REMOVAL OF PHENOL BY

ELECTRO,COAGULATION AND ADSORPTION

A DISSERTATION
Submitted in partial fulfillment of the
requirements for the award of the degree
of
MASTER OF TECHNOLOGY
in
CHEMICAL ENGINEERING
(With Specialization in Industrial Pollution Abatement)

By
PACHIMATIA RAJESH

DEPARTMENT OF CHEMICAL ENGINEERING

INDIAN INSTITUTE OF TECHNOLOGY ROORKEE
ROORKEE -247 667 (INDIA)
JUNE, 2009
 CANDIDATES DECLARATION

I hereby declare that the work, which is being presented in the dissertation
entitled REMOVAL OF PHENOL BY ELECTROCOAGULATION AND
ADSORPTION in the partial fulfillment of the requirements of the award of the
degree of Master of Technology in Chemical Engineering with specialization in
Industrial Pollution Abatement, submitted in the Department of Chemical
Engineering of Indian Institute of Technology Roorkee, under the kind guidance of
Dr. B.PRASAD, Associate Professor, Chemical Engineering Department, Indian
Institute of Technology Roorkee, Roorkee.

The matter embodied in this dissertation has not been submitted by me for the
award of any other degree of this or any other Institute.

Date: June2,1/009

Place: IIT ROORKEE (Pachimatla Rajesh)

CERTIFICATE

This is to certify that the above statement made by the candidate is correct to the best of
my knowledge.

(Dr. ASAD)
Associate Professor
Department of Chemical Engineering
Indian Institute of Technology
Roorkee
 ACKNOWLEDGEMENT

I take this opportunity to express my deep and sincere gratitude from the
bottom of my heart to Dr. B. Prasad, Associate Professor, Department of Chemical
Engineering, Indian Institute of Technology Roorkee, for his valuable guidance and
generous help at all stages of the work. In spite of his busy schedule, he rendered help
whenever needed, giving useful suggestions and holding informal discussions. The
invaluable guidance, constant encouragement, painstaking efforts and moral support
throughout the course of the work are gratefully acknowledged.
My thanks to lab staff Mr. Suresh Chand, Mr. Bhatnagar, Mr. A.Prathap Sing
and all other employees of Chemical Engineering Department for their help.
I am greatly indebted to all my friends whose enthusiastic support,
encouragement and help, made me come up with this report. Though it is not possible
to mention everyone, none can be forgotten for their direct/indirect help.
This report saw the light of the day only due to the encouragement and
unflinching support and love of my parents and brother. Utmost thanks are due to the
Almighty, for providing me the knowledge and wisdom for the successful completion
of this report.

(Pachimatla Rajesh)

ii
 ABSTRACT

The present study focuses on the possibility of using electrocoagulation (EC) to remove
phenol from the wastewater using a cell with vertically oriented aluminium electrodes
which are used as sacrificial anode and as cathode. The removal of phenol was
investigated in terms of various parameters such as: Initial pH, Sodium chloride
dosage, Inter electrode distance, Current density, Operating time and Initial phenol
concentration. And the present study also includes the effect of addition of Granular
activated carbon (GAC), in EC cell, on phenol removal efficiency. Removal of phenol
during EC is due to combined effect of sweep coagulation and adsorption. It is
generally accepted that coagulation is brought about primarily by reduction in net
surface charge to a point where colloidal particles, previously stabilized by electrostatic
repulsion, can approach closely enough for Van der Waals forces to hold them together
and allow aggregation. In the EC process, coagulant is generated in situ by electrolytic
oxidation of an aluminum anode material.

Results obtained with synthetic wastewater revealed the most effective removal
capacities of phenol could be achieved when the initial pH was 7. The results showed
that, at high current density of 25 mA/cm2 and at solution pH 7, remarkable removal of
90% of phenol was achieved in 2'/2 h. The rate of Electrocoagulation was observed to
increase as phenol concentration decreases; the maximum removal rate was attained at
50 mg/L phenol concentration. The addition of GAC as adsorbent resulted in
remarkable increase in the removal rate of phenol at lower current densities and
operating time, than the conventional electrocoagulation process. By the addition of
GAC in the dosages of 50, 100, 150, 200 and 250 mg/1 increases the efficiency by the
amount of 13.95, 19.95, 22.7, 26.2 and 28.8 percentage resp., after 30 min of process
with comparative to electrocoagulation without GAC. Similarly, after 120 min of
process the increase in efficiencies were found to be 3.8, 4.6, 6.7, 9.1 and 14.4
percentage resp. The experimental results with addition of GAC shows that the highest
percentage removal 97 was achieved for 120 min operating time and current density of
25 mA/cm2 which was approximately 15% more, by Conventional EC process. It is
also observed that a percentage removal of 70.1% is achieved at an adsorbent dosage of
250 mg/I whereas at an adsorbent dosage of 50 mg/I, 55.25% observed. Therefore, it

iii
has been concluded that addition of adsorbent enhances the process of
electrocoagulation, reduces the operating time and energy consumption which is
economical. The present study shows that, EC of phenol using aluminum electrodes
with Addition of GAC is a promising process.

Keywords: Electrocoagulation, Adsorption, phenol removal, Granular activated

carbon.

iv
 INDEX

CANDIDATES DICLARATION
AKCNOLEDGEMENT ii
ABSTRACT iv
LIST OF FIGURES viii
LIST OF TABLES ix
NOMUNCLATURE

1. INTRODUCTION 0

1.1. Wastewater Generation Standards 1

1.2. Major Sources of phenol 2
1.3. Sources of Phenols and other related aromatic compounds in
Waste water 3
1.4. Major Uses of phenol 4
1.5. Phenol effluent standards from different industries 4
1.6. Effects of phenol 5
1.6.1. Effects of Human Exposures 5
1.6.2. Effects of Animal Exposures 6
1.7. Abatement Technologies for Phenol in Wastewater 7
1.7.1. Separation by adsorption 7
1.7.2. Separation by steam distillation 8
1.7.3. Separation by extraction 9
1.7.4. Membrane Process 9
1.7.5. Membrane Pervaporation 9
1.7.6. Oxidative polymerization with oxygen in the presence of
enzyme 10
1.7.7. Oxidation with hydrogen peroxide
10
1.7.8. Heterogeneous Fenton Process 10
1.7.9. Photo catalytic oxidation 10
1.7.10. Application of electrical discharges to degradation
of phenol 11
1.7.11. Biochemical abatement 11

2. ELECTROCOAGULATION FUNDAMENTALS 13

2.1. Phenol electrochemical 14

2.2. Theory of EC 14
2.3. Theory of adsorption 15
2.4. Electrochemistry 16
 2.5. Different Electrode Connection Mode 18
2.5.1. Monopolar electrodes in parallel connections (MP-P) 18
2.5.2. Monopolar electrodes in serial connections (MP-S) 19
2.5.3. Bipolar electrodes in serial connections (BP-S) 19
2.6. Coagulation 19
2.7. Flotation 20
2.8. Electro coagulation Vs. Chemical Coagulation 20
2.9. Advantages and Disadvantages of Electrocoagulation 21
2.9.1 Advantages 21
2.9.2. Disadvantages 22
2.10. Factors Affecting Electrocoagulation Process 22
2.10.1. Effect of Current Density on the Process 23
2.10.2. Presence of Nacl 23
2.10.3. Effect of pH on the Process 23
2.10.4. Effect of Inter-electrode Distance on the Process 24
2.10.5. Effect of electrolysis time on the Process 24
2.10.6. Effect of Initial Concentration on the Process 24
2.11. Objective of the present study 24

3. LITERATURE REVIEW 26

3.1. Literature review on Phenol removal by electrocoagulation 27

3.2. Literature review on Phenol removal by Chemical, Biochemical
and other technologies. 34

4. EXPERIMENTAL PROGRAMME 44

4.1. General 45
4.2. Materials and Method 45
4.3. Experimental Apparatus 46
4.4. Experimental Procedure 48
4.5. Analysis of Phenol samples by 4-Amino antipyrene method 49
4.6. Characterization of Aluminium Electrode and Sludge 50
4.6.1. Scanning Electron Micrograph (SEM) and EDAX 50
4.6.2. Thermal Analysis 51
4.6.3. Phenol solution Analysis 51

5. RESULTS AND DISCUSSIONS 52

5.0. General 53
5.1. Batch Electrocoagulation study 53
5.1.1. Effect of Initial pH (PH.) on Percentage Removal of Phenol 53
vi
 5.1.2. Effect of sodium chloride dosage on percentage removal 53
5.1.3. Effect'of Inter electrode distance on Phenol Removal
Efficiency 54
5.1.4. Effect of Current density and Operating Time on Phenol
Removal efficiency 54
5.1.5. Effect of Initial Phenol Concentration on removal efficiency
And E.Consumption 54
5.1.6. Influence of Sodium Chloride on E.Consumption 55
5.2. Batch electrocoagulation with addition of GAC studies 55
5.3. Characterization of Aluminum Electrode and Sludge 56

6. CONCLUSIONS AND RECOMMANDATIONS 72

6.1. Conclusions 73

6.2. Recommendations 74

7. REFERENCESS 75

8. APPENDIX 82

Table.A-1. Effect of Initial pH (P140) on the removal of phenol 83

Table.A-2. Effect of Sodium Chloride Dosage on the removal of phenol 83
Table.A-3. Effect of Initial Phenol Concentration on removal efficiency 83
Table.A-4. Effect of Current density and Operating Time on Phenol
removal efficiency 84
Table.A-5. Effect of Inter electrode distance on Phenol Removal
Efficiency 85
Table.A-6. Effect of Initial Phenol Concentration on E. Consumption 85
Table.A-7. Influence of Sodium Chloride on E.Consumption 85
Table.A-8. Effect of GAC Addition on % phenol Removal 85
Table.A-9. Effect of GAC Addition on % phenol Removal 86

vii
 LIST OF FIGURES

Fig No Title Page No

2.1 Schematic diagram of two-electrode electrocoagulation cell 17

2.2(a) MP-P System 19

2.2(b) MP-S System 19

2.2(c) BP-S System 19

4.1 Phenol structure. 44

4.2 Schematic Experimental setup 45

4.3 Experimental Setup 46

4.4 Calibration curve. 49

5.1 Effect of Initial PH0 on Percentage Removal of Phenol 58

5.2 Effect of sodium chloride dosage on percentage removal 58

5.3 Effect of Interelctrode distance on Phenol Removal Efficiency 59

5.4 Effect of Current density and Operating Time on Phenol 59

removal efficiency
5.5 Effect of Initial Phenol Concentration on removal efficiency 60
5.6 Effect of Initial Phenol Concentration on E. Consumption 60

5.7 Influence of Sodium Chloride on E.Consumption 61

5.8 Effect of GAC Addition on % phenol Removal 61

5.9 Effect of GAC Addition on % phenol Removal 62

5.3.1 Aluminium anode plate surface prior to use in 63

electrocoagulation experiment
5.3.2 Aluminium anode plate surface after used in electrocoagulation 64
with dents
5.3.3 scanning micrograph of Granular activated carbon before use 65
in electro coagulation at lk magnification
5.3.4 scanning micrograph of Sludge produced after electro 66
coagulation with GAC addition at lk magnification.
5.3.5 Scanning micrograph of Sludge produced after electro 67
coagulation at lk magnification.
5.3.6 DTA-DTG-TG plots of Granular activated carbon at various 69

viii
 conditions in air atmosphere
5.3.7 DTA-DTG-TG plots of electrocoagulation of generated sludge 70
at various conditions in air atmosphere
5.3.8 DTA-DTG-TG plots of electrocoagulation of generated sludge 71
at various conditions in Nitrogen atmosphere

LIST OF TABLES

Table No Title Page No

1.1 Wastewater Generation Standards 1
1.3 Sources of Phenols and other related aromatic compounds in 3
waste Water
1.5 Phenol effluent standards from different industries 4
3.1 Literature review on Phenol removal by Chemical, 33
Biochemical and other technologies
4.1 Physical and Chemical Properties 44
4.2 Chronic Toxicity Summary 45
4.3 Reactor Specifications 47
Table.A-1 Effect of Initial pH (PHo) on the removal of phenol 83
Table.A-2 Effect of Sodium Chloride Dosage on the removal of phenol 83
Table.A-3 Effect of Initial Phenol Concentration on removal efficiency 83
Table.A-4 Effect of Current density and Operating Time on Phenol 84
removal efficiency
Table.A-5 Effect of Inter electrode distance on Phenol Removal 85
Efficiency
Table.A-6 Influence of Sodium Chloride on E. Consumption 85
Table.A-7 Effect of GAC Addition on % phenol Removal 85
Table.A-8 Effect of GAC Addition on % phenol Removal 86

ix
 NOMENCLATURE
ABBREVATION

COD Chemical Oxygen Demand (mg/1)

EC Electrocoagulation
SEM Scanning electron microscope
XRD X-ray diffraction
EDAX Energy dispersive X-ray analysis

NOTATIONS

Cf Final phenol concentration (mg L-1)

C. Initial phenol concentration (mg III )
I Applied current (A)
m Weight of treated wastewater (g)
M Molecular weight of aluminum (g/mol)
t retention time (s)
V voltage (V)
pH. Initial pH

T Temperature
Greek letter
Wave length (nm)
 CHAPTER -1

INTRODUCTION

1_11 _,
* ; 01
 Phenol is a highly toxic and carcinogenic compound and its biodegradation is very
important to meet the environmental regulations. Phenols are widely consumed in the
industry such as in preservers of paint, leather and textile goods, and in the production of
resins, disinfectants, medicine, caprolactam and bisphenol. Phenols are among the more
refractory, hard to treat components of refinery wastewater. They may arise from various
refinery operations including catalytic cracking and effluents from caustic treating processes
using in gasoline sweetening.
Improper handling of these compounds and/or inappropriate disposal of their wastes
into water is a major pollution, as many of phenolic compounds are resistant to conventional
water treatment processes, and some are recognized as suspected carcinogens Phenolic
compounds are common contaminants in wastewater, where they appear as a result of
imperfect manufacturing and/or inadequate treatment operations in petroleum, petrochemical,
coal, and phenol producing industries. Phenol occurs naturally as coal tar, and is formed
during decomposition of organic materials. Much of the phenol that is present in the
environment is due to anthropogenic activities such as wood burning, smoking, rubbish
incineration and car exhausts.

1.1. Wastewater Generation Standards (Source CPCB website)

S. No. Industry Quantum

I Integrated Iron & steel 16 m3/tonne of finished steel
2 Sugar 0.4m3/tonne of cane crushed
3 Pulp & Paper Industries
(a) Large pulp & paper
(i) Pulp & paper 175 m3/tonne of paper produced
(ii) Rayon grade pulp 150 m3/tonne of paper

(b) Small pulp & paper

(i) Agro-residue based 150 m3/tonne of paper produced
(ii) Waste paper based 50 m3/tonne of paper produced
4 Fermentation Industries
(a) Maltry 3.5 m3/tonne of grain processed
(b) Brewer 0.25 m3/kL of beer produced
(c) Distillery 12 M3/kL of alcohol produced
5 Caustic Soda
(a) Membrane cell process 1m3/tonne of caustic soda produced
excluding cooling tower blowdown

1
 (b) Mercury cell process
6 Textile Industries: Man-made fibre
(i) Nylon & Polyster
(ii) Voscose Staple Fibre
(iii) Viscose Filament Yarn
7 Tanneries
8 Starch Glucose and related products
9 Dairy
10 Natural rubber processing industry
Fertiliser
(a) Straight nitrogenous fertiliser
(b) Straight phosphatic fertiliser (SSP &
TSP)
excluding manufacture of any acid
(c) Complex fertiliser
II Biochemical oxygen demand (3 days at
27°C), mg/I, max.
4 m3/tonne of caustic soad produced
(mercury bearing). 10% below down
permitted for cooling tower.
120 m3/tonne of fibre produced
150 m3/tonne of product
500 m3/tonne of product
28 m3/tonne of raw hide
8 m3/tonne of maize crushed
3 m3/kL of Milk
4 m3/tonne of rubber
5 m3 /tonne of urea orequivalent
produced

(a) Straight nitrogenous fertiliser

(b)Straight phosphatic fertiliser (SSP & 0.5 m3/tonne of SSP/TSP

TSP) excluding manufacture of any acid

(c)Complex fertiliser Standards of nitrogenous and

phospathic fertilisers are applicable
depending on the primary product

1.2. Major Sources of phenol

■ Phenol enters the environment from natural sources such as coal tar as well as chemical
wastes from industries that manufacture resins, plastics, adhesives, rubber, iron, steel, and
aluminium and from pulp mills and wood treatment facilities.
■ It is also found in disinfectants, cleaners, cigarette smoke, and motor vehicle emissions
■ Phenol is released from municipal wastewater treatment plants. The major industry
sectors include the pulp, paper and wood products sector, the mineral (non-metallic)
products sector, the chemical products sector, the steel and metal products sector, and the
petroleum refining and products sector.
• Phenol is produced as a result of burning wood and automobile exhaust.

2
• Natural sources of phenol in water are animal wastes and decomposition of organic
wastes.
■ Phenol contamination of ground water occurs secondary to leaching from contaminated
soil after spills of phenol and hazardous releases.
■ Another source of phenol is the mainstream smoke from tobacco products. The
concentrations of phenol released into environment in this side stream smoke range from
100 to 420 micro grams per cigarette.
■ Phenol is used heavily within the pulpwood industry, and so this is one of the more
common occupational exposure sites. Exposure and absorption of phenol if mainly via
dermal or gastrointestinal pathways.
• Industries and occupations associated with phenol exposure are pharmaceuticals and the
iron and steel, leather-tanning, aluminum-forming, electrical. Organic —and plastic
manufacturing, paint and link formation, and rubber industries, Phenol containing
medicinal uses include mouthwashes, throat lozenges, and phenol containing ointments,
nose and ear drops, analgestic rubs and antiseptic lotions.
■ Phenol is present in the atmosphere as an emission from motor vehicles and as a photo
oxidation product of benzene.

1.3. Sources of Phenols and other related aromatic compounds in waste

Water
Source Significant phenolic compounds
Petroleum Refining Hydrocarbons (alkanes, cycloalkanes, polyaromatic HC), benzes,
substituted benzenes, toulenes, n-octanes, n-decanes, naphthalene,
hepatanes, phenol, cyanide, sulphide and ammonia, butadiene.
Petrochemicals and m-amino phenols, resorcinol, dinitrophenol, p-nitrophenol,
Basic organic chemical trinitrophenol, benzene sulfonic acids, aniline, chlorobenzenes,
manufacture toluene.
Coal refining Phenols, catechol, o-, m-, p-cresols, resorcinol, hydroquinone,
pyrogallol, polyaromatic hydrocarbons, pyridines, pycolines,
litidines, xylene, toluene, benzoic acid.
Pharmaceuticals Toluene, benzyle alchohols, phenyl acetic acid, chlorinated
products of benzene, chloroform, ether, ethy 1 alchohol
Tannery Tannin, catechin, phenol, chlorophenol, nitrophenol
Pulp and paper mills Lignin, vanillin, vanillic acid, dehydrodivanillin, ferulic acid,

3
 cinnamic acid, synringic acid, vieratic acid, protocatechuic
acid,gentisic acid, benzoic acid, guadiochols, catechol, coniferyl
alchohol, dehydroconiferyl alchohol, phenyl propionic acid.

1.4. Major Uses of phenol

A Phenol is used to make many items including plastics, fertilizers, paints, rubber,
adhesives, paper and soap, iron, steel, aluminium.
A Phenol is also used in the preparation of cosmetics including sunscreens, hair dyes, and
skin lightening preparations.
A. Phenol has antiseptic properties. It is widely used as an antiseptic and anaesthetic in
sore throat lozenges.
➢ It is also the active ingredient in some oral anesthetics such as Chloraseptic spray.
➢ Phenol was also the main ingredient of the Carbolic Smoke Ball, a device marketed in
London in the 19th century as protecting the user against influenza and other ailments.
• It is also used in the production of drugs (it is the starting material in the industrial
production of aspirin), herbicides, and synthetic resins (Bakelite, one of the first
synthetic resins to be manufactured, is a polymer of phenol with formaldehyde).
➢ Compounds containing phenol moieties can be used to prevent ultraviolet light-
induced damage to hair and skin due to the UV-absorbing properties of the aromatic
ring of the phenol.
➢ These compounds also act as free radical scavengers and are claimed without evidence
to prevent premature aging and cancer caused by oxidative stress.
➢ It is also used in cosmetic surgery as an exfoliant, to remove layers of dead skin.
➢ It is also used in phenolization, a surgical procedure used to treat an ingrown nail, in
which it is applied to the toe to prevent regrowth of nails.
A It is widely used as a disinfectant for industrial and medical applications.
A It also serves as a chemical intermediate for manufacture of nylon 6 and other man-
made fibers and for manufacture of epoxy and other phenolic resins.
➢ As a solvent for petroleum refining.

1.5. Phenol effluent standards from different industries (source CPCB website)

Sno Type of industry Discharge limit

1 Coal washers (Phenolic) 1.0 mg/1

4
2 Coke oven (Phenolic as C6H5OH) 5 mg/1
3 Dye& dye intermediate industry 1.0mg/I
(Phenolic as C6H5OH)
4 Integrated iron& Steel plant 1.0 mg/I
5 Cotton textile industry 5.0 mg/1
6 Oil refinery 0.35 mg/1
7 Oil drilling& Gas extraction Industry 1.2 mg/1
8 Organic chemicals manufacturing industry 5 mg/I
9 Paint industry 1.0 mg/I
10 Pesticide industry 1.0 mg/1
11 Petrochemicals 5.0 mg/I
12 Pharmaceuticals industry 1.0 mg/I
13 Small scale industry 5.0 mg/I

1.6. Effects of phenol

1.6.1. Effects of Human Exposures

Probable routes of human exposure to phenol are inhalation, ingestion, and dermal contact.

✓ The information that is available on the health effects of phenol exposure to humans is
almost exclusively limited to case reports of acute effects of oral exposure, dermal
exposure, or occupational exposures, including some exposure by inhalation.
✓ Phenol is a strong eye and respiratory irritant. It is corrosive to the eyes and skin upon
direct contact.
✓ Acute inhalation exposure may cause nausea, vomiting, cardiac arrhythmias,
circulatory collapse, convulsions, and coma.
✓ In one study, muscle pain, weakness, enlarged liver, and elevated levels of liver
enzymes were found in an individual after inhalation and dermal exposure to phenol
and other chemicals.
✓ Phenol poisoning is associated with headache, fainting, vertigo, and mental
disturbances which are likely symptoms of neurological effects well documented in
animal studies.
✓ Ochronosis or discoloration of the skin, and other dermatological disorders may result
from dermal phenol exposure).

5
 ✓ Several investigators have reported that the use of phenol in the surgical procedure of
skin peeling can produce cardiac arrhythmias although specifics of dose received
were not determined and would be expected to be high.
✓ Arteriosclerotic heart disease, emphysema, disease of the digestive system, and
cirrhosis of the liver were inversely related to the extent of phenol exposure.
✓ No studies were located regarding adverse developmental or reproductive effects of
phenol in humans.
✓ Workers exposed continuously for an unspecified period of time to an average air
concentration of 4 ppm phenol experienced no respiratory irritation. No adverse
effects were reported among workers in a Bakelite factory who were exposed to levels
of phenol up to 12.5 mg/m3 (3.3 ppm). In this study urinary phenol levels were
measured and were observed to return to pre exposure levels within 16 hours after
exposure indicating a relatively rapid clearance of phenol from the body.

1.6.2. Effects of Animal Exposures

✓ In animal studies, a number of sub chronic and chronic studies employing oral and
inhalation routes of exposure are available as well as shorter term studies using the
dermal route of exposure.
✓ Responses observed in animal studies include: pulmonary damage (inhalation
exposure), myocardial injury (inhalation and dermal exposure), liver damage
(inhalation exposure), renal damage (inhalation exposure), neurological effects
(inhalation exposure), developmental effects (oral exposure) and dermal effects
(dermal exposure).
✓ Comparison of the three routes of exposure found that oral exposure was less
effective at producing systemic toxic effects possibly due to the rapid metabolism of
phenol to sulfate and glucuronide conjugates by the gastrointestinal tract.
✓ Comparison of health effects among studies using dermal, oral and inhalation routes
of exposure finds that inhalation is a sensitive route of exposure for laboratory
animals.
✓ Deichmann et al. (1944) exposed guinea pigs, rats, and rabbits to concentrations of
phenol between 26 and 52 ppm for 28-88 days depending on species. Guinea pigs
exposed for 7 hours per day, five days per week, for four weeks, displayed signs of
respiratory difficulty and paralysis primarily of the hind quarters, indicating
neurological effects. Five of twelve animals exposed at this concentration died at 28

6
 days. At necropsy, extensive myocardial necrosis, lobular pneumonia, fatty
degeneration of the liver, and centrilobular hepatocellular necrosis were observed in
all animals exposed at this level. Guinea pigs that were necropsied at 41 days also
exhibited pulmonary inflammation, pneumonia, bronchitis, endothelial hyperplasia,
and capillary thrombosis. Rabbits exposed at these same concentrations did not
exhibit any signs of discomfort, but showed similar findings at necropsy at 88 days.
Rats were less sensitive in this study with an apparent NOAEL of 26 ppm phenol for
these effects. In this study, guinea pigs were the most sensitive species

1.7. Abatement Technologies for Phenol in Wastewater

Phenols are present in wastewater of various industries, such as refineries (6—

500mg/1), coking operations (28-3900mg/1), coal processing (9-6800mg/1), and manufacture
of petrochemicals (2.8-1220 mg/1). Phenols are also the main organic constituents present in
condensate streams in coal gasification and liquefaction processes. Other sources of waste
stream water containing phenols are pharmaceutical, plastics, wood products, paint, and pulp
and paper industries (0.1-1600mg/1). Due to the toxic nature of some of these compounds the
Environmental Protection Agency has set a water purification standard of less than 1 part per
billion (ppb) of phenol in surface waters. This section gives about the brief discussion about
the different processes for separation of phenol from wastewater and destruction of phenol in
wastewater like Conventional technologies including extraction, adsorption on activated
carbon, steam distillation, bacterial and chemical oxidation, electrochemical techniques,
irrad iation [2] .
1.7.1. Separation by adsorption
Adsorptive processes are widely used in the purification of polluted streams and
diluted wastewater. The adsorption technique is also used to reducing phenols in wastewater.
In fact, wastewater treatment using activated carbon is one of the most important uses of
activated carbon. The content of phenolic compounds in industrial wastewater (about 200-
2000 mg/L) is usually higher than the standard limits (mostly less than 0.5 mg/L) established
for their release into aquatic environment. There is scope for developing adsorbents from
low-cost materials, such as fertilizer wastes, sawdust, wood, and rice husk, by several
chemical treatments. Adsorption Processes are low cost and efficient processes even though
they certain limitations. Coal, Residual coal, and Residual treated with 1-13PO4 are used as the
adsorbents. Low cost adsorbents such as coke, coke breeze, Fly ash, rice husk, and rice husk

7
char have also been used. The adsorbent capacity of Residual coal increased after treatment
with phosphoric acid which give a better result as compared with above adsorbents[3].
Phenol also effectively removed by agro-waste adsorbents like Carbon rich black gram husk
(BGM), green gram husk, and rice husk. Equilibrium adsorption data for phenol by the
adsorbents can be best represented by the Redlich—Peterson isotherm and BGH seemed to be
the best adsorbent of the three for the removal of phenol from its aqueous solution. For the
removal of small amounts of phenol by biological treatment using adsorbent like granular
activated carbon, bagasse ash and wood char coal for which efficiency of phenol removal are
found to be 98%, 90%, 90% [4] and we can also use neutralized red mud as adsorbent for
removal of traces of phenol. Some resins also used for phenol removal XAD-2, AP-246 and
OC-1074 in GAC found to be effective [5]. There are also new processes for removing the
pollutants in aqueous Solution like activated alumina bed in pulsed high-voltage electric field
was investigated for the removal of phenol. The phenol removal rate increased with
increasing applied voltage, increasing pH value of the solution, air aeration, and adding Fe2+.
The addition of sodium carbonate reduced the phenol removal rate because it was a radical
scavenger. The additive of Fe2+ could promote the phenol degradation mainly due to the
formation of •OH. With the discharge progressing, phenol could be mineralized to form CO2
and H2O. Although this method needs some energy consumption, its advantage is obvious. It
can produce many active species, such as .0H, 03, H202, and so on synchronously, which
has high oxidation potential and can oxidize organic pollutions effectively.Conventional
fixed bed processes involve a saturation, adsorption or loading step, followed by desorption,
elution or regeneration steps. However, regeneration may be not possible or not convenient:
in this case the saturated adsorbent bed is removed and disposed or, in case, destroyed by
burning in appropriate furnaces. The following possible interactions between the carbon
surface and the phenols have been proposed by [6]: (a) electron donor—acceptor interactions
between the aromatic phenolic ring and the basic surface oxygen's, such as carbonyl groups;
(b) dispersion effect between the aromatic phenolic ring and the electrons of the graphitic
structure; (c) electrostatic attraction and repulsion when ions are present. On the other hand,
Terzyk et al.distinguished the following three stages of the mechanism of phenol adsorption
on ACs: adsorption at the infinite dilution, micropore filling, and adsorption in larger
micropores and mesopores. Owing to the amphoteric character of a carbon surface its
adsorption properties may be influenced by the PH value of the solution.
1.7.2. Separation by steam distillation

8
 Guide et al. mentioned about the removal of phenol from organic media by steam
distillation processes, just based on the steam volatility of phenol. On the other hand,
distillation may allow the drying of phenol from rich phenol—water mixtures. Phenol—water
solutions have a minimum azeotrope, at 9.21% phenol (w/w), corresponding to a molar
fraction of 0.019, 94.5°C at 1 atm. Azeotropic distillation and/or steam stripping should also
allow the purification of water from phenol impurities. The azeotrope, recovered as the head
fraction, should split and the phenol-rich phase may be recovered, while the water rich phase
may be refluxed to the column [7].
1.7.3. Separation by extraction
Several organic solvents, such as hydrocarbons and oxygenated compounds, may
allow the extraction of phenol from water. Among others, n-hexane and cyclohexane,
benzene, toluene, ethyl benzene, cumene, acetate esters, di-isopropyl ether, methyl-iso-butyl
ketone. The so-called "Phenosovan" extraction process, is used to remove phenol from
waters in gasification plants, as well as in coke oven and carbonization plants, in the phenol
industry, and in coal hydrogenation plants. The filtered and cooled phenolic effluent is treated
counter-currently with a suitable solvent, usually di-isopropylether (DIPE) in a multistage
extractor [7].

1.7.4. Membrane Process

Among the different processes described for removal or degradation of phenolic

compounds, hybrid processes that combine pressure driven membrane processes with
adsorption processes have been developed. In order to optimise those hybrid processes, a
detailed study of the effectiveness of the membrane process step is necessary. Some factors
related to molecular characteristics of phenol, such as solubility, acidity or hydrogen bonding
ability, favour phenol to be sorbed into the membranes and to be transported across them,
resulting in low rejection values. Those factors explain the decreases of rejection when
pressure is increased [8].

1.7.5. Membrane Pervaporation

Pervaporation is a quite recent technology applied to the removal of organics from

water. Pervaporation membranes separate water at the feed side and a vapour at the permeate
side, simultaneously evaporating the permeating compound. Polyether—polyamide block
copolymer (PEBA) membrane, which is particularly useful for the separation of aromatics,

9
was also found performant to separate phenol from water in an earlier study .The separation
of a phenol-water mixture can be done efficiently by polyurethane membrane.

1.7.6. Oxidative polymerization with oxygen in the presence of enzyme

Enzymes called tyrosinase (also known as polyphenol oxidase) and laccase convert
phenols using oxygen into o-quinones. These compounds are further converted into heavier
oligomeric species that may be more easily filtered and/or adsorbed on a solid. Chitosan is
apparently particularly active useful in the absorption of these compounds [8].

1.7.7. Oxidation with hydrogen peroxide

Hydrogen peroxide (H202) has effective oxygen content, low cost, safe storage and
operation methods, and above all, an environmentally friendly nature. The standard reduction
potentials of hydrogen peroxide

H202 +2H+ +2e- —> 2H20 = 1.77V

H02- +H20 + 2e- 30H- = 0.87V

Imply that it is a strong oxidant in both acidic and basic solutions. The reactivity of hydrogen
peroxide is generally low and largely incomplete due to kinetics, in particular in acidic media,
while being much enhanced by homogeneous and/or heterogeneous catalysts.

1.7.8. Heterogeneous Fenton Process

The application of conventional homogeneous Fenton reaction is complicated by the
problems typical of homogeneous catalysis, such as catalyst separation, regeneration, etc.
Moreover, it is necessary to control PH carefully to prevent precipitation of iron hydroxide.
Typically, the activity of microporous catalysts in phenol oxidation with H202 is maximal at
PH 3 to 4 and is accompanied with substantial iron leaching. Particular interest has been
devoted to microporous catalysts. One of the most popular is Fe-ZSM-5 zeolite [7], which
has been found to be very active but may suffer from diffusion limitation due to relatively
small size of its pores.

1.7.9. Photo catalytic oxidation

Heterogeneous photo-catalysis using semiconductor catalyst under UV irradiation is
highly successful in mineralization of phenol. Photo-catalysis process depends on redox
reactions taking place on the surface of the semiconductor catalyst/solution interface upon

10
irradiation of semiconductor particles with light of specific energy (wavelength), higher than
the band-gap [9].
1.7.10. Application of electrical discharges to degradation of phenol
Interest in the application of electrical discharges for the degradation of organic
pollutants in aqueous solution has grown enormously, mainly because of high removal
efficiency and environmental compatibility of these techniques. Several different processes,
such as electro-hydraulic discharge (EHD), pulsed corona discharge (PCD), and glow
discharge electrolysis (GDE) are being developed. Among them, PCD has received the most
extensive investigations because it can directly inject the electrical energy into an aqueous
solution through plasma channels.
1.7.11. Biochemical abatement
In recent years, phytoremediation which was defined as the use of green plants to
remove, contain or render harmless organic or inorganic environmental contaminants has
been recognized as a cheap and eco friendly alternative technology that can be tried out for
the remediation of organic contaminants. Moreover, it has many advantages in comparison to
other methods [2]. Many microbial strains capable of degrading phenol have been cited such
as Pseudomonas putida, Pseudomonas fluoroescens, Acinetobacter, Trichosporon cutaneum
and Candida tropicalis. Co-aggregates may enable the proper spatial location of different
species and facilitate the opportunity to form essential partnerships within the growing bio
films, thus influencing the overall development of the complex microbial community.
Nocardia hydrocarbonoxydans, an actinomycetes, was found to effectively degrade phenol, to
be resistant to contamination and to have higher inhibitory concentration level, as compared
to many microbial species degrading phenol [7]. Brassica napus hairy roots as a source of
enzymes, such as peroxidases, which were also able to oxidise phenol in wastewater. Hairy
roots could be re-used, at least, for three to four consecutive cycles. Peroxidase activity
gradually decreased to approximately 20% of the control, at the fifth cycle. For the phenol
removal so many bacterias are used as like bacterium with high biodegradation activity and
high tolerance of phenol, strain PD12, which was isolated from the activated sludge process.
This strain was capable of removing 500 mg phenol in liquid minimal medium by 99.6%
within 9 h and metabolizing phenol at concentrations up to 1100 mg/L [11]. In order to carry
out phytoremediation studies, some scientists have introduced the use of in vitro cultures of
plant tissues, like hairy root cultures. These cultures proved to be excellent model systems to
study phytoremediation, including their several strategies of action, such as phytoextraction,
phytoestabilisation, as well as rhizofiltration of organic and inorganic pollutants. Hairy root

11
cultures are powerful tools in such studies mainly because of their biochemical and genetic
stability, easy maintenance and because they allow to perform studies without any microbiota
interference. Tomato hairy roots were able to remove phenol from water and the reduction of
this compound within the root tissue was associated with the catalytic activities of basic
peroxidase isoenzymes, which showed higher affinity and catalytic efficiencies than acidic
peroxidise isoenzymes [10].

12
 CHAPTER - 2

ELECTROCOAGULATION FUNDAMENTALS
 Using electricity to treat water was first proposed in UK in 1889. The application of
electrolysis in mineral beneficiation was patented by Elmore in 1904. Electrocoagulation
(EC) with aluminum and iron electrodes was patented in the US in 1909. The elec-
trocoagulation of drinking water was first applied on a large scale in the US in 1946. Because
of the relatively large capital investment and the expensive electricity supply, electrochemical
water or wastewater technologies did not find wide application worldwide then [12]. The
techniques include: environmental compatibility, versatility, energy efficiency, safety,
selectivity, amenability to automation, and cost effectiveness. In addition to these the
following advantages can be added: electrochemical based systems allow controlled and
rapid reactions, smaller systems become viable and, instead of using chemicals and micro-
organisms, the systems employ only electrons to facilitate water treatment.

2.1. Phenol electrochemical

Wastewater containing phenolic compounds presents a serious discharge problem due

to their poor biodegradability, high toxicity and ecological aspects. Phenols are widely
distributed as environmental pollutants. They exist in different concentrations in wastewaters
disposed from many industrial processes, including coking, synthetic rubber, plastics, paper,
oil refineries, petrochemical, ceramic, steel, conversion processes and phenolic resin
industries Waste waters containing phenols and other toxic compounds need careful
treatment before discharge into the receiving bodies of water, Biological treatment, activated
carbon adsorption, solvent extraction, chemical oxidation and electrochemical methods are
the most widely used methods for removing phenol and phenolic compounds from
wastewaters. Such problems as high cost, low efficiency, and generation of toxic by-products
are associated with the above methods, Biological and electrochemical methods have little or
no harmful effects on the environment, because these techniques do not involve the use of
harmful reagents.

2.2. Theory of EC

Electrocoagulation is the process of destabilising suspended, emulsified, or dissolved

contaminants in an aqueous medium by introducing an electric current into the medium. In its
simplest form, an electrocoagulation reactor may be made up of an electrolytic cell with one
anode and one cathode. The conductive metal plates are commonly known as 'sacrificial
electrodes' and may be made of the same or different materials (anode and cathode).

14
 Electrocoagulation is the electrochemical production of destabilisation agents (such as
Al, Fe) that brings about neutralisation of electric charge for removing pollutant. Once
charged, the particles bond together like small magnets to form a mass. This process has
proven very effective in removing contaminants from water and is characterised by reduced
sludge production, no requirement for chemical use, and ease of operation.

Colloid — destabilising agents that effect on-charge neutralisation are produced by

electrolysis in the EC process. For example, aluminium anodes are used to produce
aluminium cations which have the same effect as the addition of Al-based coagulants in
conventional treatment systems.

And finally aggregation of the destabilized phases occur to form flocs (Mohammad. et
al. 2009).

The destabilization mechanism of the contaminants, particulate suspension, and breaking of

emulsions has been described in broad steps and may be summarized as allows.

➢ Compression of the diffuse double layer around the charged species by the
interactions of ions generated by oxidation of the sacrificial anode.
➢ Charge neutralization of the ionic species present in wastewater by counter ions
produced by the electrochemical dissolution of the sacrificial anode. These counter
ions reduce the electrostatic interparticle repulsion to the extent that the vander waals
attraction predominates, thus causing coagulation. A zero net charge results in the
process.
➢ Floe formation: the floe formed as a result of coagulation creates a sludge blanket that
entraps and bridges colloidal particles still remaining in the aqueous medium.

2.3. Theory of adsorption

Electrocoagulation has been successfully used to treat oil wastes, with removal
efficiencies as high as 99%. A similar success was obtained when treating dye-containing
solutions, potable water, urban and restaurant wastewater and nitrate or fluoride containing
waters. In addition, a great deal of work performed in the last decades has proved that
electrocoagulation is an effective technology for the treatment of heavy metal containing
solutions. On the other hand, adsorption on activated carbon has been found to be a suitable
alternative for wastewater treatment. The contaminants are generally physically adsorbed or

15
chemically adsorbed onto the surface of the adsorbent. There has been a tremendous increase
in the use of adsorption for wastewater treatment over the last few decades in an attempt to
search for a low cost adsorbent. Several low cost adsorbents like bagasse fly ash, activated
slag and biosorption using green algae have been used. However, bagasse fly ash has an
alternative use in the cement industry to modify the compactive effort and shear strength
properties of cement [13]. Due to the operational difficulties and high cost of treatment of
electrocoagulation for large-scale treatment of wastewater rich in Phenol in developing
countries like India, adsorption process using low cost adsorbents (GAC) has been coupled
with electrocoagulation in this present study for the removal of Phenol [14].

Subsequently, studies on the treatment of heavy metal and organic compounds

containing effluents have revealed adsorption to be an equally effective technique for the
removal of these from waste streams, with wide use of activated carbon as an adsorbent.
Additionally, adsorption has been found to be superior to other techniques for water reuse in
terms of the initial cost, simplicity of design, ease of operation and insensibility to toxic
substances. Contaminants can be physically (physisorption) or chemically adsorbed
(chemisorption) onto the GAC which acts as an adsorbent while the adsorbate phenol will
accumulate on the GAC surface [14]. Traditional theories like Langmuir and Freundlich
equations cannot be used separately to study the extent of adsorption on percentage removal
of phenol. These equations have to be coupled with the kinetics of electrocoagulation to
determine the effective percentage removal and, to the best of our knowledge no such studies
have been carried out, till date.

2.4. Electrochemistry

The electrocoagulation process is intrinsically associated with electro flotation since

bubbles of hydrogen and oxygen are produced at the cathode and anode, respectively. The
success of an electrocoagulation process and for that matter electro flotation process is
determined by the size of the bubbles as well as by the proper mixing of the bubbles with
wastewater. It is generally believed that the smaller bubbles provide more surface area for
attachment of the particles in aqueous stream, resulting in better separation efficiency of the
electro flotation process. To improve the performances of an electrocoagulation it may be
necessary to interchange the polarity of the electrode intermittently [15].

16
 A simple electrocoagulation reactor is made up of one anode and one cathode. When
a potential is applied from an external power source, the anode material undergoes oxidation,
while the cathode will be subjected to reduction or reductive deposition of elemental metals.

DC Voltage source

Pollutant rise to the surface

H2O

..4...
Flotation

112
M(OH), (gas)
(hydrated Pollutants
canons)
OH"

$
Water pH
Anode (Oxidation) Cathode (Reduction)
Precipitate

Fig.2.1. Schematic diagram of two-electrode electrocoagulation cell [14].

The electrochemical reactions with metal M as anode may be summarized as follows:

At the Anode:

M(s) Moon+ + n e-

21120(1) > 4H+(aq) + 02(g) + 4 e"

At the Cathode

M(aq)n+ n e- M(s)

2H20(1))+ 4 e H2 + 30H-

If iron or aluminum electrodes are used, the generated Fe (43+ or Al (aq)3+ ions will
immediately undergo further spontaneous reactions to produce corresponding hydroxides
and/or polyhydroxides over a wide pH range. The main reactions at the electrodes are [12]
Anode: Al Al(aq)3+ + 3e- (5)

17
at alkaline conditions

A13+ + 3011+ Al(OH)3 (6)

at acidic conditions

A13+ + 31120 Al(OH)3 + 311+ (7)

Cathode: 3H 20(I) + 3e" 3/2 H2 + 3011- (8)

In addition, there is oxygen evolution reaction

2H20 + 4e 02 + 4H+ (9)

On the other hand, the cathode may be chemically attacked by OH- ions generated
during H2 evolution at high pH values.

2A1 + 6H20 + 2011" 2A1(OH)4-+ 3H2 (10)

Al(aq)3+ and OH- ions generated by electrode reactions (5) and (6) react to form various
monomeric species such as Al(OH)2+, Al(OH)2+, Al2(OH)24+, and AI(OH)-4 and polymeric
species such as A16(OH)153+, A17(OH)1744, Al8(OH)204+, A11304(01- )247+, and A113(014)345+,
which transform finally into Al(OH)3 according to complex precipitation kinetics. Formation
rates of the different species play an important role in the decolorization process. Several
interaction mechanisms are possible between dye molecules and hydrolysis products, and the
rates of these depend on the pH of the medium and types of ions present. Two major
interaction mechanisms have been considered in recent years: precipitation and adsorption,
each one being proposed for a separate pH range. Flocculation in the low pH range is
explained as precipitation, while that in the higher pH range (>6.5) is explained as adsorption.

2.5. Different Electrode Connection Mode

2.5.1. Monopolar electrodes in parallel connections (MP-P)

Anodes and cathodes are in parallel connection, the current is divided between all the
electrodes in relation to the resistance of the individual cells. Hence, a lower potential
difference is required in parallel connection, when, compared with serial connections As
shown in Fig.2.1. (a).

18
 A

00

V
r.

(a) (b) (c)

Fig.2.2. (a) MP-P System, (b) MP-S System, and (c) BP-S System.

2.5.2. Monopolar electrodes in serial connections (MP-S)

Each pair of sacrificial electrodes is internally connected with each other, because the
cell voltages sum up, a higher potential difference is required for a given current As shown in
Fig.2.2.(b).
2.5.3. Bipolar electrodes in serial connections (BP-S)
There is no electrical connection between inner electrodes, only the outer electrodes
are connected to the power supply. Outer electrodes are monopolar and inner ones are
bipolar. This connection mode has simple setup with and has less maintenance cost during
operation As shown in Fig.2.3.(c);.

2.6. Coagulation

Coagulation is a key feature of all electrocoagulation reactors, describing the

interaction between the coagulant and any pollutant material. The coagulant's role here is to
destabilize the colloidal suspension by reducing any attractive forces, thereby lowering the
energy barrier and enabling particles to aggregate. It is worth noting that both claim that the
coagulation mechanism for electrochemical and chemical dosing is very similar, yet neither
author support their claim with rigorous experimental evidence. Aluminium is the most
frequently used sacrificial anode in an electrocoagulation reactor [19]. The aluminium cation
has a variety of paths available (depending upon the pollutant properties, solution pH and
concentration) it could directly interact with the pollutant, it could hydrolyze to form a hydro-
aluminium complex, or it could precipitate.
2.7. Flotation

The production of electrolytic gases is an inevitable by-product of electrocoagulation.

These gases lift pollutant particles and coagulant aggregates to the surface by a flotation-like
process, while encouraging contact between pollutant particles and coagulant by providing a
certain amount of mixing action. The main difference between this "electrolytic flotation"
and more conventional flotation techniques is the method of bubble production and resultant
bubble size. Expertise from other flotation techniques, including electroflotation, dissolved
air flotation (DAF) and air-lift reactors can be employed to understand the flotation process in
electrocoagulation reactors. Electroflotation describes the production of electrolytic gases for
the sole purpose of pollutant removal [20].

2.8. Electro coagulation Vs. Chemical Coagulation

1. The EC technology is the distinct economical and environmental choice for industrial,
commercial and municipal waste treatment. The capital and operating costs are usually
significantly less than chemical coagulation. It is not unusual to recover capital costs in less
than one year.
Chemical precipitation in wastewater treatment involves the addition of chemicals to
alter the physical state of dissolved and suspended solids and to facilitate their removal by
sedimentation. The inherent disadvantages associated with most chemical unit processes is
that they are additive processes. This problem is eliminated in the Electrocoagulation process.
These chemicals are not only expensive, but, more importantly, the net increase in the
dissolved constituents in the wastewater render it impractical or impossible to reuse.
2. The handling and disposal of the sludge resulting from chemical precipitation is one of
the greatest difficulties associated with chemical treatment. Sludge is produced in great
volume from most chemical precipitation operations, often reaching 0.5 percent of the
volume of wastewater treated when lime is used
The total sludge generated by EC contains less than 0.5 percent added coagulant.
Total sludge generated by Chemical precipitation contains 49 percent added coagulant. The
added sludge generated by chemical precipitation effectively doubles the sludge disposal
volume. The hazardous waste issue may increase the cost 20 to 30 fold. When compared with
alum treatment, Electrocoagulation provided approximately 83% less sludge volume and a
76% improvement in filtration rate.

20
3, Electro coagulation can produce an environmentally friendly sludge in the 6 to 7 pH
range. The metals in the sludge at this pH range are stabilized in a non hazardous form as
Oxides.
Chemical precipitation on the other hand, usually creates a sludge in the caustic pH
range above 10. The metals precipitate as hydroxides, a hazardous form because the metals
will become soluble again at the natural pH range around 7.
4. Chemical precipitation tend to generate large volumes of sludge with high bound water
content that can be slow to filter and difficult to dewater. These treatment processes also tend
to increase the total dissolved solids content of the effluent, making it unacceptable for reuse
within industrial applications.
An electrocogulated flock tends to contain less bound water, is more shear resistant
and is more readily filterable

2.9. Advantages and Disadvantages of Electrocoagulation

2,9.1 Advantages
✓ Electrocoagulation has the potential to be the distinct economical and environmental
choice for treatment of wastewater and other related water management issues.
✓ System capable of operating without additional additives which results in less residual
waste production.
✓ Sludge formed by electrocoagulation tends to be readily sellable and easy to de-water,
because it is composed of mainly metallic oxides/hydroxides. Above all, it is a low
sludge producing technique.
✓ Floes formed by electrocoagulation are similar to chemical floe, except that
electrocoagulation floe tends to be much larger, contains less bound water, is acid-
resistant and more stable, and therefore, can be separated faster by filtration.
✓ The electrocoagulation technique can be conveniently used in rural areas where
electricity is not available, since a solar paned attached to the unit may be sufficient to
carry out the process.
✓ Electrocoagulation is an efficient technique since adsorption of hydroxide on mineral
surfaces is a 100 times greater than on pre precipitated hydroxides when metal
hydroxides are used as coagulant.
✓ Electrocoagulation needs simple equipments, designable for virtually any size. It is
cost-effective, and easily operable. The start-up and operating costs are relatively low.

21
 It requires low maintenance cost with no moving parts. Since practically no chemical
addition is required in this process, it brings minimum chance of secondary pollution.
✓ It needs low current and it can be run even by green processes, such as, solar,
windmill sand fuel cells.
✓ Electrocoagulation process can effectively destabilize small colloidal particles. It
produces minimal sludge. Gas bubbles produced during electrolysis can enhance
flotation.
✓ It removes the smallest colloidal particles efficiently in compared with the
conventional chemical and biological techniques, because the smallest charged
particles have greater probability of being coagulated by the electric field that sets
them in motion.
2.9.2. Disadvantages
➢ The 'sacrificial anodes' need to be replaced periodically. It requires a minimum
conductivity depending on reactor design, limiting its use with water containing low
dissolved solids.
➢ Electrocoagulation cannot remove materials that do not form precipitates such as
sodium and potassium. If a contaminant cannot form floes or cannot flocculate the
process will not work out. Therefore the contaminants such as benzene, toluene or
similar organic compounds cannot be removed.
➢ In case of the removal of organic compounds & some toxic chlorinated organic
compound may be formed in situ if chlorides are also present. Wastewater with high
humic and fluvic acid content may be amenable to the formation of trihalomethanes.
If phenols and algal metabolic and decomposition products are present, chlorine may
lead to bad taste and odor.
➢ An impermeable oxide film may be formed on the cathode that may interfere with the
performance of the electrocoagulation cell. However, changing polarity may help
reduce this interference. The cost of operating electrocoagulation may be high in
those is as where the cost of electricity is high.

2.10. Factors Affecting Electrocoagulation Process

The treatment of waste by electrocoagulation is affected by a number of factors such as:

1. Current Density
2. Presence of Nacl

22
 3. Inter-electrode distance
4. Electrode Area/Solution Volume
5. Electrolysis time
6. Initial Concentration

2.10.1. Effect of Current Density on the Process

The supply of current to the electrocoagulation system determines the amount of Al3+
or Fe2+ ions released from the respective electrodes. A large current means a small
electrocoagulation unit.However, when too large current is used; there is a high chance of
wasting electrical energy in heating up the water. More importantly, a too large current
density would result in a significant decrease in current efficiency. In order for the
electrocoagulation system to operate for a long period of time without maintenance, its
current density is suggested to be 20-25A/m2 unless there are measures taken for a periodical
cleaning of the surface of electrodes. The current density selection should be made with other
operating parameters such as pH, temperature as well as flow rate to ensure a high current
efficiency [17].

2.10.2. Presence of Nacl

Table salt is usually employed to increase the conductivity of the water or wastewater
to be treated. Besides its ionic contribution in carrying the electric charge, it was found that
chloride ions could significantly reduce the adverse effect of other anions such as HCO3-,
S042-. It is therefore recommended that among the anions present, there should be 20% Cl-
to ensure a normal operation of electrocoagulation in water treatment. The addition of NaCI
would also lead to the decrease in power consumption because of the increase in conductivity
[18].

2.10.3. Effect of pH on the Process

The effects of pH of water or wastewater on electrocoagulation are reflected by the

current efficiency as well as the solubility of metal hydroxides. It is generally found that the
aluminum current efficiencies are higher at either acidic or alkaline condition than at neutral.
The treatment performance depends on the nature of the pollutants with the best pollutant
removal found near pH of 7. When conductivity is high, pH effect is not significant. The
effluent pH after electrocoagulation treatment would increase for acidic influent but decrease
for alkaline influent. The increase of pH at acidic condition was attributed to hydrogen

23
high-energy efficiency. So, electrochemical oxidation method for removal of phenolic
compounds has attracted a great deal of attention.

The Objective of this study is to investigate the feasibility of aluminium electrodes for
the removal of phenol, which is commonly found in effluents of different industrial processes
such as oil refineries, plastic plants, paper plants, synthetic chemicals, pesticides, coal
conversion. The whole work deals with study of various parameters in electro coagulation
processes. The experiments were carried out to study the effect of pH, interelectrode distance,
current density, initial concentration, Nacl dosage and Addition of Granular activated carbon.
The aim of this work is to study the conjunctional effect when integrating the catalyst
(adsorbed onto active bentonite) into the electrochemical system and find out the Effect on
phenol removal efficiency and possible mechanism of decomposition of phenol was also
proposed.

25
 CHAPTER - 3
LITERATURE REVIEW
evolution at cathodes. In fact, besides hydrogen evolution, the formation of Al(OH)3 near the
anode would release H+ leading to decrease of pH. In addition, there is also oxygen evolution
reaction leading to pH decrease. Hence, the increase of pH due to hydrogen evolution is more
or less compensated by the H+ release reactions above [12].

2.10.4. Effect of Inter-electrode Distance on the Process

The inter-electrode distance also influences the Phenol removal efficiency. The
increase in the electrode gap between anode and cathode increases the power consumption
for the required current supply. As the distance between electrodes was increased, the current
density is decreased and the rate of removal also decreases proportionally.

2.10.5. Effect of electrolysis time on the Process

During electrolysis, the positive electrode undergoes anodic reactions while cathodic
reactions occur on the negative electrode. The released ions neutralize the particle charges
and thereby initiate coagulation. The Phenol removal efficiency depends directly on the
concentration of ions produced by the electrodes. When the electrolysis period increases, the
concentration of ions and their hydroxide flocs increases. Accordingly, with an increase in
the time of electrolysis there is an increase in the Phenol removal efficiency.

2.10.6. Effect of Initial Concentration on the Process

The initial concentration of the solution also effects the Phenol removal efficiency.
Generally as the concentration increases the Phenol removal efficiency decreases. This is
may be attributed to the fact that at a constant current density the same amount of aluminum
ions passes to the solution at different phenol concentrations. Consequently, the formed
amount of complex aluminum Hydroxide was insufficient to coagulate the greater number of
phenol molecules at higher phenol concentrations [12].

3. Objective of the present study

In wastewater treatment the removal of phenols is of great importance due to their

toxicity. Electrochemical oxidation has been proposed as an efficient method for the
treatment of wastewater polluted by organics since mineralization of organic pollutants can
be completely achieved at different anode materials. Electrochemical method offers the
prospect of relatively simple equipment, environmental friendliness, and the possibility of

24
3.1. Literature review on Phenol removal by electrocoagulation

Noureddine et at (2009)., This study is about the removal of organic pollutants based on electro
polymerization on an anode was performed in the case of phenol in alkaline solution. The polymer
formed by a process involving less than two electrons per molecule of phenol, is then precipitated by
decreasing the pH and finally filtered and disposed. The electrochemical polymerization of phenol (Co
= 0.105M) in alkaline solution (pH= 13) at 86 °C has been studied by galvanostatic electrolysis, using
a range of anode materials characterized by different 02-overpotentials (Ir02, Pt and p-Pb02).
Measurements of total organic carbon and HPLC have been used to follow phenol oxidation; the
morphology of the polymer deposited on the electrode surface has been examined by SEM.
Experimental data indicate that phenol concentration decreases by oxidation according to a first order
reaction suggesting amass transport limitation process. Polymeric films formed in alkaline solution
did not cause the complete deactivation of the anodes. SEM results show that the polymeric films
formed on Ti/Ir02 and Pt anodes cannot be mineralized. On the other hand, complex oxidation
reactions leading to the partial incineration of polymeric materials can take place on the Ta/ p -Pb02
surface due to electro generated HO• radicals which have an oxidizing power much higher than that of
intermediaries formed respectively on Ir02 and Pt. It is assumed that the polymer films formed on
these anodes have different permeability characteristics which determine the rate of mass transfer of
the phenol. The fractions of phenol converted in polymers were 25, 32 and 39% respectively with
Ti/Ir02, Pt and Ta/ p-Pb02, a series of materials in which the 02-overvoltage increases.

S.S. Mahmoud et al (2009) In this study electro catalytic oxidation of phenol on Ni—A1203 composite
electrodes was investigated in wastewater. Firstly Ni—A1203 composite-coating electrodes was
prepared by electro deposition of Ni—A1203 composite on the mild steel substrates from the citrate
bath containing NiSO4 as a source of nickel and alumina Particles. The electrodeposited composite
coating was heat treated at 400°C and characterized by using different techniques such as scanning
electron microscope (SEM), electron dispersive X-ray analysis (EDX), and X-ray diffraction (XRD).
On using this composite coating as electrodes it was found that the highest electro catalytic activity
was achieved in presence of [H2SO4 (2 g/1) + FeSO4 (20mg/1)]. In presence of each of NaOH and
H2SO4 the activity of the electrode was poor. The electro-Fenton's reagent was the most suitable
oxidizing agent for the oxidation of phenol. The highest electro catalytic activity of the investigated
composite for the degradation of phenol was achieved in the presence of (H2SO4 +
FeSO4).Controlling the operating factors such as current density, solution pH, temperature,
electrolysis time, concentration of FeSO4 leads to complete electro catalytic degradation of phenol in
(H2SO4 + FeSO4) on the Ni—A1203 composite-coating electrodes.

Guifen et al (2009) In this paper, the feasibility of using carbon aerogels (CAs) as bed electrodes in a
three-dimensional electrode reactor for the electrochemical treatment was studied. It was found that
the removal efficiency depended on the air flow, the feed phenol concentration, pH, the ratio of
aerogels mass to solution volume, and repeated times. Compared with commercial carbon particle
electrodes, the CAs prepared exhibited stronger and longer-term activity to remove phenol simulated
waste water. For 250mg of phenol solution, 98% of the initial phenol chemical oxygen demand
(COD) can be removed after treatment for 20min. Moreover, high removal efficiency can be kept
basically after being reused many times (e.g. 93% and 82% after 20 times and 50 times, respectively).

Hongzhu et at (2009) In this paper, the electrochemical oxidation of phenol in synthetic wastewater
catalyzed by ferric sulfate and potassium permanganate adsorbed onto active bentonite in slurry bed

27
electrolytic reactor with graphite electrode has been investigated. In order to determine the optimum
operating condition, the orthogonal experiments were devised and the results revealed that the system
of ferric sulfate, potassium permanganate and active bentonite showed a high catalytic efficiency on
the process of electrochemical oxidation phenol in initial pH 5. When the initial concentration of
phenol, was 0.52 g/L (the initial COD 1214mg/L), up to 99% chemical oxygen demand (COD)
removal was obtained in 40min. According to the experimental results, a possible mechanism of
catalytic degradation of phenol was proposed.

Miao Li et al (2009) In this study Electrochemical degradation of phenol was evaluated at two typical
anodes, Ti/RuO2—Pt and Ti/Ir02—Pt, for being a treatment method in toxic aromatic compounds. It
was found that Ti/Ru02—Pt anode had a higher oxygen evolution potential than Ti/1r02—Ft anode,
which will increase the current efficiency for electrochemical degradation, and the instantaneous
current efficiency (ICE) was relatively higher at the initial time during phenol electrolysis. HOC1
formed during electrolysis would play an important role on the oxidation of phenol. For the Ti/Ru02—
Pt anode, phenol concentration decreased from around 8mg/L to zero after 30min of electrolysis with
0.3 g/L NaCI as supporting electrolyte at the current density of 10mA/cm'. Although phenol could be
completely electrochemical degraded at both Ti/Ru02—Pt and Ti/Ir02—Pt anodes, phenol degradation
was slower at the Tiar02—Pt anode than at the Ti/Ru02—Pt anode due to the fact that passivation was
to be found at the Ti/Ir02—Pt anode.

Manickam et al (2008) Mediated electrochemical oxidation (MEO) process is one among the latest
treatment technologies for the destruction of toxic organic pollutants under ambient temperatures and
at atmospheric pressure which was discussed in this paper is a further extension of the conventional
electrochemical treatment for the removal of toxic organics with powerful mediator oxidants in acidic
medium. In this report the experimental results of using silver and cerium as mediator ions were
compared with respect to their electro-oxidation behavior within the limitations of each mediator
metal ion and their destruction efficiencies were compared for destructing phenol in continuous
feeding mode. The following conclusions were drawn: (i) the optimum nitric acid concentration was
found to be 8 and 3M and the optimum temperature was found to be 60 and 80°C for silver and cerium
electro-oxidations, respectively; (ii) in the case of Ag (II)-MEO of phenol the maximum destruction
efficiency achieved was 98% at 70°C based on CO2 evolved; (iii) for Ce (IV)-MEO of phenol the
maximum destruction efficiency achieved was 93% at 90°C based on CO2. The results may provide
baseline information on the use of suitable mediator metal ion in treating the target organic wastes by
MEO process.

Marcio et al (2008) In this study oxidation of phenol in aqueous media by electro-Fenton process
using carbon felt cathode has been studied. The salts of iron, cobalt, manganese, and copper were
used to provide the metal cations as catalyst of Fenton reaction to produce hydroxyl radicals. 10-4m of
soluble iron(II) sulfate salt supplied the optimum catalytic condition, allowing to remove 100%of total
organic carbon (TOC) of aqueous phenol solutions. The main reaction intermediates formed during
electro-Fenton treatment were identified as hydroquinone, p-benzoquinone, and catechol. Carboxylic
acids such as maleic, fumaric, succinic, glyoxylic, oxalic, and formic were predominantly identified as
end products, before complete mineralization. The absolute rate constant of phenol degradation by
hydroxyl radicals was obtained in acid medium (2.5 < pH < 3.0), being equal to (2.62 ± 0.23) x 109
M-1 S l , experiments with e]ectro-Fenton oxidation of each aromatic intermediate allowed to propose
a complete mineralization pathway.

28
Hui Wang et al (2008) In this study by using a self-made carbon/polytetrafluoroethylene (C/PTFE)
02-fed as the cathode and Ti/Ir02/Ru02 as the anode, the degradation of three organic compounds
(phenol, 4-chlorophenol, and 2,4-dichlorophenol) was investigated in the diaphragm electrolysis
device by electrochemical oxidation process. The result indicated that the concentration of hydrogen
peroxide (H202) was 8.3mg/L, and hydroxyl radical (HO•) was determined in the cathodic
compartment by electron spin resonance spectrum (ESR). The removal efficiency for organic
compounds reached about 90% after 120min, conforming to the sequence of phenol, 4-chlorophenol,
and 2,4-dichlorophenol. And the dechlorination degree of 4-chlorophenol exceeded 90% after 80min.
For H202, HO• existed in the catholyte and reduction dechlorination at the cathode, the mineralization
of organics in the cathodic compartment was better than that in the anodic compartment.

Leonardo et al (2008) In this paper a comparative study on the electrooxidation of phenol in H2SO4
medium using pure Pb02 or F-, Co- and Co,F-doped Pb02 electrodes in filter-press cells was carried
out. The oxide films were obtained by galvanostatic electrodeposition using an electrolytic bath
containing sodium lauryl sulfate as additive and Pb2+,F,Co2+ or Co2+ +F, under magnetic stirring (to
obtain 4-cm2 electrodes) or ultrasound waves (to obtain 63-cm2 electrodes). The best results were
attained with Pb02 electrodes doped with low-Co content (1mM Co2+ in the electrolytic bath) along
with F: the chemical oxygen demand (COD) and the total organic carbon content (TOC) of the
simulated wastewaters were removed by about 75% and 50%, respectively. When pure Pb02
electrodes were used, the COD and TOC removals were about 60% and 45%, respectively. For the
smaller electrodes, an average current efficiency (ACE) and an energy consumption (EC) of about
16% and 70 kWh kg-' COD, respectively, were obtained. For the larger electrodes, the ACE and EC
values were about 18% and 105 kWh kg-' COD, respectively. Stability tests of the electrodes showed
that they are suitable for use in the electrochemical treatment of phenol wastewaters.

Yujie Feng et at (2008) In this study the performance of electrodes for the electro-catalytic
decomposition of a model pollutant (phenol) was enhanced using Gd-doped Ti/Sn02-Sb electrodes
prepared by a thermal deposition method. Phenol degradation followed first-order rate kinetics, with
the maximum rate achieved using a 2% Gd doping level (molar ratio based on Gd:Sn) for tests
conducted over a doping range of 1-10%. The first order rate constant with 2% Gd was 0.044 min'',
versus 0.026 min"' obtained with the control (plain Ti/Sn02-Sb). TOC removal and UV scans revealed
that different intermediates were produced for different Gd contents, and that destruction efficiencies
of these intermediates also varied with Gd doping levels of 1-5%. Electrodes were characterized by
scanning electron microscopy, X-ray diffraction, electron dispersive spectrometry, and X-ray photon—
electron spectroscopy. It is suggested that the state of specific active sites on the electrode surface and
the oxygen transfer activity at the electrode/electrolyte interface affect the performance of anodes with
different compositions.

MAO Xuhui et at (2008) In this study the mineralization of phenol in aerated electrochemical
oxidation has been investigated. The results show that a cathodic Fenton process can occur when the
Ti-0.3Mo-0.8Ni alloy material is used as cathode in solution containing ferric or ferrous ions;
moreover, the reinforcement of cathodic Fenton process on the total organic carbon (TOC) removal
rate of phenol is quite distinct. Among the metallic ions investigated, the ferric ion is the best catalyst
for the electrochemical mineralization of phenol at initial pH 2.0, and the optimal concentration range
is from 50 to 200 mg/L. The favorable pH range and supporting electrolyte (Na2SO4) concentration
for mineralization of phenol in solution containing ferrous ions are 1.8-2.3 and below 0.10 mol/L,
respectively. UV radiation can improve the TOC removal rate of phenol, but the enhanced effect
varies in different solutions. In the solution containing ferric ions, an equal sum or synergetic effect

29
can be observed. The optimal effect of electrolysis system under UV radiation is achieved in the
solution containing 50 mg/L Fe3+ with a final removal percentage of 81.3%.

M. Pa kula et al (2007) In this paper Cyclic voltammetry and spectral FTIR studies of the influence of
activated carbon surface modification on the co-adsorption of metal cation (lead or iron) and phenol
from aqueous acidic solution were carried out. The diversity in surface chemical structure was
achieved by applying different procedures of inorganic matter removal and by modifying the carbon
samples in various ways: heating under vacuum, aminoxidation in an ammonia—oxygen atmosphere,
oxidation with concentrated nitric acid. The quantities of adsorbed metal ions (Pb2+ or Fe3') and
phenol from solutions containing cation or phenol separately or in a mixture were determined. The
electrochemical parameters of electrodes made from the carbon samples were estimated, and some
possible electrochemical reactions were determined from voltammograms recorded in acid electrolyte
solution containing adsorbed species (separately or as a mixture). Relationships were found between
metal ion adsorption and electrochemical behavior of Pb2+/Pb4+ and Fe3+/Fe 2+ couples on the one
hand, and the presence of phenol in the solutions tested and the influence of surface chemistry of the
carbon electrodes on electrochemical processes on the other. The changes in adsorption capacity with
respect to the adsorbates used and the changes in FTIR spectra of the carbons as a result of adsorption
and/or coupling phenol molecules are discussed.

Di Wu et al (2007) In this paper, salicylic acid (2-HBA) was used to trap •OH in the process of
electrolysis with a couple of Ti-base lead dioxide electrodes in different conditions. Aqueous solution
of 2-HBA, a couple of Ti-base lead dioxide electrodes and an AC power were used in the course of
•OH formation, and then the solution containing 2-HBA and 2,5-dihydroxybenzoic acid (2,5-DHBA)
was analyzed by High Performance Liquid Chromatography (HPLC) with fluorescence detector. This
method can help us to better understand the reaction mechanism of •OH from the viewpoint of
quantity.In the same conditions of electrolysis, Total Organic Carbon (TOC) of phenol solutions were
detected to identify the effects of some factors during this electrochemical process, because the strong
oxidation ability of •OH can mineralize the organic pollutants totally and finally achieve the goal of
water treatment. The results show that high pH value of electrolyte and high frequency of the AC
power are favorable for the generation of •OH, however, C032-is opposite to them.

Yusuf et al (2006) In this study, electrochemical oxidation of phenol was carried out in a parallel
plate reactor using ruthenium mixed metal oxide electrode.As a result of the study, removal efficiency
of 99.7% and 88.9% were achieved for the initial phenol concentration of 200mg/L and chemical
oxygen demand (COD) of 480mg/L, respectively. In the same study, specific energy consumption of
1.88 kWh/g phenol removed and,mass transfer coefficient of 8.62x10-6 m/s were reached at the
current density of 15mA/cm2. Electrochemical oxygen demand (EOD), which can be defined as the
amount of electrochemically formed oxygen used for the oxidation of organic pollutants, was 2.13 g
02/g phenol. Electrochemical oxidation of petroleum refinery wastewater was also studied at the
optimum experimental conditions obtained. Phenol removal of 94.5% and COD removal of 70.1%
were reached at the current density of 20mA/cm2 for the petroleum refinery wastewater.

Carvalho et al (2006) In this work, the electrochemical oxidation of phenol was studied on a
zeolite/graphite composite electrode. The oxidation of phenol was studied by cyclic voltammetry and
a well-developed wave, due to the oxidation of phenol, is observed. When the concentration of phenol
is sufficiently low, the electrode is not fouled by the electrochemical process and the change in the
concentration of phenol induces a reversible change in the intensity of the oxidation wave. For higher
concentrations of phenol it is likely that some deposition of oxidation products occur at the electrode
surface and inactivation is observed. The overall process seems to be due to the oxidation of the

30
species that is inside the porous volume of the electrode system and not to diffusion-controlled
processes involving the solution bulk. Electro-oxidation of phenol over zeolites may have a significant
bearing for applications either in the removal of these pollutants or, for example, the production of
fine-chemicals.

Xiao-yan et al(2005) In this study laboratory experiments were carried out on the kinetics and
pathways of the electrochemical (EC) degradation of phenol at three different types of anodes,
Ti/Sn02-Sb, Ti/Ru02, and Pt. Phenol was readily mineralized at the Ti/Sn02-Sb anode, but its
degradation was much slower at the Ti/Ru02 and Pt anodes. The analytical results of high-
performance liquid chromatography (HPLC) and gas chromatography coupled with mass
spectrometry (GC/MS) indicated that the intermediate products of EC phenol degradation, including
benzoquinone and organic acids, were subsequently oxidised rapidly by the Ti/Sn02-Sb anode, but
accumulated in the cells of Ti/Ru02 and Pt. There was also a formation of dark-coloured polymeric
compounds and precipitates in the solutions electrolyzed by the Ti/Ru02 and Pt anodes, which was
not observed for the Ti/Sn02-Sb cells. It is argued that anodic property not only affects the reaction
kinetics of various steps of EC organic oxidation, but also alters the pathway of phenol electrolysis.
Favourable surface treatment, such as the Sn02-Sb coating, provides the anode with an apparent
catalytic function for rapid organic oxidation that is probably brought about by hydroxyl radicals
generated from anodic water electrolysis.

Yanqing et al (2005) The electrokinetic process is an innovative technology that shows much
promise for the remediation of contaminated soil and groundwater. The pH can significantly affect the
migration of contaminants. It was easier to remove the weak organic acids such as chlorophenols at
higher pH value. However, partial degradation of chlorophenol occurred close to the electrodes. The
contaminated soil can be remediated by the combination of the electrokinetic process and
electrochemical reaction. After 140 min of treatment, the removal efficiencies of four phenol and
chlorophenols could reach 85% at voltage 1200 V m"' , current10 mA and pH = 9.8.

Canizares et al (2004) In this study the electrochemical oxidation of 2,4-dinitrophenol (2,4-DNP)

aqueous wastes has been studied using both, bulk electrolysis and voltammetric techniques. To carry
out the bulk electrolysis, a bench-scale plant with a single compartment electrochemical flow cell was
used.Boron-doped diamond (BDD) materials were used as the anode and stainless steel (AISI 304) as
the cathode. According to the obtained results, a simple mechanistic model has been proposed. The
oxidation of 2,4-DNP leads to the appearance of phenol and quinonic compounds and to the release of
the nitro groups from the aromatic ring, in a first step. In a second step, these organics are transformed
into carboxylic acids (mainly maleic and oxalic acid). The process ends with the formation of carbon
dioxide (CO2). The effects of the waste characteristics (composition and pH) and of the operation
parameters of the process (temperature and current density) have also been studied in this work.The
complete removal of the organic compounds contained in the waste has been obtained in all essays.

Bahadir et al (2003) The electrochemical treatment of phenolic wastewater in a continuous tubular

reactor, constructed from a stainless steel tube with a cylindrical carbon anode at the centre, was
investigated in this study, being first in literature. The effects of residence time on phenol removal
was studied at 25°C, 120 g 1-1 electrolyte concentration for 450 and 3100mg phenol feed
concentrations with 61.4 and54.7mAcm-2 current densities, respectively. The change in phenol
concentration and pH of the reaction medium was monitored in every run and GC/MS analyses were
performed to determine the fate of intermediate products formed during the electrochemical reaction
in a specified batch run. For 10 and20min of residence time phenol removal was 56% and78%,
respectively, with 450mg 1-1 phenol feed concentration and above 40min of residence time all phenol

31
was consumed within the column. For 1, 1.5, 2 and3 h of residence time, phenol removal achieved
was 42%, 71%, 81%and98%, respectively, at 3100mg phenol feed concentration. It is noteworthy
that more than 95%of the initial phenol was converted into a non-passivating polymer without
hazardous end products in a comparatively fast and energy-efficient process, being a safe treatment.

Feng et al (2003) In this study three kinds of Ru02-base electrodes were prepared by thermal
deposition, which were coated by the oxides of Ru or by Ru, Sn and Sb or by Ru, Sn, Sb and Gd on Ti
metal surface, respectively. Another electrode Ti/ Pb02 was prepared by electro-deposition method
with Pb02 coated on Ti. A Pt electrode was chosen for comparison. Characteristics of the typical five
electrodes were investigated by cyclic voltammetry, SEM and its degradation ability for phenol.
Performance for phenol degradation of the three Ru02 electrodes lie in: Ti/Sb—Sn—Ru02—Gd> Ti/Sb-
Sn—Ru02> Ti/Ru02 and the electrode with b-Pb02 coating was superior to Ru02-based electrodes and
Pt electrode. Aromatic ring opening take place at all researched electrodes and it is supposed that
electrolysis run stop at different intermediates, such as benzoquinone, maleic acid, etc. Under the
present experimental conditions, whole mineralization to CO2 takes place only in the b-Pb02 anode. A
pathway of electrochemical degradation of phenol was suggested based on the experimental analysis

Zareie et al (2001) In this study the formation of non-passivating polymeric structures was
investigated during electrochemical conversion of phenol using carbon electrodes and NaCl as
electrolyte. Unlike previous work, non-passivating solid polymer was produced at high voltage and
current density values in the presence of NaCI. The most orderly polymer formed at 912mg initial
phenol concentration, current density 32.9mAcm-2, NaC1 concentration 120 g 1-1 and temperature
25°C. Higher operational parameters yielded disorderly formed aggregates of the polymer in
decreasing surface density on STM images. Along with the polymer, only toxic mono-, di- and tri-
chlorophenols were formed as intermediate compounds during the electrochemical conversion, which
eventually were polymerized and/or oxidized to final products. FTIR analysis and enlarged STM
image implied the repeating phenol units in the polymer structure. The results may lead to appropriate
techniques for the removal of phenol from wastewater in the form of a solid polymer.

Mihir et al (1997) An electric current was passed through a granular activated carbon (GAC)
column to investigate changes in the surface characteristics of the GAC and the adsorptive
capacity for phenol. Using potentiometric titration, it was observed that the GAC was less acidic after
cathodic treatment and more acidic after anodic treatment. Oxic and anoxic isotherms were compared
using statistical methods to evaluate changes in the adsorptive capacity of GAC for phenol. Under
oxic conditions, the adsorptive capacity of GAC decreased after anodic and cathodic treatment. Under
anoxic conditions, a decrease in adsorptive capacity in the lower range of phenol concentrations
investigated was observed after anodic treatment, while cathodic treatment may not have significantly
altered the adsorptive capacity. The observed changes in adsorptive capacity could not be definitely
correlated with the observed changes in the measured surface acid group concentrations in this study.

Boudenne et al (1995) The electrochemical oxidation of an aqueous phenol solution was studied via
a novel process. Experiments were conducted by recirculating a slurry electrode made of the product
to be treated(phenol) and a catalyst (carbon black) through a flow-by electrolyser with a vertical
stack of perforated Ti/Pt electrodes. Both the capacity of high adsorption of organic compounds and
gases and the conductivity properties of Carbon Black allowed the acceleration of the degradation.
Other experiments under nitrogen and oxygen flow were performed in a closed reactor cell and
proved that oxygen generated by Ti/Pt electrodes is sufficient to obtain the full degradation of phenol.
The effects of CB concentration (ranging from 0 to 4 g1-1), of the nature of CB and of the applied
current (from 0 to 20 A) were investigated. An increase of CB concentration and applied current was

32
found to shift product distribution to favour the formation of carbon dioxide. A removal efficiency of
100% was obtained in a reaction time of 15 min under the following conditions: an initial phenol
concentration of 1 mmol 1-1, 4 g1-1 of CB, an applied current of 10A, a flow rate of 10 mls"' and a
temperature of 30°C.

Chia-Yu et al (1988) In this study a reductive amperometric detection method has been developed
for the high-performance liquid chromatographic determination of phenols in aqueous samples. The
phenols were derivatized to form the corresponding quinoneimines employing the 4-aminoantipyrine
reaction prior to reversed-phase chromatographic separations. In contrast to the conventional
oxidative detection of phenols with a high applied potential of over +0.95 V, a low potential of -0.20
V vs. Ag/AgCI was used successfully to detect the derivatized phenols with a glassy carbon
electrode. The principal advantage of this method is that oxygen removal from the mobile phase is not
required. This is because the applied potential is so low that oxygen reduction is not detectable at this
potential. A linear dynamic range of concentrations between 104 M and 104 M was observed for
some selected phenols.

33
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0 ,42 x •
5.
‘,0 n, ka) ti) 6-• = 74 c) a.)
-o .15 a u a) ..J E 6,
en > N :47-1 0 g3 >-,
.... ct C.
- a) o
Oa) o ti ! O
5 5 -) Q E cr.+ t
a) CI, • I. s a) ' FA' n--,d. -ua 0 g
6 - , u O) a.) 6.-. al ›, 1...
....• ,.0
0 lU
'Z1
0 ° .-
0
= (5) Q
5' a.) 5
::
3)
,...,_, -4,74, _," a) 0 a) Clkr) .0 0 a) .0
g o EL
o O. 0 0 -0
.0 n ...0 O 0
y fa■ CU ..- 5 cl) EA •
NE V) V)
CO E.) 0 .0 El.)
N 0 o
r "0
%._/ Li-, 0 0 0. 0 0o 46. 42 ''',. .... 0 C.) 0 Q
o f) •- a) .0 0 0 0 e- 0 el)
0 .0 • ,-, 0 21), r4 O
a) .0 0.
° --5 °u 0:1, o
U -- N N '0 N ta. •

0 E 0 cr •.:C > ,) 0 rl
.0 '10 a)•••:L
.0 tu. v
U
Cd c-•,,)
1 •-• cu
ell
• "' "Fu Lo (, 2 ..0
C..)z iz3•2 -ats
cs
9E;,... 0 Q. 0 1-,4 I- zz -rd
ocs - g 8 5,)
P.; 4c7i a)) a)
,..
.> c >, 5
00 t P. 0 € E ,) •-• •`•1•' E "0 et .0 1..0) .6 *.
,.c . ...
ti F-1 .
0 0
-0 cat to i-it 5 a) :0 c.) t0
73 ell
CO C4-I w 0 Cr
o..
< o LI c.) a)
0 2 R. O
o 1- cn .0 ■1
-• 7--•)• "a
EE '1)
°•0 ct
E a.=
concentration,
E

0
Cd
pH and temperature

Salt concentration,
Cd
adsorbents dose, P

>7.
119
0
a)

G.
activated sludge + photo-
activated carbon/batch

Electro coagulation

membrane process

Amour et al.,

id
N
N O
O O
id
O
CC:1


c.... c-
'''
cat ..0
o a.) 5 --
2o 0 o Tu3 o cs
3 '5 G 3 o .-., cr.) 0 .5.0 Ictai 4 g
o o -O 0
-0 ..0e1/40
Nam
a -5 E ti..1 I
>,
4..
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0 c:D
r:::.
r. a 0
70 0 0 .OA-
....
a cl
70
,,)
1/4.0 CO
1/4•-■
T0 '4) 0
as E U c . .!., . . s kg
.ge
:
C E ,, -S 70
(..) 0 g ° •
MI U
I-. .OD
=> 0 N 'ci.- 3 C•1 _. 0 cel 0 CA 0
CD 0 f.
CZ, Z 4--.07 o...0 .-0
0'')0
> 0
C \ i C) o 4g 4) 0 " 0 <4 o N 4- g cat 2 -6 .0 0 •,_.
...:,..a.F
0 0 ..,-. e_s ,_
a) c4 3 p. ......_
e- . 0 ff., z 0.) a) ,...
o E c4-)
:E

i;
0 (7) 0 rt: c.) -0 0 cs0 °`
-,5, °'U (4. CC1o2 -a sa. 0 U a) -o
a> 0 g
00 0< . 4a, (-) .0
0 -o a, o (.,1 0
u
0
o
t ) .,=. .z.,'
cv o
•.....
-. ,......
.0 >., U
0 G tif:
.5 ° ..==a.)=8-0
=.3.) -5 c:•!
4... •Zt.
=etra)
. 6 E = = •C 0 0 Crs
O
uo cl En 0 c-1-.
- o= 7:1
.,.. -0 g el)
al 0
0 tw:c c
C.) 4.0 -0
r_
_0_. ... D. . 0 0
0 -CI
co g
■ 0 0
on >-■ .1.... Z ' (,)
03 00. v) r-S W :a
-01 •.°
CL) 4, 0
... . Ctl a
= in 0 t)
Q brl • ! a al `g
O g
Z ,!.....) E ot Ct
cr I...
CL) 0 "a.
II .5
15 .f2 N 7s. '61,,...
0
-0 oti) 0
0 0= 7:;
..-• ,, !0
e,o 0
p.,
... .4 E E 7.a -0v
4 C) . .4 u
g (5' .-Cl ",
') E 41 csi
E ez vz) -.5 -'-' 4... .-.
›N .0 cl -E
o ',7) 0
c... 0 -c • - "5 (..) V)
0 7$‘ "q
cl ,:;:,
''
4-d >, -s-, .a4
. 1. a. .
"Fu
U
cu c) cr' 4.. -°„
75 a ..o 3 c.)
0 ca. 0 L.) a 2 -0
a> votr.°.`g 001,...
„,)
0 Z 0. a. u
U 0 E I.;
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--. a) (A c 0 -0
a> •-o .... -'-' .2
a U -cr ti
tkO
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c.4- 72 4 4-,
•-•
ca 2 .0- .- 7 7:1 ,... =00 0
H cd i
2 m1). q,270 7:0 M
o E ,_.7,
To E E 4,t 0. V,
t„ '743
E „, 5 ••
U
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0 a ..e.g, !-?. o c.-
r1) 0 g Ti04 ,-

5 fg o ca '8 o ,.... al,

0

- 14
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0 1
0
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0 CD
4.) 0 .)=.■
(1.) 1...i $-ce. 7) ..2 cn ° lit tIO tall E --.
a. 0 S, ...a. al
•""' .C2 "C) " 0 c+-■ O
6 •401 .0 t"1 I-1.
° 0)
0 ›".
4-i
1
00 70 GU .1- 0 N f.3) .E o
4-• kr)
.0
••••• o g 1- "a• 03 I-. -0 C t 4 ) 6 "1::., C.) 0
Z ,'-' 10 'L. kj (4.
..S .0 0 el) ,4.
.7im e4-o ct la -0 -cs 0 0
'4=
U' .2
4/7 a,
0 u )3)
2 sE
o g 0
=•-'...... (1),, O G 3 -5 .,s1 .-.- 0 1,1 tall .cct
0 , 0 z -0 tall -, c.. .-. ,
s M
•b I-. 7:
9
4-k
t•... E 9 ' w U 0 0 = =
Cl) . 71 -
cri 6 "
tt) I '0 0 .0 b.()
`cei 7-1 0 at.: fa. [_...
,= 0
0 o
cn .2 o
.....ca.
a. 0
() 0 C_,)
0 u). •-•
E --00 ..00
,-, ci41 >N T o 2 E o 5 c, 0
._,
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-a U)
> 4.4 a H -,' g. --r-t' 5 5 c>
01/4 H
-(71 O O
)-) a 0
U a)

=
CL)
initial concentration

Er
,
cvw
0

.° EL)

4:1 °
L) "tj
cd
N U)
0
•-.
Acinetobacter sp.

O &J)
H tn 0
cp
o
5
o ,° 0

a) -0
ad. 0 O.

CC
N N
O U O
O O
N
N


0 '5 4.) 7:$ cu 0.1) -0 v.) ›.- a) g

rtt =
as 6 c)
as. s-. 0
< 4e4 E
v "E. u
• c7; o .-- tu 0.)
cd CC/) 0 O u kr) _0 0)
O O cr.) 3. •■-o 0 N 0 0 ra, crs
U C7 un ,4C). Q 0 4) (I)
0 0 .0 O 0
W a)
kr ) Z5 E-• 0 0 CU 0 "C3 73
... 0.0
C'd
-4-, •O 5
S" 4.6 E
-- -5 6
0.0 CI" ,,,,) 0- •
rd V)
y_, )
.L.34 `+6 (-1 7:1 Q
Ce 2 LE a) -0 75 oa; ,,,
7 "C) ••Z
CO
ci I-, 0 > ;ox) "Zt cd
0 )
0C..) ?-4
Ci.)
75.
N2
-0 .... ..0 ta.
. a) 0 0L.
C kr) Y a-) •• I
<
o cu
° 0 +6.
te-■ la. as > ad C4-1
9
a.
0 tt
••A
0 0
0
31" ,,,3 E .... 0
P.O
`cp
cn 0) 48 0.0 CT 0 ON
0 ....a)-_
.51 ,a) -E 00..,-,
0) .... Lt..; O os,
0 3..
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ci a.)o
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co .0 :--- 0 g 0 -0 4)
CQ •0 4 c..) 0 .0 -o c, ao Tri
a. E- <=> N 0
t4-•
•
CO -Clas 8 E:;
E g U 0
,... 0
(4 v ° 174 0 .0
on %A C-) ra.,
■••■ c c.) el9
-0 er -2 •t4za-3 C)
•- 0 0.0 0 O E
c■-) 0)
a) .= YO C 0
h. c>
a 2 15 C 0. 0 0
cat
42 ^A
u1' 0 tA •t
-• 4., 0
"CS $••• cYd O
0 '1' "
ce) cat10cd 0 • O O :73111 E
ca: cc) 9) "••
> C.2
cn "0 cif 0 o a)
o
e 0
tD4 c. 0 O u, ('I)at
cQ as .I-.
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O 0_a oU cd kr) o's 0
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C' O...., -0 a.), C, 4.1 •-• g
g ,4..g
-■-■ .)" ", (1-1 vi •-.
_ 4...
0 41
N
N
O
icd ,
4e., 0 ..., -
at -0 -,-.
7:3 0 a. E g E
" tal ^0 4), 0
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(4 4-• o .0 .0 0 ".45 0
-0 .0 0 "0 .0 C.1 0 E
0 0 > ° Tua -0 -0
cN , cu ,,. cas 0 0
E F. -° V) 42 *CS
cd " 0 a) 0.)>. 0 2 P' 3 a.) .N .4;4 X 0 0
2
a)
( 0 0 0 3 73 c..) Ut•-• .?;.•-1 -5
E 0 o *-0 0 •■•••••■ Cl..) 0 0" 0
0 0
0 0
. LT. Q
o 0 (NI . .0
E •1:•:
a) -0 c„, 4:1
-0 r-- ,_.1 r.i., o 0
~ w C) 0. '4O=1
CI II 4-, .5 ;1 0
4, a, LY 0 ' > -0 o cal 4.) r
a) 0 "FL
cd
04 ;
at 3 cn a) = ad ..-4- 4-'71 g
.2 6-
Cd F. 43) c4 e 0 ca. -0
cd
-CU C) E g (-1
"CS
cd "-F.•

0
0 NO
LL,
5'
O

a- t.
cat
e
to 0
cd e ^
._. 4.s$
c
.= -
47.1 • •-• > 5,)
7:3
0
CV
Activated alumina bed/

OC g
'EA
CnCi)
CCI E
U -0 -0 E
Mukherjee et al.,

0
T's cd
VD
a) O O O O
O
N O O O
0.0 8
O
0


0 >, o‘i
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CU CU >,-, Cka 'V
CL,
c7. 44,
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0 0" 0 d,
0
0 "0 01„ 4. :P. Sl..) 2 c.,... e v a) 3
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cd c . ) cl)
„„ -0 .0
-0 0_, 4-, ..= 0
e., 0
= .--2‘
0 tF4 0

o = 1:10 0
-0 a) ." -.-, (/) 0 ,,c 0 0
o
...... o t's1 a.3 C t
t ci. 00
0 • E7)' a) X c) 6 OA =
(2,
-0 co ox 2 °
a° to 0 ....
a ")
ct •
-o o E -
c.) ", el 0.) a) 0
0 -0 cd . - 0. c?1 CL, V ct
..= .- 3
..., 0. 0 •9 v) -,,• > le
.0 0 , rzi 0
7= tu 0 0 ,,- _
. O.) cn 0 ^F,
C 4c.:_,)
_0 .2 ..,...
.... 3 Ts 45 cc),-,= c) 0
0
-o
.-cd
4g .0
.8 -0
''' t) o g ..0 .. c,;
55' 0
o o
+6 -0 VI o - OE
4)
ccl t4-, . 0 0.0 1̀) U 4.)
,,,
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,
0 "0
..- cz .
v) al
C.) cn 4.) FA as
cr t4
0.) 11.) co 0 'f 49
3,b
>-0 0 a) 0 t:45 •5 (..4 cl 4)
cy tn 0
71' cb% `u
a ,... --"="
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'1° a
bo
E' "
2
0
E E- 2 o O
N -6 rw)" 0 a) -61 .4 , 0) t4 c„I
...-
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a.) • = ,...,
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0 c..)
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cn 0 cn = E 0 "0 = E
5 .E -.
=
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a.) ._ ...0 0 cn = v ,..... -,1 a c,
-4-,
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2 0 el) o
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0 76 2 2
0 o a)
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111

00 . - it) a) '12. 0
E ;
5 _5
u 0 0 >. - izT ,4 ..... cl)
-t- .0
0 0
o 0 _.=
.c...) a) 6 al *,„ 4-9
1
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0 E 0 -0 +a
cd
0., eu
u
at ..6 C E-• a)
Fal -10 0. ...6 1-6 u
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g
P
q)
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8 t..) ,,,
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1 --0
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4..)0
0 ,• 0
a ,...
0 0.0 0 a .... > 0
E o ria:
a) v9 a) ti1
,, a) 0 .... N
a.) O •g • u X 0 ci,og •-u„.....
o4-.--..,
7.., ,,,,
a) 0)
01.• LQ - F. '2: :), . ,4- 4
4-,
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0 y, (..... 6 0 o :-6 ' _a 0 E ' ..
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7.)
0 4) -c) E-. c) = 8 ,g a) 0 7, -0 v>
ci 0 *0 -')
> 1.) 2, 8
ccs 1-; .....
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+.. 0 cll• t4-, o
u g = ,. •.-- - 0 0
il 14) 2 4-4 2 0 1-. •-• 4-. 0 0 -0 .r.)' Z a•)
V) 4-. S-■„.., n 0 F, (4-. cl.) 0 c4-,.,__> -0 .•-• -0 .,-, 0,;$ c4_, 0
0 -4-■ • 5. g-, 75. 0 > • 0 cci CL -c-
J Rs ,48 vl 0
0 •
a) ...
9 00 6. al 0 0,d
0 .0 75 0, -
0 0 00 4 ot.
.5 i_. .0 = 71 = . = 6
E -0E
a) 0 to -0
a. It. a.

-0 w 0 0 _.; . o c.) t.1) 0 =

al a) -5 '4-' a) 2, ..E
,_:. as .... ct
•-• a..) ;- 0 -,, v) 0,3 r0 :9 q..) 0. -,0 = -0
-,-,
0 I
-- 1-•
-0 •- O •.- - .n 0. 0 p•• a 4- as
a.) Vu 0,7! 0 ca. c.3 e. -.6
...
o. ,.....
" "8 8

E 0 z a.) tl cid,
,... c...) 4.) C (1)
040
-o 0 a)
to-• tz,- 0 ..C$
v)
-
•..z ,.... cc ..o I-:
,L.
; a)
04 t)i) cu o v ,...a.) co 0
o -0--, 0
a) 0
E sa. 14-. 7:3 3v -. -o
co c.... = = o
* >
g 5 c) g `" co
0. 0 • •••■ •-• v) 7.1 o 0 czt fa. ,--. = 4-, '..... -0
= o = z = co m
Salt concentration, salinity

a .
cd vi
4-, V)
Initial concentration

0 a)
a) 0
CI.
4-.
4-, s.
0 0 0 c.) 1
-71
f1. E a)
è.4
. 0 42
a)
cl) a
ai a. a.
neutralized red mud/batch

Coal ,residual coal/

0
cd
N

cd U
Eduardo et al.,
Polaert et al.,


a) "0 >-. U a C> 0 a) I0 6-

2 .0 ',0 > 0 0 0 > 0 ..0 N g .4 cl
4.
0 -0 cd .-, .v) ^. ..-. .5-, v) H 1/40 7,en
1.... el) 2 >
0 >1.
a) LI.) -,,, 4. 0
c..... .., ..-a i)
R a) 2 el
CU ..-0 0 Cl
= ...6 rto
0 UO cii- 1̀1 ft Lc' la '' tn
.0 t0 a 0 v) U 1.4 Wtd F:' 0 .0 -.: 0.) ti-.V)f:r :) 2 il
17"
.> .40. 171 1Z$ .r)

E .Z.:...
>_•-, 0) 0 0
_ u 4.) :1: ;5 cd mt 6 h. :-
o . - (4- ,,,
b 0 tt2
., 0 ti7) ,- .0 -cpi) •- a) .--
',
c.)
g o.
,,,) (4- -6 0 t • =
0474
• bl) (.1-1
-o 0 • .•-•. v)= •- a
..., 0 '-' 0 oo
0 of c-) ) ' a a) .0 0
0 ..o a) C)
a o a cp E 0
t'
g -2 c+-
O g- bo
a) eic vC ..,
. • ..., =
-2 o
,.... ..= -a a a
al ) •
-bbl)6.
'RI = 0 0 a, 0 (4-, a o 00 o 1
-'
0 -0 vi al no 2 0 U cn
-.° a) v, a) 0 t ° O. V = 2
a)
..- en a.> al c,s =
4= (') 0
4,°
., 0 - 8 .- i-,c N 0 (4 I-. = r"
o cL. ..., 7
04 0 .C . j
M
= a -0 -4-. 0
00 VI 0 4-' j5 G = coo
.. N ct E a)..-4-4 :-Ey-
>, 0)
..= ..0 ari ,,r ,._.,, •.E. .14 C)
gl .
0 a 0 bl) co tu 4-. 4. 0 0
=
ye' b.( cu ....
O
7:3
ctt 4p0000
..4-. a) cu CS > 2 3 ti o O
(4 4-, o
":4 0N1 -4 ' (•)•
)... ., -4-. .) ‘1■1
1.2 43, 4.r)

d
z ..= 4.- a) -io
E-.. a
N
0 ..-
■0 .0 th 0 co -1° 0 c .e. (... .4s t.> "
<4 •---, ..._ cd := Z.?
O
U a. 0 -F. al ''-' • °
Fi
v.. -5,_ Li-. ‘V CI) 0 *"-• Q.
-o c 2 Vf
0 3 t5 -= C i 64
- a
v) a) a 0 a.)
cl" 4') 8 5 ?, c./3' "0 0 '''' =
a 4=.
,.
. o >. 44

t4.'.
^ 4C-). 5 -,5 ct cgs ,,,, 0 >+ :-' ct/ • 7< (A g 6 1) .5' "'
C.) V) s... V; $.4
,..I.46) 4) cn
td H a. 0 cr.. -' --
a>-,0 t '0 0 t) ,n 7 ) 0
p.. '-o ;..-
6. . O 4-. V) ct tn
0 1, 0 -. ...a_
0) `1'
•■.. CA

8 2- (1) a) 4 a.)
• ()
0., "d
a•A, 64 tv ,0, 6 .* 0 0) `1) "C:) 0 C) >1
a)
e, IS
$'
1) -=,...
g c.) a)
g .0 . F.. .
a.)
a) 61 -0 2 :6 ,t 0 °
CA 7)
removal rates

0 trzi Q. 2 ...E ..= I c; E 0.) cA -45. ccl

0
a = ..
8...
3 =0 ki
a) 0
a> E,.. t- o) al 0 '4
0
;... - 0
a
v v)
>, a) 0 a 0 ...,5
U 4. . ci) ti) ....
.-
a) .9. 8 -,=.
:

o 0.0
T3:2' 0c t; -

Q04 0 4 ' 4) 4 ' '-a, 1:3

4' 2 73 >,
-0 ,cci O -o 5
- _a tr.
d 0 0 co
m < 0 .4-. -.4 . 6
°
7
:::3.- :
-zi c6
. -0 ta.
-g c..
w 0.::
a
cz • E -a '5 Pc C
U
)
a)
el =0
:I I )-
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":
4):j .,L,
c c.)
6:11
cl o
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1: .c..
.
(....) 0 xdo .iaso, I ::, 8.
-o C ..5 ,.`,8 ??)
= ........_ a)
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cc, E to 0 a.
a)
a)
a) 0 4.)
:-.=..0 1-0.45 ., az
(.., = IL. -o W -a
0 to - ,..,
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o a -a c.,) ct 0 0 ed 4. ON "o
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a) 4 .5 ..a
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4'::"
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CU ••-■ 0 0.)
•Im. ta, ..„
c.)
c.4 a) ,5') = = .- .E 0 O
0 ''-' va 0
a) 4. 0 --
oaa =
v) > 0 ) 0
4-
0 0 4:: t4C.
:
.1' •.2 " 4. 4. L.
(....
0 7:1
0
I 0
4-.
z a.)
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0 < a) r3
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a.) ou H
:
0
6
11 , :: .-I
0., 5 .6
: :v
O
Ni: ;
a. I.- • 49 -*'
0u (.40
cd•-•! :
c,- ..4̀
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--. <I. !
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4 1), 1.
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0 a, 0:3 'al c1
0 .-. •-•. .., 405 X ,.. 17. ?2) Tp)
8 0 $.-. 0 C...) 0
v >
tr)l)
0,.., a
-" a, •.;_-; u ..vo '
0"
a) 6 474) a) 44
Z 0 -45-■
..... a. cn ....
0.) c. •0
,-. 2 o
O
0, a) a)> O 0 a) g 6 2 E U 0., . cc a) < u -a cl TA a)
2 -o 0 .0 ,-.
0 0.. -5 ,,, -0 •+0 cd a 4. C- > +4 en 0
0 .20-, 7 0 et g

cn

0
u-4-, 0 sa. ct 0 C)" .V. L4
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•..s
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g
0 Cr 1 0v.. 7:,' '4,-
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0 -5 c
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9 "c - v N 0 V 4, (4-, CD .14 C\1 -0
r■ 1
4- 0 C1 ON • •-• 71 a) 4) _ U 0. t'•
1E, :i.:•, (.2 Eno O
.--, el -0
c3-' .-
0 -
0 •4 E c*"
o. a C)
t4.. --
0 0
= 6) = 0 VD X cl
1--■ fa. 4, r,
>, '...,
o. 0 -0 N.I. -a
,r-, .4
a. 0x< Cl> E a a.
PH , initial concentration

Cl

ai 0
O Ts

N 4)
a.
'C7 E
0 a) 0
E °
Activated carbons
Tziotzios et al.,

Takashi et al.,

Cl cd

vr-v a)
O Cl C) M
0 O
O O 0 C>
N N 0
ti


,---. 1) = a)
0 .1:••2s 0, E. - -u 4 + :9 i:c UU oZ
1:: 2 5
.1; a a) ° , 0 0 [-- ° 0 N En
o .0 a
pi) 0 c 441-.: c.) 0 E . 0. 5
..0 cl)
= (A a) .<,. „) pp ci
i-
,:i V ''E 3roczt...5
c U
'''' E E "FS 4-, - 0 5-,
0 4. V.:
0 0 , :E3 ›., 0:1 c < -0 0
•
et 0 0 0 Th.._
0 ct 4-, .-.•
c.5 0 0 ..- ,,,, 0 -5 0 C
g to v0 4., > cl''
ca4, ed CL I:4 0
° '4.
8 0 - v .g g c..) d.)
0 00 0
N 0
E E=E0E .5. n 0, 0 .
i a) a) "0
br., 0 0
0 .7, 0.0 t.,=,
(4-4 trl 0
C (1.)
=o c.) 1,::)j a)
-d .o'0 a)
40 t) 0 kr) c
i... 0 0 a) >) c.) 0 Zs c 0 g b1)
S ....•
°•
o. (1.) (-)
0 • C..) :__, 5 A 0 0 11 CNi
trl * m .2
0
CI-, cn m L >, 0.) > v)
C. b' 0
_ 0. B Ed "Ci .."
-0 >, ti) 0
z 02 5
■„.4
a) g g 0 0. ... ao 0
,..-
5, 0 o ..5
I ) -a -0 9. '' >, .0 -0 0 ...
0 ..a 0 0 8 a. 0 ..- 0 =
E -8 c c,; U 0-7; 7,,t (E. .5 cal -
0 :„ - 4-,
•,,.., 0V
Z
0 0ti•-■ o 0 > .g 0
3 0 c,.., ._ .i.., <1,,, .-- 0 o cr .-
46, a) -0
0,
,,, ..= 0.),... ,...
,
a) T<. 0 4 Q = .r... 5 .c,?. >0.) w--,..
(.3 "0 4c71 '-' ti' •
0.0
5z ti-, 0 5 ›N .0 3 v"
x 9 8 0 a.) 73 a. cd 5 (1) c. 0 cl
VI
=
0 cci 0 ..... a) ct z 0 3
.5 - t4.1 Ti 5 -6 c.) ca t, 5 ,..,0*
0 am s) ..0 i- ort 170 .5 eu
... -0 g 1.- 0
(4...
0 os .:
-7., .. a 0
0 -E 0
,,, cr3 E cd
i O 0. .4 MI $,
0 ..1e.. 9., ° 0 5•a) 0
1...
= cd 5 d -° 0 ..o 6 3 -.5‘ 0.) c VD g CL 4-, ..c)
4-
0 .-
° SIP o
0 0 _a ,,._, c) (..) a 1cl
- - a) re ..= a- 0 4...
1) 0 u ..=
t) ...■
-0 o(4-.
.....
)-• 0 (::, ....., • x A f- 4) g r:'- 1:5 5 ti 0.) 4-,.
0 ..= ct -5
a) .5, 4) -0
Ca,
-o0 „
o -oH. >) c ' - I-
a*0 5 r"I-n (4... 0
-F.,
CL g
V cc; .--.c• -tr,
,.,
" z aS a •-■ 0 0..
75. 0 0 ."-' cri ..0 (IP "t :4' AD 0 t,.-, o u ,,
.4 a)
1-. 4) .) "0 2 >, _.
■•"" cti 4-, '•-• ...., 00 0 r... .t
ci).)..,
L tu
vi z .2 o 75
o 0 ,...
rz. c o _>_-..
tA c..) 0 °A 0 -o $-,
••-' 0 = = 0 >- o .2, (4-,a) cc) E .4 „ .> ...,.;,) bo 0
. ■--• (:)
.' a/..., 4a. co; 0-13 5, .5 o a) -- cu-0 4•• c;'-.
..= aki " E , u t; >, -c u
0 00 8
20 0 cu -- 3 Ts cl) 1-A t.... •,-' ... '''::
al. = ¢ fu .. -a E -
czi cri 4) ._ -0 n g -g t 8 2 s. -.5. Ed - .;,. ..- o -.... ,,,--... 0., 0 mi 0
cat
t'n g" .- b
.- t 0 c
a ell) .10 ,4
4..) Cl) .0 0 .=
0 19
474
g .- 4) .0 'EL L) 0 4t-, E
c 0
cl .-,..,c..)o- ou= 75. ,c) , ., ,..,; u >...=
X> -0 --* 5 >,.F., ri
vi 0 17)
-o .t)
0 2 t)>.76
0 8
0 (It 0 0
0 sa, 0 ,,,, 0 = .... , „rs . .5., 03 ,,,- 0 <
te' TA= 00
8
..,, 5 .79) g .a) ,ii: 5
1
11 75
0.9, .73 : 2, ..-. ..0
= .__,
z p 'fa 4 0
(14)• M t).) 91,
5: ..0
0a..
U z 0 2
-0 0 5 c-si
= =7.. ,cd.-..4
.t ,c .2 0= . - g
'-' U) 0 ,-" >, a) ..(6 -o 0 tti ›, till -0 `3`47 0.. ■0 '11) CI)
-.5, ''4g ,,
•••-• N t'<-'i) 0 ..=
4) N
3[...,.
L._ a) ,.c ozs 0 ..•-■ a.) u .a
0 ■.o ii.0c+. 'Fd - es 'a
0 C-• H 0 -0 0 E ,_, 0 -, •
-0 t--: - .2.. • 0 , . c ?.
N 1----
0-)a.)...a .= •.
o0 a,.....
a. , 1-...,.. 0, 1- c.9) 4,-/, 0.4 "C) '85.,.' ••a.
E D; a) 0 ..0 4,1 8
.1-.. 0 ••••
0
2 u00>-.7,s. 0
73 . ;..1 30c)
0 (/) 0 17.. ■,._■ et ..=
2
"E
0
IDA •a tab "0 0
..0 ....-■ ,,,...
. ' re% =
ri) 3 = el E74
:E 0 '6) ( 1 ) . .;<' .2. ..a 0 5. = 0coa-) 5
0 E-uui=08g R -.F. -.. = $-. -0 a.) -Qr.
E E--, (.4-) Q • ,... 0

a)

O
U

O
-0
0
-0a a)
rd.
ClS
U o UeC
Dorotea et al.,

CC
CI) NI
O • 0
O O
Csi
,••■••,


ti-• >, •c.) a) 00)`48 ,- .t, C/) Q -,z, 2 g -ti 60 ...., 2 cid
0 v)0..0 a = "0g
o 03in 0 0 .0 41.) -• = te)
al 03 -. 0 0 >. .,..,
,43 c 7,:„ til .= +
0
.....u c.)
. a) e4 e g
) 75 2 F._, o a)• cra 0 0
00 0. a) d > 0 0 0 .0 0
" -0 -C
E 0 e t) .,,, 76 v c;74 . 0" i X -2 Y,
,... t.,_-, . .To:= •.b..,
-
ms o ...0
. 0
.0 Cr 7:1 0
-0 FC:i 0 CI) I-. 0 .() •B. cu .0
V' 4CI) o 0 5 '' -12 8-4-.Is a? *".- 1 ci- C")
o.‘ Ct = 0. ..0 0 a) E o >
cd 0 ..c)
0 ca. 0 cy "
,.... ,,_, 1 EE ,42 .2 O
,-.
<U
tt a. .0U *- 0 tt.t..1
til `,`,) E -.U cu
..0 t,.., -0 -3 > 0,0 3 cu> 1-.cl

evaluate the
I- g c) 0 0 CL. 0 c4-4
F..1) -3 a) 74 '' E-' a) - = '0 0 0 6)
cr Q730. ....., •-•
..0 0 cd a)
...0 .-. E30
a.) En 4-4 8 E).Fi)° --- 0 v) cL) •-• .0 1:"
E-i)' 0 .- ..5, 7?)
c' - .- -0 a) =
U:.c)
0 77 -E
cr1 cl a) x ..... W v) cn C
0 o o 04 0
0 cl) in
= a) 4)
:ct) H9,L...5 00 0 c --
0 cip -0 el) 0
-45,=
0 2 cn
0..r.- - = a,
t,- E re , 4.) vi .0 t) •
as C L: ,-c 5
t• • :-0.,. •-•
cts) -....., g 0 "0 0 4-.
0
. C.)
E o .1...... 01-4co
cd v) v) a) .0
s... 0..
0 a) E ~'-'
,_. 0 a) § 11 al 0- ct 0 C.) • ^' ;a -S
4-4 °1 a) ,,, C.)
•- .4 7: IN3 s.
..0
.... : '5
lo -4;=
.1) (I)
:i .0 .....,44-4 0 2
- E 43 4-' -0 El ,..., a
Tu. ..0 .,7)
.-., a) er.
1. 4...
,,,, E #05... is 174
a
,-- ...0
-.... '45
v
0
(4-4 7.s cii
O
1-•
1. CU s-•
U 0 -o >, -0et, .2 0 4-. 0 0 a) °
i.4-. E >)
° •DI ,..%) 0 cn 4-, 0 '0, ,,,
En
-,i -o - ,.. 0.00
-0 ...., ,`u-c't',0 0 0- o 4-•0
al E 2 _0 " 0 00= .r, 0
a) X a) $-.a)..o .0 -.0, = o
.0 E . .- a) c..) `a o
c.) g 04 4' (4
,-.,
a
4
0 ... ti cl a) 0 a)
0..a)0
4EC4a) cciE 9. >, • 0 0°,.. >- ),"°` •••••0 a° 1-4 •••••
1
- 5) 'a .rii ,.. 0 X il) tip
T.)
■-■ 0
-.4444 0 0 TS C.) ctj CD 1/1 -ri
8 .c.) a. E t; "7 -0 0
C) 0 V)
E 0 al irci g 00c.) ....=,-04)..5., .4 a) ›x.%
ii. a) 6 6 c .0 co 0 c// i•-• C0 .
L_ cl -0 7) .2
-= .-_-; '4
N ad 0 .c.2, cci
(. t)c...
= a) ,......, 0
54 go V) [.._ 0
-0 P, os 017..X a) ,...!?
7..-. 6, :=-... ...:::: _.„-- 0 ---, ° 4) g .-.., ° 4.-, = + 00.. b .4.J01 7:1O a)
TS ,. .0 r.,, -. 0 ::-0' 0 0 -0.'-, -E. :E 0 5 ° 23"o -0 ra. ON -0 rr, = ,.., .,.., >
... o cn U ..... C.) 77 aal• i4.-i °C 0 "" 0
, 4:.. cl 0 .;:..1 c.4 0 0 g ,9, .E... cdH.- ...
>, 0 = ,..., 0
c 0 v, ..0 ,. . .in cl). .5 a)
-10 r.... 0R. --
>-, 7.F)
0 • 4■I
o -6 ..... • ..-
0 0 a) ba oi) 0 lli a. ".E. a) g ..= ,„•'
0 o .0, ,__. y2
H .0 i....
g
i-. 3 -8 -0 4.) tu
0
a) 00 a)
...' 1...
O 0 c) o c)
1-c1)
2 00 1,5. 0, = c.)
1...
-i-i ,.= 1.0)
,......
i.,
ce-.0 v)
v 0 ‘--. 2 V) 0 ,0 0
a) - :0 -6 co p., o
0
'' .5 E 0 t-.. tai4. 8
,.= 0 +a'

,,,
17 0 D x
0 ti. .2
0 ..,- 0
45 a
0 ..0 t..4
0 - 0 8 cl) *,,) -= .2
.fi .
0. °I a)
a) 0 ..- 0
C
.-. al E co .0 ..0
....
0 ..0 8 ,t5. tz.
,})
t O
i1) o td)
a)
, ...E
c•-, W c.18:1'
0 0-. 0. -.E. --El) F.)
"
8
" a) 0
v)) • 05 0 0-.
0 ' 0-. (ri ,.. 5 ti) •-5 >, ' ....
O o f..; o c4- 0 -.0. 0" k2 il t 1
.,.., 0....
„., 0
0 .-0
0 0 7) E.
2 cl
a) crs C4-4 0 ''' 0 't al ./0 •47). cd T.: -l) 4° cci co 0 > 0 .-
1-4 -47) .o g Ts ii-,
0 .a.4 -a, *1 1::, 174 .+
7: a:1 a,_1- .'1---1 . - - •-• 3 0.
. ''' N _0
0 -iii 4.,
9 x. <4. co
0 u c0 Lou •E p .- E
r. c il E Z S) - E an t) • -rs. : 3 ZU 0
..... 33 co a) .... ,..) 0
a) *t 0 , o u .() 52 0 2._2 o -0 -0 0c.)
ci
to Eo -4-.
73
.- 0
le, 0 v) a) 0E
,..) 1-6.. .0 " 0 c) 0 t) c.) E.b c.cy rs E
•- .0 000g .- .ia. 7d E) czt ,4 o : .-.... ... .7-fa, o z 7) ..0
`-'-' E E .° •:'' -0 ra., 4 .,,,-,), ..0cd. E* 0.1) '.«-• 6 a) 4-. .o a) a) 77 Cr 't,,, t)i)
‘..
6.) • '-' Cl.) +-5 4/1 < ty. -o E4 .•S g 6 0 •--4
(4.., -.5-• 0- To '-' No 0a) --,
2 -0
t,E
0 z 44 V) 4- ••■-..
. a) cd a.) a) 0 3 4 1 0 .0
, 0
0 CI a) 0 ›N "Tti >-ori 15 --- x 28 8 K. „:9 2 ° -0 et: co > 13 •= ..0 -0
4 Cj- " ,-,
0(1) Ea) 77
2 0 `48 . 0. 0 c 0 ,..,
,.. >. o
77 0 E I) .0 0 ;rd.
V C.) ,...
0 0- E •-• 00 ... .4.-.: a, ,... 1,-. = .0 ) a) aa., a.) 3.....c))0 -o .›,0.. ._6., g ,
by
• n+ C..) 0 Cr$
° I
4.) a) P'
- -° .><
0 > ,>_. 0 -al o , E- c2 0 0. 0 E „,,
-‘0
,, -0 --, 0.) ,..0 v, Q.
o0 a) 0 -0 1- 0 ,.. •!•'
2
'8. :-.
-lo- "t
.c1
-:1 '47
g :is -6
(,) a) 0 0. 0 74 ae. .5. a., vr,,....
09v)' .) .G., a..)
.75. -'a.)
•=i ..a. El u , 0 4-) 0 0
4 .4 -. Q.0- 0 :0
.... 0
a) a) . r.: 0 cd0 a) 4.
= . ,.,
0 00ti-, ON = -0=00.0 .. -0 .....,._. 0 0.
E--• il..-s o 0.. 0 at ..o 0 .- 0 0 VI 14 &0)‘ Cv) l) -0 E E-• Cl. 0. 0 --. M.

0
0

a) a)
O
O
0
Photosonochemical

"0 t
g 'S
0, a.)
a) co -0
cod
c.)
:3 '5
Chunde et al.,

4•-•
O 0
O O
N N


1 ..0 06. 0 . 0 0 ai v;
° • I 0CL) 0 0
..= 0 0 al5 .-6 g o 7>4:3
an 7
c.r) > a)
,... ... ,..0 a)
2 -8
v). 74 09 o
g 0 cci cd .-0 En o o 11. 5
0 ? C.) 6-) .--4 vi
0
0 0
0 0 0 C..) .0 0. ,(3 0
,_
71' •g N ...a 2
.-
-C a)
0. (I)
-0 t'l a) = 0
1..... °' 0 4-'0."v)- 0
.-■ = v) >1.
-
o
o
• 5
o
L: ! LL) --
cu
n 0
''
1
0 0 ct.
0
:6 -0
6
0. u
us f__, >, „z0-
a. c....
° 0 0
000 " 5.'
.... I.4.
s•-. r) cn
1) L..
N o
o 3 -0.
t)4
z
O
u a
'A ad vi ..0 .
a) . c+ii-- 4--, • a)-• (1'
(4-
orD
) ..0 -.. 8 O. ..6 0) o
0. ° 0 b 0 (-) 7) 6, LE:
•a ,...) = --5. g.
- 22
0 ctF■
o
v; 6 '4* E
C9 ..... a .Ca
a) 0 tit ..>-'
0<4-, a) c
E on 5
fa, en
o - 4 ,...
4-, „t-2, a) z 2
-o
p 0_
that the presence of Fe2+ enhanced TOC removal of phenol solutions.

0 cn p - 0 zy g P•-
5 E 0 ... -E. = >., 'c.) 0
r) to-. (1-1 * • 5
. ,.)
a) rts 0 ".05 V 0 0.., =
•-> .-0
- "0 a) cn v'Zcn = 0 ,Ni ,,,.., v)
= cd0 g 0 0 0 04 0 Cd.-. tu= •• Q 0.0 .2 U
.4M ° I' - 000 • 01... .0 0 U 4-. •-• 1..., CO CU (1) ..0 - p • 4) . 0
a) {... 0. 0 eta 117 CL ',2 g RS ..,-,1
Jo .,..
0 0 CL) V •-• 0 a) p 0 F. p
O

C i -1.-.
i - ' 0-.
= 0 Rrt 2. -I : I: "5 >.r
= 0. 0 a)
aztu .
z0 a)
-0 a) •)?.., -0 -0
o
0 z, P 0 W.^, '40 = 0 0. u
•-.0.,.
• •-• > V) m.- -=
...0 0 (1) = g _c 0 , 0 70 ..a
. e'D
.. E
vi
a) 0
. i•-•
•'-' t)..) 0 a.) a -0 0. -0 -I.,
Q A ?
tu '5 0
0 3-4 V) U -Fs't.)
9 :4.-, a) {.„ ..= g
x 0 0.)
CL CL)
E ,42 -8. 0 a) 0
.0
) ....
'003 .do cr. P
z :.,5 0 ed 5 1-, O. cn
4.)
t.:..z- . _
E g E
ci 8 ..-
... ) 1-4 ....
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4-. cd(4--, 0..
at ,_) u
.... ,.=a). ,... ..0 .;-. ...r.
g 0
5 0
z u ti..) •.-.
.
.0 o vs F, =
...a 7..d .4 "6
0 . c..) to E c`j o
4-. I. CF. 0
V CI) 0 ..
E
1.a) a) r.:,., ''"
"IQ E 1 .
-0 E °
CCS. . 2 a rzl ,,,,
o
" -, Z1 :.5 .4. -
CCI 4) .4.-■
p C> ;)
-4-, •c.n..
.•.15
rd .4,74 0 • -• CA .10 0. ,.., ._. a) .... o
C....) CV .47+ 0 2L
s-. adI)b.0
4) 0... $•-, ..0 '3.)
cd 0 .7J +, Z 1.) 11 a) = ,.= 4:43 c-4 Ls-.
0 0 .0
= t...
cz = . 0 1,.., 0
4) ...., (1) ° g '
= ..0 0 .0
0 1- '7 ..= 4-, ,.. ,....
E!
• -• ...c.
CIA 'z
" n 0 e.)
••-• ...0 a te-, 0N 0 o ci) .0 v) 0 = 4.) 0 ;14) C4.1
ri) -0
(1) =kt 4-+ j o E
.d Le-. 0
0 0) c"
"0 E ''''" = .,7,. 4 i
4 ,0 ,.4_, Q .cn,_ .4‹ "0 "N. 4)
0 "0 o a = ' ,_)
'-- 0 t--- 0 MS 0.)
0 ... X 0 -0
> E 8 0 .... E a)
C1' ,C'. . ') V) •0: >. 5o 0. .c; 0 b 4,
. to
> a.> 0 . a) >-.
6- -0 ;.. u -0 0 CIO - E.
: ,
' as -o 0 o
RI 0 § -0 0 Z
0 o)
v) 0 4) 0 cn = ,.., 6, -0
an ..0 1- a "0 Cl. 0 1.) ta v X 8 ,
.. -
8 ',
8 .....
''D a)
0 0 cn v,0
- ...F
V I.. °

a
cd -0
4-. P0
"‹ al >
o0 CID

= (..) "
E ■ g V i. as rTh
tg . = ›, CD
>l .0 V
i. ..".' o v) ...= ki
e E to w 0 0 rd
..c
..0 JZ M.. ..0 • >„. c.• .4... 0 0 00 .5

--: ig ,12 >. cn u 0 .0 co >.

•E

z c
°
Ct. 0 v .--'
i. .71 a) _ p '.)•a) P
ai v) .._, 1.:i ..
-.' ti 4)
a) 1:--)
x .1- 0 = .> vl ›.c0 vs
O
a.) ' ...= ' Fa't 4-, 0 .2
°-) __, .5 fa. .4 O
ki gj
ro
u'L r).
1
5 4 2 fa
) -.3e, R. 0.-. 0 74 45 0
.4. 0 . -
E 0 0 E "It" ,..=
()
--"' (4-, - t5 ).<
[-, X 0 a.), a) E cn
4 co
Er -. ,-. 74 a
' 1?.. 0 3 E

Susbstrate concentration
PH, In itial concentration
PH. initial concentration

p
0
ed

a).
+0
O
cd

Sa

O
tn.
XAD-4 resin

0
0
N
0O

0 CIZ
Edwards et al.,

ci cd
N
cd
I■11

0 ca CO u e-. 5 a)c,,,) • - Lig en .;.'' W .' .... .0 ,4
•-•
0 0 -E, -1- 71 C 0 od a E 0 -' ,,_, su f V.
CL +"' 0 E - o ''' g
0 4 Z 0
3 E 1-4 ' .9.. .-z 00 s.s. 0 0 to 2 .8
Q 1-A t 8 0Cd crs ' Cd 4
,,
. g. . :1-.e•---:•
E. 19
N a fas 1.-. cn
'

0 -
c 4-. a) cz c
..a
t? , _
5-1
. . o
CI) E 2 .,...
= o
E
a ) o
a) ,..• s.
0 0-
P kr) a..) 2, a 0.) >:4/-
;.., 1 ,t
•E 4.) ...0 7, .0 Cd C.)
N
cd
...= 37:1
d 7.4
o as „ -o a c) 6
-.5, E-. -lc) a 4) o c' =
s.. = 0 (4
4
6 a) - 0 E a. o 4.) 0 E 0
-o 0 o -1° 6' 0 CI 0 E
1 g 0 74
M • - in
Ci. .4Z .0 u9 rd ort
v) *10 1 G.) O a) 0(,)cd cd E ,....
2 1 C4-I
E . ...,g 0 E ...5, 0E- 0 ) _0
0 0 -
ul..g a -,-,
c)
70 0 cd 0
C0 • ". la 12"' 4. ..0 cr: 46' 3 •-' ° 0 a) -. 0 ci) ,,
tu) z • 'Es' - = ,c1
88 = I -0 , 44-i..a71 a ,,, 4,74 .-
o-8
-I°
o ¢
- "
E -ci E 8 a) x 2 8. g C, ,.., ,oaE .0 °1-1 ,. ..=
,-, ...a
0 (1) a) -35, en
a ccl 0
X
-codo x •- -c E 50 1. Q u
s.. E X a) 0
6) 0 0
CI r4

CL g C.) '0 C;) 1-C'.4 sE.

0 c..) o e, ° ° 0 bh ,..-. o 7,
3 .- °11cl) 3 u
(.; 0 0 0) Ca.
Ce.

ri „, ;_. o
o °
U o , I g o $-■ tt
0

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 CHAPTER - 4

EXPARIMENTAL PROGRAMME
4.1. General

In the present study, aluminium electrodes were used for the treatment of Phenol
bearing aqueous solution. Experimental details of the study have been presented in this
chapter. These details include characterization of electrodes and sludge, reactor design and
batch electro coagulation study with aluminium electrodes.

4.2. Materials and Method

4.2.1. Material

The Laboratory reagent Grade Phenol used in this project were purchased from
WISWAMI Chemicals Pvt. Limited, India. The molecular structure of Phenol is shown in Fig
4.1 and properties of Phenol are summarized in Table 4.1 and Chronic Toxicity in Table 4.2

OH

Fig 4.1. Phenol structure.

Table 4.1. Physical and Chemical Properties

Description Colourless to light pink solid

Molecular formula C6H5OH
Molecular weight 94.11 g/mol

Density 1.0576 g/cm3 at 20°C

Boiling point 181.75°C
Melting point 40.9°C
Vapour pressure 0.3513 torr at 25°C
Odor threshold 40 ppb (150 mg/m3)

Solubility 86,000 ppm in water, very soluble in alcohol,

Carbon tetrachloride, acetic acid and liquid
 sulphur dioxide
Henry's Law Constant 3.97 x 10-7 ATM-M3 /M01 (25°C)
Flammability limit in air (vol %) 1.7 (Lower)
8.6 (Higher)

Flash point (°C) 79 (Close up)

Autoignition point (°C) 715

Table 4.2. Chronic Toxicity Summary

Inhalation reference exposure level 200 Rg/m3 (50 ppb)

Critical effect(s) Twitching, muscle termors, neurological

Impainment; elevated serum liver in rats.
Hazard index target(s) Alimentary system; circulatory system;
Kidney; nervous system.

4.3 Experimental Apparatus

Power source

Al Cathode

Rheostat

Electrocoagulation
cell Phenol Solution

Magnetic bar stirrer

0
I 0 Magnetic stirrer

Fig 4.2. Schematic experimental setup

Fig.4.3. Experimental Setup.

47
 The experimental setup is shown in Fig. 4.2 and Fig.4.3. The thermostated electro-
coagulator was made of Perspex glass with the dimensions (12 cm x 12 cm x 18 cm).
Aluminium plates were used as anode and cathode. Dimensions of electrodes were 80 mm x
80 mm x 1 mm. The electrodes were connected to a DC power supply with a rheostat for
controlling the current density. All the reactor specifications are shown in Table 4.3.

Table 4.3. Reactor Specifications

Electrode
Material(anode and cathode) Aluminium
Shape Rectangular
Size 8 cm x 8 cm
Thickness (mm) 1 mm
Plate arrangement Parallel
Area/Volume 20.0m2m-3
Effective electrode surface area 5.12 x 10-2m2
Reactor Characteristics
Make Perspex (Organic glass)
Reactor Type Batch mode
Dimensions (cm) 12x12x18
Volume (L) 2
Electrode Gap 1 mm
Stirring mechanism Magnetic bar
Power supply Direct current

4.4. Experimental Procedure

The cell used in this study was a Plexiglass rectangular container having the
dimensions (l2cmx 12cm x 1 8cm). The cell was surrounded by thermostatic water bath for
temperature control. The performance of the cell was evaluated in batch mode. The
experimental setup is shown in Fig 4.3. A Vertical aluminum plate is using as the cathode
while, a Vertical aluminum plate acted as the sacrificial anode. The dimensions of the
electrodes were 8cmx 8 cmx lmm. The two electrodes were separated by a distance of 1 cm.
During electrolysis, the current density was maintained constant by using a voltage regulator.
For each run, 2 L of phenol solution was placed into the cell. The electrolyte, NaCl, was

48
added to the phenol solution at the required concentration (2 g/L), then the current density
was adjusted to the desired value and electrolysis was conducted for a certain time. Samples
were drawn periodically during each experiment, filtered to separate the sludge then were
analyzed for phenol concentration.
Before each run, organic impurities on electrode surfaces were removed by washing
with HC1 solution (10 wt%) and then washed with distilled water prior to use.

4.5. Analysis of Phenol samples by 4-Amino antipyrene method

Analysis of samples were carried out using UV-spectrophotometer by analyzing the
colour resulting from the reaction of phenol with 4-aminoantipyrine at maximum wavelength
u =500 nm.
Reagents:
4-Aminoantipyrene - A 2% stock solutions was prepared by dissolving the purified
compounds in aqueous solution.
Potassium ferricynide - 2% aqueous solution
Ammonium Hydroxide - 2N Solution
Phenol: 10-100ppm
Procedure:
Transfer 50 ml sample to 100m1 conical falsk with stopper and add 0.3ml of 2% AAP
and 1 m I of 2N Ammonium Hydroxide. Mix the content thoroughly; add 1 ml of the 2%
Potassium ferricynide solution and mix again. Reddish colour produced was compared with
the sample with standard solution prepared.
The efficiency of phenol removal, % Removal, was calculated as
% Removal = (C, - Cf) / C, x 100
Where C is the initial phenol concentration (mg/L) and Cf is the final phenol concentration
(mg/L).
E. Consumption = I V t / m
Where E.consumption, I, V, t and m are energy consumption (kWhg-I ), applied current,
Voltage, Retention time and the weight of the treated wastewater (g) respectively.

Calibration:
Known samples of Phenol were prepared by using stock solution (1000 ppm) .The pH
of the solutions was measured by pH meter and adjusted by adding NaOH or H2SO4

49
solutions. Samples produced in 4-amino antipyrene method were analyzed using a DR
5000TM spectrophotometer. Phenol concentrations were determined "using a working curve
by plotting the absorbance versus known concentrations at Itnia„ . A standard solution was
taken and the absorbance was determined at different wavelengths to obtain a plot of
absorbance versus wavelength. The wavelength corresponding to maximum absorbance
(k„,,y) was determined from this plot. The pmax was found to be 500 nm. Calibration curve
was plotted between the absorbance and the concentration of solution. The linearity of
calibration curve Fig. 4.4 indicated the applicability of the Lambert-Beer's Law.

0.35 - y = 0,009x + 0.084

R2 =0.999
0,3 -

0.25 -

co 0.2 -
0
`" 0.15 -
.0

0,1 -

0.05 -

0
0 5 10 15 20 25 30

Concentration, mg/I

Fig 4.4. Calibration curve.

4.6. Characterization of Aluminium Electrode and Sludge

4.5.1. Scanning Electron Micrograph (SEM) and EDAX

Scanning Electron Micrograph (SEM) images and compositions of (a) Aluminium

electrodes (anode) before and after electro coagulation treatment (b) sludge procured after
treatment at different steps (c) Unloaded Granular activated carbon were obtained
SEM/EDAX QUANTA 200 FEG (specifications: accelerating voltage from 200 V to 30 KV,
resolution of 2 mm and magnification up to 1000KX) in Institute Instrumentation Centre
(HC), IIT Roorkee.

50
 From EDAX, the composition of the elements in weight percentage and atomic
percentage are obtained along with the spectra for overall compositions and particular local
area compositions.

4.5.2. Thermal Analysis

Thermo gravimetric analysis (TGA), differential thermo gravimetric analysis

(DTGA), and derivative thermal analysis (DTA) curves for the sludge obtained during
flotation after the post-treatment of the EC treated solution by Perkin Elmer PYRIS Diamond
Thermo gravimetric/ Differential Thermal Analyzer.

4.5.3. Phenol solution Analysis

Parameters studied for Phenol solution as COD was obtained by DR 5000TM

spectrophotometer and conductivity was measured by Water Analyzer kit.

51
 CHAPTER - 5
RESULTS AND DISCUSSIONS
5. General

Removal of Phenol was done by Electrocoagulation process using aluminum

electrodes in a batch process. The detailed discussion on the results of the experiment
conducted is given in this chapter. These results include:

> Batch Electrocoagulation studies.

> Batch electrocoagulation with addition of GAC studies.

> Characterization of aluminum electrode and electrocoagulation sludge.

5.1. Batch Electrocoagulation study

In order to study the effect of different parameters the batch operations were
performed. The entire runes were performed at room temperature. In each run 2 L of the
phenol solution was poured into the electrolytic cell. The effect of various operating
parameters like Initial Concentration (CO), Initial pH (PH0), current density, and inerelctrode
distance is studied and presented here.

5.1.1. Effect of Initial pH (PH.) on Percentage Removal of Phenol

It has been established that the pH is an important operating factor influencing the
performance of electrochemical process, Current efficiency as well as the solubility of metal
hydroxides. To know this effect, pH of the phenol solution was adjusted by using IN sodium
hydroxide and 1N hydrogen chloride. During the experimental work phenol removal
efficiency was determined in the pH range from 3 to 10. The results are shown in Fig.5.1.
From which the variation of removal efficiency of phenol with the solution initial pH could
be clearly identified. The efficiency of removal was very low either at low pH or at high pH.
The optimal pH was 7, at which higher phenol removal efficiency could be reached. This
behavior was attributed to the amphoteric character of aluminum hydroxide which does not
precipitate at very low pH. Moreover, high pH leads to the formation of Al(OH)4`, which is
soluble and useless for adsorption of phenol. Therefore, further increase of the influent PH
would decrease the phenol removal efficiency.

5.1.2. Effect of sodium chloride dosage on percentage removal

Usually salt is employed to increase the electrical conductivity of the solution. For
example Electrical conductivity of phenol solution for 2 g of Nacl /l of solution was found to
be 4.1[Ls whereas for 3g of Nacl / I of solution was 5.8 [is. In the present study a Nominal

53
value of Nacl concentration in the range from I to 2.5W1 was used to increase the ionic
conductivity of the solution in order to minimize energy consumption. And also, the presence
of chloride ions remove the passive oxide layer form on electrode surface, hence it increases
the availability of aluminum hydroxide in the solution and improves the efficiency of phenol
removal which was shown in Fig 5.2.

5.1.3. Effect of Interelctrode distance on Phenol Removal Efficiency

Interelctrode distance is also an important factor which effects the Phenol removal
efficiency. Increase in the value of electrode gap between anode and cathode increase the
consumption for a required current supply. Once electrode distance increases, the electrical
current gets decreased for a constant voltage supply. With increasing distance, less interaction
occurs between the dye ion and hydroxyl ions. In the other words, decrease of both the local
concentration and the electrostatic attraction are the reasons for decrease in the removal of
phenol. The effect of electrode distance on phenol removal efficiency was shown on Fig. 5.3.

5.1.4. Effect of Current density and Operating Time on Phenol removal efficiency

The supply of current to the electrocoagulation system determines the amount of A13+
ions released from the electrodes. A large current means a small electro coagulation unit.
However, when too large current is used, there is a high chance of wasting electrical energy
in heating up the water. More importantly, a too large 'current density would result in a
significant decrease in current efficiency. Fig. 5.4. Depicts the effect of current density (c.d),
on electrocoagulation removal efficiency with increasing time. It has found that after 150 min
the maximum removal efficiency of phenol were 89.8, 86.1, 78.2 and 72.4 for current
densities of 7.8, 14.06, 20.31 and 25mA/cm2, respectively. This is ascribed to the fact that at
high current densities the dissolution of anode electrode increases according to Faraday's law,
the resulting aluminum hydroxides produces more sludge with a consequent significant
removal of phenol due to sweep coagulation. Furthermore, more bubbles are generated at
higher current and this improves the degree of mixing of A 1 (OH)3 and phenol which
enhances floatation ability of the cell with a consequent increase in the phenol removal
efficiency.

5.1.5. Effect of Initial Phenol Concentration on removal efficiency and E.Consumption

The Initial Concentration of Phenol solution also effects the removal efficiency. As
the Concentration increases the Phenol Removal efficiency decreases. This is because of the
formation of insufficient hydroxide complexes to coagulate the greater number of phenol

54
molecules at higher concentrations. Fig.5.5 represents the relation between the percentage
removal of phenol and initial solution concentration. The percentage removal was gradually
decreased from 96.4 to 38% as the phenol concentration increased from 50 to 250mg/l. This
is may be attributed to the fact that at a constant current density the same amount of
aluminum ions passes to the solution at different phenol concentrations. Consequently, the
formed amount of complex aluminum Hydroxide was insufficient to coagulate the greater
number of phenol molecules at higher phenol concentrations. But by increasing the
concentration of phenol the energy consumption per gram of phenol removed will decreased
from 0.745 kWh/g of phenol to 0.375 kWh/g of Phenol as shown in figure 5.6. as phenol
concentration increased from 50 to 250 mg/l.

5.1.6. Influence of Sodium Chloride on E.Consumption

As Increasing Nacl amount not only increases electrical conductivity, besides its
electrical conductivity it was found that chloride ions could significantly reduce the adverse
effect of other anions such as HCO3-,S042-. The existence of the carbonate or sulfate ions
would lead to the precipitation of Ca2+or Mg2+ ions that forms an insulating layer on the
surface of the electrodes. This insulating layer would sharply increase the potential between
electrodes and result in a significant decrease in the current efficiency. It is therefore
recommended that among the anions present, there should be 20% Cr to ensure a normal
operation of electrocoagulation in water treatment [12]. Fig 5.7. Shows that the energy
consumption decreased from 0.466 kWh/g of phenol to 0.348 kWh/g phenol removed. This
indicates the importance of the presence of NaCI in solution on the economy of
electrocoagulation process.

5.2. Batch electrocoagulation with addition of GAC studies

In order to study the effect of Granular activated carbon on phenol removal efficiency
by EC system, the batch operations were performed. The entire runs were performed at room
temperature. In each run 2 L of the phenol solution was poured into the electrolytic cell. To
know the effect of dosage of GAC on Phenol removal efficiency 50 to 250 mg of GAC/1 of
solution was added which was first crushed and screened with 850 micron size sieve. Fig.5.8
and fig.5.9 shows the Effect of GAC dosage at optimum Initial pH = 7 after 30 min and 120
min respectively.

➢ As the adsorbent Dosage increased keeping all the parameters constant the Percentage
removal of phenol increases as shown in Fig. 5.8& 5.9.

55
> The highest percentage removal was 96.8 (Initial Concentration = 100 mg/I; Interelctrode
distance = 1cm; Electrolysis time = 120min; Nacl = 2g/1; No.of Electrode = 4; PH0 = 7) is
at adsorbent dosage of 250 mg/l.
> By the addition of GAC in the dosages of 50, 100, 150, 200 and 250 mg/1 increases the
efficiency by the amount of 13.95, 19.95, 22.7, 26.2 and 28.8 percentage resp., after 30
min of process with comparative to electrocoagulation without GAC. Similarly, after 120
min of process the increase in efficiencies were found to be 3.8, 4.6, 6.7, 9.1 and 14.4
percentage resp., as shown in Fig 5.8 and 5.9.
> It has been established that a percentage removal of 96.8% (Initial Concentration = 100
mg/1; Interelctrode distance = 1cm; Electrolysis time = 120min; Nacl = 2g/l; No. of
Electrode = 4; PH0 = 7) was achieved at an adsorbent dosage of 250 mg/1 whereas there
has been only 55.25% phenol removal (Initial Concentration = 100 mg/I; Interelctrode
distance = lcm; Electrolysis time = 30min; Nacl = 2g/1; No. of Electrode = 4; P140 = 7)
with adsorbent dosage of 50 mg/l. Therefore, it has been found that addition of adsorbent
increases the extent of phenol removal.
> It is also observed that a percentage removal of 70.1% (Initial Concentration = 100 mg/1;
Interelctrode distance = 1cm; Electrolysis time = 30min; Nacl = 2g/1; No. of Electrode =
4; pH° = 7) is achieved at an adsorbent dosage of 250 mg/I whereas at an adsorbent
dosage of 50 mg/1, 55.25% observed (Initial Concentration = 100 mg/1; Interelctrode
distance = 1cm; Electrolysis time = 120min; Nacl = 2g/l; No. of Electrode = 4; PH„ = 7).
Therefore, it has been concluded that addition of adsorbent enhances the process of
electrocoagulation and reduces the operating time.

5.3. Characterization of Aluminum Electrode and Sludge

Scanning electron micrograph (SEM) images of aluminium electrode and

electrocoagulation sludge before and after electrocoagulation treatment were obtained along
with EDAX by LEO 435 VP Scanning microscope to compare the surface texture before and
after electrocoagulation And also the composition of the elements in weight percentage and
atomic percentage are obtained along with the spectra for overall compositions and particular
local area compositions from EDAX.

Fig.5.3.1 shows the original aluminium anode plate surface prior to its use in
electrocoagulation experiments. The surface of the anode is uniform with nanosized crystals.

56
Fig.5.3.2 Shows the SEM of the same anode after several cycles of its use in electro
coagulation experiments. The anode surface is now found to be rough, with a number of
dents. These dents are formed around the nucleus of the active sites where the anode
dissolution occur producing aluminum hydroxides. A magnified view of one such dent on the
electrode surface is shown in Fig.5.3.2.The formation of large number of dents may be
attributed to the anode material consumption at active sites due to the generation of dioxygen
at its surface. These dents end up as deep holes, which tend to entrap degradation byproducts
such as microflocs and sludge particles. Thus, the active surface in the dent is blocked for
further participation in degradation of phenol. Adsorbed species from the solution onto the
active sites of the dents and onto microflocs and sludge particles (which is shown in
Table.5.3.1 EDAX results) also show higher resistance to degradation. Thus,
electrocoagulation activity gets retarded on the exposure of anode surface for longer duration
during electrocoagulation treatment. After repeated cycles of electrocoagulation runs, these
dents increase in size leaving an eroded surface. Similarly the SEM image of granular
activated carbon which is used electrocoagulation in shown in Fig.5.3.3.

The residues pose problems to their disposal and management. The recent trend
emphasizes on utilizing them for some beneficial purpose and rendering them innocuous and
benign to the environment. The use of electrocoagulation for the treatment of various
wastewaters generates large volumes of solid residue. These solid residues have great
potential for energy recovery. The dried residues can be used directly or by making fire-
briquettes in the furnace combustors/incinerators to recover energy value. The residus were
studied for its thermal degradation characteristics by thermo-gravimetric (TG) instrument.
The principal experimental variables which could effect the thermal degradation
characteristics in air and nitrogen flow in a TGA are the pressure, the gas (purge gas), flow
rate, the heating rate, the weight of sample and the saple size fraction. In the present study,
the operating pressure was kept slightly positive, the purge gas (air or nitrogen) flow rate
maintained at ml min-1 and the heating rate was maintained at 10°C min-I.

The thermo gravimetric analysis (TGA), differential thermal analysis (DTA) and
differential thermal gravimetry (DTG) curves of the residues in oxidizing and inert
atmosphere at the heating rate of 10°C mine as shown in Fig.5.3.7 and 5.3.8, respectively.
The TG traces for the residues (Fig.5.3.7) in oxidizing atmosphere shows that loss of
moisture and the evolution of some light weight molecules including waster take place (7%
weight loss)from 25 to 100°C. Higher temperature drying occurs from 100 to 220°C due to

57
loss of the surface tension bound water of the particles. The rate of weight loss was found to
increase between 320 to 600°C (11% weight loss) and 5% weight loss between 600 to
1000°C. In the last temperature range residues oxidize and lose their weight gradually. The
strong exothermic peak centered between300°C to 500°C is due to the oxidative degradation
of the sample. This broad peak as that observed from the first derivative loss curve may be
due to the combustion of carbon species. At higher temperatures (third zone), the samples
present a gradual weight loss up to 1000°C. This weight loss has been reported to be
associated in part with the evolution of CO2 and CO.

Thermal degradation characteristics in flowing nitrogen atmosphere shows moisture

removal of about 9 % up to 100°C as in the air atmosphere followed by removal of light
volatiles up to 1000°C. Only fixed carbon is left after 1000°C and it is about 67% of the
original sample weight. This shows that the EC generated residue have a high potential to be
a very good heating fuel.

Similar thermal analysis is carried out for Granular activated carbon in the atmosphere
of air which is shown in Fig.5.3.6. Moisture removal of about 13 % up to 100°C fallowed by
a drastic change in weight loss about 80% in temperature range 499°C 637°C may be due to
residues oxidize and due to combustion carbon species it lost weight drastically. The strong
exothermic peak centered between500°C to 700°C is due to the oxidative degradation of the
sample. This broad peak as that observed from the first derivative loss curve may be due to
the combustion of carbon species. At higher temperatures (third zone), the samples present a
gradual weight loss up to 1000°C. This weight loss has been reported to be associated in part
with the evolution of CO2 and CO.

58
 90

80

70

60
70
0 50
>
E
40

30

20

10

0
0 2 4 6 8 10

pH

Fig.5.1 Effect of Initial Pilo on Percentage Removal of Phenol (Initial Concentration =

100 mg/I; Interelctrode distance =1cm; Electrolysis time = 120min; Nacl = 2g/I;).

90

80

70
70
>
0 60
cc

50

40

30
0 0.5 1 1.5 2 2.5 3

Nacl Dosage, mg/I

Fig.5.2 Effect of sodium chloride dosage on percentage removal (Initial Concentration =

100 mg/I; Interelctrode distance =1cm; Electrolysis time =120min; PII0 = 7).

59
 87

86

85
%Removal

84

83

82

81

0 0.5 1 1.5 2.5

Interelectrode distance, cm

Fig.5.3 Effect of Interelctrode distance on Phenol Removal Efficiency (Initial

Concentration = 100 mg/1; Electrolysis time = 150min; Nacl = 2g/1; PH0 = 7).

100

90

80

70

60 c.d (mA/cm2 )
% Removal

50

40 —0-14.06

30 —6— 20.31
20 —44-25

10

0 50 100 150 200

Time, min

Fig.5.4 Effect of Current density and Operating Time on Phenol removal efficiency
(Initial Concentration = 100 mg/1; Interelctrode distance = 1cm; Electrolysis time =
150min; Nacl = 2g/1; P' 0 = 7).

60
 120

100

80
%Removal

60

40

20

0
0 50 100 150 200 250 300

Initial concentration, mg/I

Fig.5.5 Effect of Initial Phenol Concentration on removal efficiency (Initial

Concentration = 100 mg/I; Interelctrode distance = 1cm; Electrolysis time = 150min;
Nacl = 2g/I; P110 = 7).

0.8

0.7

0.6
E.Cononsumption

0.5

0.4

0.3

0.2

0.1

0
0 50 100 150 200 250 300

Initial Concentration, mg/I

Fig.5.6 Effect of Initial Phenol Concentration on E. Consumption (Initial Concentration

= 100 mg/I; Interelctrode distance = lcm; Electrolysis time = 150min; Nacl = 2g/1)

61
 0.5

0.45

0.4

0.3

0.25

0.2
0 0.5 1 1.5 2 2.5 3

Sodium Chloride, g/1

Fig.5.7 Influence of Sodium Chloride on E.Consumption (Initial Concentration = 100

mg/I; Interelctrode distance = lcm; Electrolysis time = 120min; Nacl = 2g/l; PHo= 7).

75

70

65
% Remmoval

60

55

50

45

40
0 50 100 150 200 250 300

GAC Dosage, mg/I

Fig.5.8 Effect of GAC Addition on % phenol Removal (Initial Concentration = 100

mg/1; Interelctrode distance = lcm; Electrolysis time = 30min; Nacl = 2g/1; Pilo = 7).

62
 98

96

94

To
92
?
a,
rt
90

88

86

84

0 50 100 150 200 250 300

GAC Dosage, mg/I

Fig.5.9 Effect of GAC Addition on % phenol Removal (Initial Concentration = 100

mg/1; Interelctrode distance = 1cm; Electrolysis time = 120min; Nacl = 2g/1; PH.= 7).

63
 Fig.5.3.1 Aluminium anode plate surface prior to use in electrocoagulation experiment

EDAX Results:
c:),edex32\genesieVenmaps.spc 02-Jun-200914:46:45
LSecs: 6

1.2 — AIK galMall MO At%

i
AIK 100.00 100.00
1.0

Matrix Correction ZAF

0.7 —

KCnt

0.5 —

0.2 —

.0
1.00 2.00 3.00 4.00 5.00 6.00 7.00 0.00 9.00 10.0
Energy- keV

64
Fig.5.3.2 Aluminium anode plate surface after used in electrocoagulation with dents.

EDAX Results:

c:,,edax324genesistgenmaps.spc 02-Jun-200914:54:48
LSecs : 7 Eftwifi Ogi At%
821- AIK

CK 12.62 22.49

657-
OK 14.98 20.04

AlK 72.41 57.46

493-

Matrix Correction ZAF

328-

164-

OK

1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.0
Energy- keV

65
 Fig.5.3.3 scanning micrograph of Granular activated carbon before use in electro
coagulation at lk magnification.

EDAX Results:

c: edax321genesiskgenmaps.spe 02-Jun-200915:25:35
LSees : 8 t ffilMaa Wt% At%
103

CK 100.00 100.00
83
Matrix Correction ZAF
AIK
62 K

Al

OK CIK

20
NaK

IK ,
itt4J11114114111 LAIL113.116■1.111 in aiily ftli laity 2.1 I lintrik huh (.. A ..., ....... ,4
1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 10
Energy - keV

66
 Fig.5.3.4 scanning micrograph of Sludge produced after electrocoagulation at 1k
magnification.

Tble.5.3.1 EDAX Results:

j gadra
cnedax32Veneaunuenmapa.spt 10-Jun-2009 1517:59
< Pt 1 Spot, LSecs : 16 EN3 At%
519- CIK

Hal( CK 36.55 - 32.18

415-

OK 17.89 15.21
311-
NaK 12.06 20.25
207- AU(
AIK 18.35 17.52

103-
0 I(
CIK 15.15 14.84

U4'
1.00 2.00 3.00 4.00 5.00 0.00 7.00 8.00 9.00 10.0
Matrix Correction ZAF
Energy - keV

67
Fig.5.3.5 scanning micrograph of Sludge produced after electrocoagulation with GAC
addition at lk magnification.

Table5.3.2. EDAX Results:

c:Iedax32InenesitAgenmape.spc 02-Jun-2009 15:08:23

LSecs : 8
MEM Wt% At%
321-

CK 59.86 71.07
QK
257-

OK 21.67 19.31

192-
NaK 02.99 01.85

128- AIK 12.13 06.41

C1K 03.35 01.36

64 -

Matrix Correction ZAF

0 , AAA le l 1 , .12
o
1.00 2.00 3.00 4.00 6.00 6.00 7.00 8.00 9.00 10
Energy- keV

68
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 CHAPTER - 6

CONCLUSIONS AND RECOMMENDATIONS

6.1 Conclusions

➢ The present work deals with phenol removal by electrocoagulation and Enhancing
this removal efficiency by addition of Granular activated carbon to electrocoagulation
system.
➢ A series of experiments were performed in order to find the effects of Operating
parameters for phenol removal by EC. The effect of various operating parameters
(viz. Initial pH (PH0), Initial phenol concentration, Nacl dosage, Interelectrode
distance, time, current density and GAC dosage) on phenol removal were investigated
and optimized. The experimental results revealed that the phenol percentage removal
is enhanced by sweep coagulation and adsorption.
➢ It was concluded that phenol removal efficiency was more at initial pH = 7 i.e. at
neutral conditions.
➢ It was found that for initial concentration of 100 mg/1 the percent removal was about
87% with electrolysis time beyond which the removal efficiency was found to be
negligible. And with increase in Initial phenol concentration from 50 to 250 mg/1 the
removal efficiency decreased from 96% to 38%. So initial concentration greatly effect
the phenol removal efficiency and also energy consumption which decrease by the
increase in initial concentration.
➢ Increase in Current density and sodium chloride increase in phenol removal
efficiency. The efficiency for increase in current density from 7.8 to 25 mA/cm2
increases efficiency from 72% to 90%.
➢ And it was found that sodium chloride dosage is an important factor for reducing
energy consumption. Energy consumption decreased from 0.466 kWh/g of phenol to
0.348 kWh/g of phenol with increase in sodium chloride dosage from 1 to 2.5 g/1 as
shown in the results.
➢ The experimental results with addition of GAC shows that the highest percentage
removal 97 was achieved for 120 min operating time and current density of 25
mA/cm2 which was approximately 15% more for the same condition but without
addition.
➢ It is also observed that a percentage removal of 70.1% (is achieved at an adsorbent
dosage of 250 mg/1 whereas at an adsorbent dosage of 50 mg/1, 55.25% observed.
Therefore, it has been concluded that addition of adsorbent enhances the process of
electrocoagulation and reduces the operating time which is economical.

73
➢ It can be concluded from this study that electrocoagulation is a promising technique
for phenol removal.

6.2. Recommendations

The electrocoagulation process along with effect of addition of GAC was studied in
batch operation. It was found that after a time of 120 min there was no significant
removal and it was observed that phenol removal efficiency too decreased with time
because of increase in pH with respect to time. So it is recommended that to achieve a
maximum efficiency in minimum time the pH should be adjusted continuously.
Otherwise it is recommended that the batch process should be changed in to cascadic
process with a single run operated for 120 min. The solution should be filtered and again
adjusting its p11 to 7 so as to achieve maximum removal.

And it is observed and recommended that traditional theories like Langmuir and
Freundlich equations cannot be used separately to study the extent of adsorption on
percentage removal of Phenol. These equations have to be coupled with the kinetics of
electrocoagulation to determine the effective percentage removal.

74
 CHAPTER - 7

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82
CHAPTER-8

APPENDIX
Table.A-1. Effect of Initial pH (PH.) on the removal of phenol ( Electrolysis time = 120
min; Initial Concentration = 100 mg/1; Interelectrode distance = 1 cm; Nacl = 2 g/1 ).

S.No. pH Current Voltage Absorbance Concentration % Removal

(A) (V) (Cf , mg/1)
1. 3 1.3 22.1 0.2 64.9 35.1
2. 5 1.3 22.09 0.175 50.7 49.3
3. 7 1.3 22.2 0.12 20.2 79.8
4. 8 1.3 22.1 0.0135 28.5 71.5
5. 9 1.3 22 0.156 40.4 59.6

Table.A-2. Effect of Sodium Chloride Dosage on the removal of phenol (Electrolysis

time = 120 min; Initial Concentration = 100 mg/I; Interelectrode distance = 1 cm; Initial

S.No. Nacl Current Voltage Absorbance Concentration % Removal

(g/1) (A) (V) (Cf, mg/1)
1. 1 1.3 22.09 0.153 38.4 61.6
2. 1.5 1.3 22.1 0.129 25 75
3. 2 1.3 22.9 0.12 20.2 79.8
4. 2.5 1.3 22.1 0.115 17.5 82.5

Table.A-3. Effect of Initial Phenol Concentration on removal efficiency (Initial

Concentration = 100 mg/1; Inter electrode distance = lcm; Electrolysis time = 150min;
Nacl = 2g/1; Pilo = 7).

S.no. Initial Conc. Current Voltage Absorbance Concentration %

(mg/1) (A) (V) (Cf, mg/1) Removal
1. 50 1.3 22.09 0.0544 3.6 96.4
2. 100 1.3 22.1 0.109 13.9 86.1
3. 150 1.3 22.9 0.14 31.6 68.4
4. 200 1.3 22.1 0.174 50.3 49.7
5. 250 1.3 22.2 0.195 62 38

84
Table.A-4. Effect of Current density and Operating Time on Phenol removal efficiency
(Initial Concentration =100 mg/1; Inter electrode distance = lcm; Nacl = 2g/l; p Ho= 7).
c.d = 7.8 mA/cm2
S.no. Time Current Voltage Absorbance Concentration % Removal
(min) (A) (V) (mg/1)
1. 20 0.5 9.1 0.242 88 12
2. 40 0.5 9.2 0.207 68.5 31.5
3. 60 0.5 9.09 0.181 54 46
4. 90 0.5 9.1 0.175 50.6 49.4
5. 120 0.5 9.1 0.161 43 57
6. 150 0.5 9.3 0.133 27.6 72.4
c.d = 14.06 mA/cm
S.no. Time Current Voltage Absorbance Concentration % Removal
(min) (A) (V) (mg/1)
1. 20 0.9 13.4 0.234 83.8 16.2
2. 40 0.9 13.2 0.201 65 35
3. 60 0.9 13.4 0.174 50.5 49.7
4. 90 0.9 13.3 0.167 46.5 53.5
5. 120 0.9 13.3 0.157 41 59
6. 150 0.9 13.4 0.123 21.8 78.2
c.d =20.31mA/cm2
S.no. Time Current Voltage Absorbance Concentration % Removal
(min) (A) (V) (mg/I)
1. 20 1.3 22.15 0.219 75.5 24.5
2. 40 1.3 22.1 0.185 56.4 43.6
3. 60 1.3 22.09 0.171 48.5 51.5
4. 90 1.3 22.2 0.152 38 62
5. 120 1.3 22.1 0.12 20.2 79.8
6. 150 1.3 22.01 0.109 13.9 86.1
c.d = 25 mA/cm2
S.no. Time Current Voltage Absorbance Concentration % Removal
(min) (A) (V) (mg/I)
1. 20 1.6 22.3 0.205 67.7 32.3
2. 40 1.6 22.1 0.175 49.1 50.9
3. 60 1.6 22.09 0.203 33.6 66.4
4. 90 1.6 22.15 0.22 24 76
5. 120 1.6 22.1 0.232 17.6 82.4
6. 150 1.6 22.5 0.245 10.2 89.8

85
Table.A-5. Effect of Inter electrode distance on Phenol Removal Efficiency (Initial
Concentration = 100 mg/I; Electrolysis time = 150min; Nacl = 2g/1; No.of Electrode =4;
Plio=

S.no. Distance Current Voltage Absorbance Concentration % Removal

(cm) (A) (V) (Cf, mg/1)
1. 0.5 1.3 22.1 0.108 14.4 85.6
2. 1 1.3 22.1 0.109 13.9 86.1
3. 1.5 1.3 22.09 0.111 15.5 84.5
4. 2 1.3 22.2 0.117 18.6 81.4

Table.A-6. Effect of Initial Phenol Concentration on E. Consumption (Initial

Concentration = 100 mg/I; Inter electrode distance = 1cm; Electrolysis time = 150min;
Nacl = 2g/1; Pilo= 7)

S.no Initial Current Voltage Concentration % m (g) E.Con (I.V.t/m

Con.(mg/1) (A) (V) (Cf, mei) Removal , kWh/g)
1. 50 1.3 22.09 3.6 96.4 0.964 0.745
2. 100 1.3 22.1 13.9 86.1 1.722 0.417
3. 150 1.3 22.9 31.6 68.4 2.052 0.35
4. 200 1.3 22.1 50.3 49.7 1.98 0.361
5. 250 1.3 22.2 62 38 1.91 0.375

Table.A-7. Influence of Sodium Chloride on E.Consumption (Initial Concentration =

100 mg/l; Inter electrode distance = 1cm; Electrolysis time = 120min; Nacl = 2g11; Plio =
7).

S.No Nacl Current Voltage Concentration % Removal m(g) E.Con (I.V.t/m

(g/1) (A) (V) (Cf, mg/1) , kWh/g)
1. 1 1.3 22.09 38.4 61.6 0.616 0.466
2. 1.5 1.3 22.1 25 75 0.75 0.38
3. 2 1.3 22.9 20.2 79.8 0.798 0.359
4. 2.5 1.3 22.1 17.5 82.5 0.825 0.348

Table.A-8. Effect of GAC Addition on % phenol Removal (Initial Concentration = 100

mg/1; Inter electrode distance = 1cm; Electrolysis time = 30min; Nacl = 2g/l; No. of
Electrode = 4; Plio= 7).

S.no. GAC Dosage, Current Voltage Absorbance Concentration % removal

mg/1 (A) (V) . (Cf, mg/1)
1. 50 1.6 22.09 0.164 44.75 55.25
2. 100 1.6 22.1 0.153 . 38.75 61.25

86
3. 150 1.6 22.1 0.148 36 64
4. 200 1.6 22.15 0.142 32.5 67.5
5 250 1.6 22.3 0.137 29.9 70.1

Table.A-9. Effect of GAC Addition on % phenol Removal (Initial Concentration = 100

mg/1; Inter electrode distance = lcm; Electrolysis time = 120min; Nacl = 2g/1; No. of
Electrode = 4; Pilo = 7).

S.no. GAC Dosage, Current Voltage Absorbance Concentration %

mg/1 (A) (V) (Cf , mg/1) removal
1. 50 1.6 22.09 0.109 13.8 86.2
2. 100 1.6 22.1 0.107 13 87
3. 150 1.6 22.1 0.103 10.9 89.1
4. 200 1.6 22.15 0.099 8.5 91.5
5. 250 1.6 22.3 0.089 3.2 96.8

87