23 C l2 N 15 Na 6 O 19 S 6 , 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), H 2 O 2 , 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 H 2 O 2 & 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 λ max = 630 nm by using UV-Vis spectrophotometer (Varian Cary 50).

at λ m a x = 630 nm by using UV-Vis spectrophotometer (Varian Cary 50). Fig

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 tip’s 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 H 3 PO 4 or NaOH. The experimental solution was placed in a beaker and irradiated with an ultrasonic sound and appropriate amounts of Zero Valent Ion and H 2 O 2 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) –

( )

Where, C o = Initial dye concentration C t = Final dye concentration

5.3.1. Effect of H 2 O 2 dosage:

To study the effect of H 2 O 2 dosage on removal of RG-19, different amounts of H 2 O 2 (3×10 -2 to 7×10 -2 M) 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 & FeSO 4 concentration. 10ml sample at a definite time interval was collected and analyzed.

5.3.2. Effect of FeSO 4 dosage:

To study the effect of FeSO 4 dosage on removal of RG-19, different amounts of FeSO 4 (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 & H 2 O 2 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 H 3 PO 4 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 FeSO 4 & H 2 O 2 concentration. 10mL sample at a definite time interval was collected and analyzed.

62

% =

× 100……

…………

(8)

Results & discussions

Results & discussions Fig XXVI: Decoloration of dye solution at optimum conditions at definite time intervals

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 Fe 2+ and Fe 3+, 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 (FeSO 4 0.25 g/L; H 2 O 2 5×10 -2 M). This can be explained that due to the corrosion of FeSO 4 more Fe 2+ 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 H 2 O 2 . 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)(H 2 O) 6 ] 2 +, which reacted with H 2 O 2 to form [Fe(II)(OH)(H 2 O) 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.

120 100 pH = 3 pH = 4 pH = 5 pH = 6 80
120
100
pH = 3
pH = 4
pH = 5
pH = 6
80
60
40
20
0
0
5
10
15
20
25
30
35
Concentration

Time

Fig XXVII: Effect of solution pH on decoloration (FeSO 4 = 0.25 g/L; H 2 O 2 = 5×10 -2 M; C o = 100ppm)

64

5.5. Effect of FeSO 4 dose:

FeSO 4 plays an important role as a source of Fe 2+ in Fenton/US reaction. The effects of FeSO 4 dose on the RG 19 decoloration was examined by varying FeSO 4 dose from 0.08 g/L to 0.75 g/L while keeping the remaining variables constant at suitable decoloration conditions (pH 4.0, H 2 O 2 5×10 -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 FeSO 4 in the Fenton/US system. It was evident that a decoloration efficiency of 93% was achieved within 20 min by increasing FeSO 4 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 Fe 2+ . Under the influence of ultrasound, higher doses of FeSO 4 lead to the release of greater amounts of Fe 2+ . In the Fenton process, Fe 2+ acts as a catalyst, which initiates the decomposition of H 2 O 2 to produce the reactive OH• radical. More OH• radicals were produced from the Fenton’s reaction when the dosage of FeSO 4 was increased, thereby increasing the decoloration efficiency. But when FeSO 4 dose greater than 0.25g/L was used a decrease in oxidation was found. It can be explained by at higher FeSO 4 concentration more Fe 2+ and Fe 3+ produced causing the super saturation of Fe hydroxide precipitation and therefore decreasing the availability of soluble Fe 2+ ions in the process. Moreover, excess Fe 2+ also competes for hydroxyl radicals. So the optimum FeSO 4 dose for this study is 0.25g/L.

120 100 80 FeSO 4 = 0.08 gm/l FeSO 4 =0.16 gm/l FeSO 4 =0.25
120
100
80
FeSO 4 = 0.08 gm/l
FeSO 4 =0.16 gm/l
FeSO 4 =0.25 gm/l
FeSO 4 =0.5 gm/l
FeSO 4 =0.75 gm/l
60
40
20
0
0
5
10
15
20
25
30
35
Concentration

Time

Fig XXVIII: Effect of FeSO4 dose on decoloration (pH = 4; H 2 O 2 = 5×10 -2 M; C o = 100ppm)

65

5.6. Effect of H 2 O 2 dose: Fig XXIX presents decoloration of RG 19
5.6. Effect of H 2 O 2 dose:
Fig XXIX presents decoloration of RG 19 at various H 2 O 2 concentrations and the
corresponding rate constants. The results indicate that the decoloration of RG 19 was affected by
the H 2 O 2 dose. In the Fenton/US system, the main sources of OH• radicals are majorly produced
via two reactions: (1) H 2 O 2 under the influence of ultrasound and (2) H 2 O 2 reacting with Fe 2+ .
Theoretically larger amount of H 2 O 2 should result in the generation of more active OH• radicals
if Fe 2+ 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 H 2 O 2
dosage from 3×10 -2 M to 5×10 -2 M, respectively. However, further increase in H 2 O 2 concentration
from 5×10 -2 M to 7×10 -2 M had an adverse effect on decoloration. In the Fenton system, when the
available H 2 O 2 exceeds a critical concentration, OH• could be depleted through the scavenging
of OH• by excessive H 2 O 2 and the recombination of OH• the hydroperoxy radicals (HO 2 •)
generated from the scavenging effect are less active than the hydroxyl radicals. Therefore, an
overdose of H 2 O 2 will decrease the decoloration rate. Therefore, the optimum dose of H 2 O 2 was
5×10 -2 M for the decoloration of RG 19 by Fenton/US.
120
H
2 O 2 = 3×10 -2 M
100
H
2 O 2 = 4×10 -2 M
H
2 O 2 = 5×10 -2 M
H
2 O 2 = 6×10 -2 M
80
H
2 O 2 = 7×10 -2 M
60
40
20
0
0
5
10
15
20
25
30
35
Time
Fig XXIX: Effect of H 2 O 2 dose on decoloration (pH = 4; FeSO 4 = 0.25 g/L; C o
= 100ppm)
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Concentration

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. H 2 O 2 = 5×10 -2 M; FeSO 4 = 0.25 g/L & pH = 4). A 100 ppm sample of RG 19 went through different processes like only Fenton, only sonication, Fe 2+ + sonication, H 2 O 2 + 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 H 2 O 2 & water by the presence of Fe 2+ along with sonication.

120 100 80 FeSO 4 + H 2 O 2 US H 2 O 2
120
100
80
FeSO 4 + H 2 O 2
US
H 2 O 2 + US
60
US + FeSO 4 + H 2 O 2
FeSO 4 + US
40
20
0
0
5
10
15
20
25
30
35
Concentration

Time

Fig XXX: Effect of different process on decoloration (pH = 4; FeSO 4 = 0.25 g/L; H 2 O 2 = 5×10 -2 M; C o = 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, NaNO 3 , Na 2 SO 4 , Na 2 CO 3 & Na 2 HPO 4 ) to the RG 19 solution while keeping the remaining variables constant at the conditions of H 2 O 2 = 5×10 -2 M; FeSO 4 = 0.25 g/L & pH = 4. These salts were selected because they are likely to be present in

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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 - , NO 3- and SO 4 2- . In the case of Na 2 HPO 4 and Na 2 CO 3 salt additions, the dominant species would be H 2 PO 4- and CO 3 - , respectively. The results (Fig. XXXI) reveal that the decoloration of RG 19 was not suppressed by the presence of Cl - , NO 3- and SO 4 2- species. However, the extent of decoloration was not favorable in the presence of H 2 PO 4- . A possible reason for the retardation of RG 19 oxidation is that H 2 PO 4- formed complexes with Fe(III) ion, such as ferric dihydrophosphate (Fe(H 2 PO 4 ) 3 ), which are more stable than the complexes formed by other ions (Cl - , NO 3- and SO 4 2- ). Such complicated formation greatly affects the distribution and reactivity of Fe species with H 2 O 2 . Because of the precipitation of (Fe(H 2 PO 4 ) 3 )(s) that occurs in the Fenton/US process with the addition of Na 2 HPO 4 , the concentration of Fe(II) and Fe(III) is expected to be much lower than the process without Na 2 HPO 4 . The H 2 PO 4- ion could accept an OH• radical to form the less reactive • (H 2 PO 4 ) radical thereby leading to the shortage of oxidants in the system. Same thing happens in case of Na 2 CO 3 . Presence of these two salts in wastewater streams affects the decoloration adversely.

120 100 80 Nacl NaNO 3 Na2SO4 Na 2 CO 3 60 Na 2 HPO
120
100
80
Nacl
NaNO 3
Na2SO4
Na 2 CO 3
60
Na 2 HPO 4
Without salt
40
20
0
0
5
10
15
20
25
30
35
Concentration

Time

Fig XXXI: Effect of different salts on decoloration (pH = 4; FeSO 4 = 0.25 g/L; H 2 O 2 = 5×10 -2 M; C o = 100ppm; salt conc. = 1×10 -2 M)

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OutcOme Of the study

The Fenton process with ultrasound irradiation using FeSO 4 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 FeSO 4 resulting in the continuous release of large quantities o Fe(II), which in turn triggers a more effective Fenton’s reaction. Compared to the use of the Fenton reagent alone, ultrasonic irradiation enhanced Fenton’s reaction significantly increased the production of OH• radicals. The decoloration was obviously affected by pH, FeSO 4 dose, H 2 O 2 dose, ultrasound power density and addition of salts. The optimum conditions for decoloration were: H 2 O 2 = 5×10 -2 M; FeSO 4 = 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 H 2 PO 4 in the solution, but it was not affected significantly by the presence of Cl - , ClO 4- , NO 3- or SO 4 2- . FeSO 4 can be reused; however, the rate of decolouration decreased with repeated use of FeSO 4 . 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 FeSO 4 aggregates as the catalyst is a cost- effective and secondary waste free technology for treating RG 19 if the operational conditions are properly controlled.

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CHAPTER – 6

CONCLUSIONS

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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 = 30◦C; 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 FeSO 4 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 Fenton’s reaction significantly increased the production of OH• radicals. The decoloration was obviously affected by pH, FeSO 4 dose, H 2 O 2 dose, ultrasound power density and addition of salts. The optimum conditions for decoloration were:

H 2 O 2 = 5×10 -2 M; FeSO 4 = 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 H 2 PO 4 in the solution, but it was not affected significantly by the presence of Cl - , ClO 4- , NO 3- or SO 4 2- . 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 TiO 2 as a photo catalyst. The process parameters will be optimized and advantages & disadvantages of the process will be discussed.

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