A

DISSERTATION REPORT

ON

“Comparative Study of Dye Removal by Adsorption Method and

Nanocrystalline Tio2 Thin Films”

Submitted to
SHIVAJI UNIVERSITY, KOLHAPUR
In partial fulfillment of the requirement for the degree of

MASTER OF ENGINEERING
In
CHEMICAL ENGINEERING

Submitted by

Mr. PATIL SACHIN UDAYSINGRAO

(PRN No. 1212394357)

Under the guidance of

PROF. S.T.PATIL

---------------------------------------------------------------------------------------------------------------------
DEPARTMENT OF CHEMICAL ENGINEERING
TATYASAHEB KORE INSTITUTE OF ENGINEERING AND TECHNOLOGY
WARANANAGAR, TAL. PANAHALA, DIST. KOLHAPUR, MAHARASHTRA, 416113.
ACADEMIC YEAR 2014-2015
 TATYASAHEB KORE INSTITUTE OF ENGINEERING AND TECHNOLOGY,
WARANANAGAR, TAL. PANHALA, DIST. KOLHAPUR, MAHARASHTRA, 416113
DEPARTMENT OF CHEMICAL ENGINEERING

CERTIFICATE

This is to certify that the dissertation report entitled, “Comparative study of dye removal by
adsorption method and nanocrystalline TiO2 thin films”, has been successfully carried out by
Mr. Patil Sachin Udaysingrao, in partial fulfillment of the requirement for the award of the
degree of Master in Chemical Engineering under Shivaji University, Kolhapur. He has carried
out the dissertation work satisfactorily under my supervision and guidance, during academic year
2014-2015 and to be the best of our knowledge the work reported here is does not form the part
of any other thesis or dissertation.
Place: Warananagar
Date: / /2015

Examiner Prof.S.T.Patil
Guide

Prof. S.A.Desai Dr. S. V. Anekar

Head, Principal
Department of Chemical Engineering, Tatyasaheb Kore Institute of Engineering
T.K.I.E.T. Warananagar. and Technology, Warananagar.
 ACKNOWLEDGMENT

I must mention several individuals and organizations that were of enormous help in the
development of this work. I wish to express my sincere thanks to my Project Guide Prof.
S.T.PATIL, for his valuable guidance and encouragement throughout the course of project
work. I am very much grateful to him for his continuous support .His knowledge; creativity and
devotion to the project work are the inspiring things that the students can carry with them
throughout the life. He is my supervisor, philosopher and personality with a Midas touch
encouraged me to carry this work. His continuous valuable knowledgably guidance throughout
the course helped me to complete the dissertation work up to this stage and hope will continue in
further research.
I am thankful to Prof. S.A Desai, HOD, Department of Chemical Engineering, for his
support throughout my work, for his patience, interest and guidance and for his valuable
recommendations
I also very thankful to External guide Dr. C.H.Bhosale (Co-ordinator, UGC-DSA-I
programme, Department of Physics, Shivaji University, Kolhapur) for their valuable
suggestions, critical examination of work during the progress, I am indebted to them
I wish to express my sincerely thanks to; Dr. S. V. Anekar, Principal, Tatyasaheb Kore
Institute of Engineering and Technology, Warananagar, who contributed with important
supervision in thesis preparation and for supporting me to do this dissertation work; I am very
much obliged to him. In addition, very energetic and competitive atmosphere of the Chemical
Engineering Department had much to do with this dissertation work. I acknowledge with
thanks to faculty, teaching and non-teaching staff of the department, Central library and
Colleagues

Mr. Patil Sachin Udaysingrao

T.K.I.E.T.Warananagar
November 2015.
 ---I---

ABSTRACT

Water & air pollution are main problems concerning in the today’s world in the industrial
area especially chemical industries. Most of the processes carried out in the chemical industry
uses water. Thus this water after being used generates the problem of its disposal specially
wastewater coming out from the dying industries. Wastewater coming out from the dye industry
contains the traces of the dye in it. If such water is let into the water bodies this causes serious
health problems like carcinogenic problems, skin diseases etc. Thus removal of these dyes from
industrial wastewater is the most vital challenge these days before the researcher. Many
techniques have been developed for the removal of this dye from the wastewater like electro
coagulation, flocculation, photocatalysis, photoelctrocatalysis, adsorption etc.
In this work adsorption and photoelctrocatalysis methods are studied. Here the work was
carried out to understand the effect of the activated carbon onto acid orange 7.Experiments were
conducted at lab scale to understand the kinetic data. During this experiments the effect of
various parameters like pH, acid concentration, time, and mass of adsorbent were studied. After
the adsorption data was obtained it was found to better fit the Freundlich isotherm. Also it was
found to follow the Lagrange’s pseudo first order kinetics. In this report also the thermodynamic
parameters like Gibbs free energy, change in enthalpy & entropy were studied. During study of
nanocrystalline TiO2 photoelectrocatalytic reactor various parameter studied as like pH,
recirculation rate of Acid Orange 7 over the reactor over the percent removal of dye and the
influence of time over percent removal.
 - - - II - - -

LIST OF TABLES
Tabl Table Title Page
e No. No
2.1 List of raw materials which have been used for production of activated carbon 11
2.2 List of pollutant and photocatalysts used. 12
4.1 List of Absorbance at different Concentrations 28
4.2 Effect of initial pH (pH0) 29
4.3 Effect of adsorbent dosage 31
4.4.1 Effect of contact time and initial dye concentrations 10 ppm and 20 ppm 32
4.4.2 Effect of contact time and initial dye concentrations 30 ppm and 40 ppm 33
4.4.3 Effect of contact time on % Removal 35
4.5.1 Effect of adsorption dye with time (kinetics study) 36
4.5.2 Kinetic constants for the adsorption of AO7 by AC, time 120min & adsorbent 37
of 1g/l
4.6 Effect of temperature 38
4.8 Explanations of different error function 40
4.9 Isotherm values for adsorption of AO7 by AC for initial concentration range of 42
10-40mg/l. time of agitation 6 hr and adsorbent dosage 1 g/l
4.10
4.11 The thermodynamic parameters of free energy changes (ΔG), enthalpy changes 44
(ΔH) and entropy changes (ΔS)
4.12 Adsorption breakthrough data for column scale for the sorption of Acid Orange 50
7 on different bed depth columns
4.13 Effect of the linear flow rate on the sorption of Acid Orange7 51
4.14 Adsorption capacity of activated carbon at different initial dye concentrations 52
4.15 Packed-Bed experimental data for Acid orange 7 53
4.16 Calculated constants of BDST model for the adsorption of Acid orange 7 using 56
linear regression analysis
4.17 Predicted breakthrough time based on the BDST constants for a new flow rate 57
4.18 Predicted breakthrough time based on the BDST constants for a new influent 57
concentration
4.19 Calculated constants of Thomas model at different conditions using non-linear 58
regression analysis
4.20 Effect of initial pH(pH0) 61
4.21 Nanocrystalline TiO2 thin film experimental data for Acid orange 7 62
4.22 Comparison between Adsorption method and nanocrystalline TiO2 thin film 63

- - - III - - -

LIST OF FIGURES
Figur Figure Title Page
e No
No.
3.1 SEM image of activated carbon at x 2000 zoom 18
3.2 SEM image of activated carbon at x 5000 zoom 18
3.3 SEM image of activated carbon at x 10000 zoom 19
3.4 SEM image of activated carbon at x 20000 zoom 19
3.5 FTIR of Activated Carbon before Adsorption 20
3.6 FTIR of Activated Carbon after Adsorption 20
3.7 Schematic Representation of Experimental Equipment(column study) 23
3.8 Experimental setup of fixed-bed column. 24
3.9 Experimental setup of TiO2 thin film. 25
3.10 Schematic Representation of Experimental Equipment (TiO2 thin film) 25
4.1 Calibration plot Absorbance in % Vs Concentration in mg/l 28
4.2 Effect of initial pH on % dye removal, 40 mg/l dye concentration &time 6 hr 29
4.3 Plot of AC mass on adsorption of AO7 at 40 mg/l concentration and pH 2 31
4.4.1 Effect of mass of adsorption of AO7 dye with time t and adsorbent mass 1 34
g/L
4.4.2 Plot of contact time on dye removal efficiency of AC at temperature 301 K 35
and adsorbent mass 1 g/ L
4.5.1 Second order plot of AO7 adsorption onto AC 37
4.6(a) Effect of temperature on equilibrium adsorption 38
4.6(b) plot of qe v/s Ce 38
4.9 Plot of predicted equilibrium isotherm for the adsorption of AO7 onto AC 41
4.10 Plot of RL Vs Co 43
4.11 Van't Hoff plot for the adsorption of AO7 onto AC. 44
4.12 Schema of bed depth 45
4.13 Typical breakthrough curve for activated carbon showing the movement of 48
the mass transfer zone according to the throughput volume .
4.14 Effect of a) Bed Height, b) Flow rate, c) Influent Acid orange 7 concentration 53
on breakthrough curve
4.15 Isoremoval lines for 0.2, 0.4, 0.6 and 0.8 breakthrough for different bed 56
height
4.16 Comparison of fitted curves and experimental data C0 = 100 mg/L, Z = 6 cm 59
at a) Q_V = 6.5 ml min−1, b) Q_V = 8.5 ml min−1 and c) Q_V = 10.5 ml
min−1
4.17 Mechanism of photocatalysis 60
4.18 Effect of initial pH on % dye removal, 40 mg/l dye concentration 61
 - - - IV - - -

NOMENCLATURE/ ABBREVIATIONS
A Redlich–Peterson isotherm constant (1/mg)1/g
AO7 Acid Orange 7
TiO2 Titanium dioxide
ARE Average Relative Error
B1 Temkin isotherm constant (mg/g)
BET Brunauer–Emmett Teller
B Redlich–Peterson isotherm constant (l/g)
Ct Concentration at any time t (mg/L)
Ce Equilibrium concentration (mg/L)
Co, Ci Initial dye concentration (mg/L)
EABS The sum of the absolute errors
ERRSQ The sum of the squares of the error
FTIR Fourier-transform infrared
G Redlich–Peterson constant
 ΔG Gibbs energy change (kJ/mol)
H Initial adsorption rate
ΔH Enthalpy changes
K Equilibrium constant
k1 Pseudo first order rate constant (min-1)
k2 Pseudo second order rate constant (g/(mg min))
KF Freundlich constant (mg/g)(L/g)1/n
KL Langmuir isotherm constant (L/mg)
KT Temkin isotherm equilibrium binding constant (L/g)
m, M Adsorbent mass (g)
MA Molecular weight of solute
N Freundlich exponent
N Number of experimental measurements
P Number of parameters in isotherm
qt Amount of dye adsorbed at any time t (mg/g)
qe Amount of dye adsorbed at equilibrium (mg/g)
qm Monolayer sorption capacity (mg/g)
R Universal gas constant (8.314 J/mol K)
R2 Correlation coefficient
RL Separation factor
ΔS Entropy change
t Contact time (min)
T Temperature (K)
---V---
INDEX
Chapter No. CONTENT Page No
Acknowledgement I
Abstract II
List of Figures III
List of Tables IV
Nomenclature V

Chapter 1 INTRODUCTION 1
1.1 Introduction 2
1.2 What are photocatalysis and photoelectrocatalysis? 5
1.3 Pollutants Details 5
1.4 Objectives of Work 6
Chapter 2 LITERATURE REVIEW 7
2.1 Literature Review 8

Chapter 3 METHODOLOGY 15
3.1 Characterization of activated carbon 16
3.1.1 Proximate analysis 16
3.1.2 Scanning Electron Microscope 17
3.1.3 Fourier-transform infrared (FTIR) 20
3.2 Instrumentation 21
3.3 Chemicals 21
3.4 Preparation of Dye Solution 21
3.5 Experimental work 22
3.6 Experimental Setups 23
3.6.1 Fixed-bed column 23
3.6.2 Nanocrystalline TiO2 thin film 25

Chapter 4 RESULT ANALYSIS 27

4.1 Result and Discussion 28
4.1.1 Calibration plot 28
4.2 Effect of initial pH 29
4.3 Effect of adsorbent dosage 30
4.4 Effect of Initial AO7 Concentration and Contact time 32
4.5 Adsorption Dynamics 36
4.6 Effect of Temperature 38
4.7 Adsorption Isotherms 39
4.8 Error functions 40
4.9 Non-linear method 41
4.10 Separation factor (RL) 42
4.11. Thermodynamic parameters 43
4.12. Fixed-Bed Design Models 45
4.12.1. Method 45
4.12.2. Design of the adsorption column based on bed depth
. service time 46
4.12.3. Mass transfer zone 48
4.12.4. Breakthrough curves 49
4.12.4.1. Effect of bed depth 49
4.12.4.2. Effect of Volumetric Flow Rate 50
4.12.4.3. Effect of Initial Dye Concentration 52
4.13. Modeling of different bed depth column study results about
BDST model 56
4.13.1. Modeling of column study results: Thomas model 58
4.14 Nanocrystalline Tio2 thin film 60
4.14.1 Mechanism of TiO2 photoelectrocatalysis 60
4.15. Effect of initial pH (pH0) 61
4.16 Effect of Initial Dye Concentration 61

CONCLUSIONS 64

REFERENCES 66