Som Piseth Proposal

APPLICATIONS OF FENTON AND FENTON-LIKE REACTIONS WITH
SUBSEQUENT HYDROXIDE PRECIPITATION FOR DERUSTING

WASTEWATER TREATMENT

PISETH SOM

A PROPOSAL SUBMITTED IN PARTIAL FULFILLMENT OF THE
REQUIREMENT FOR THE MASTER DEGREE OF ENGINEERING
IN CHEMICAL AND ENVIRONMENTAL ENGINEERING
BURAPHA UNIVERSITY
NOVERMBER 2013
COPYRIGHT OF BURAPHA UNIVERSITY

ii

TABLE OF CONTENT

TABLE OF CONTENT ................................................................................................. ii
LIST OF TABLES ........................................................................................................ iv
LIST OF FIGURES ....................................................................................................... v
ABBREVIATION......................................................................................................... vi
CHAPTER 1 INTRODUCTION ................................................................................... 1
Statements and Significant of Problems .................................................................. 1
Objectives ................................................................................................................ 3
Research Hypothesis ................................................................................................ 4
Scope of the Study ................................................................................................... 4
Significance of the Study ......................................................................................... 4
CHAPTER 2 LITERATURE REVIEW ....................................................................... 6
Advanced Oxidation Processes (AOPs) ................................................................... 6
Fentons Reagent and Reaction Mechanism ............................................................ 8
Basic Principle ................................................................................................ 8
Fenton Reaction .............................................................................................. 9
Fenton-like Reaction ..................................................................................... 10
Hydroxyl Radical Reaction with Organic Compounds ......................................... 11
Iron Ligand, Chelators and Coordination .............................................................. 13
Factors Affecting Fenton and Fenton-like Process ................................................ 14
Effect of pH ................................................................................................... 14
Effect of Temperature ................................................................................... 15
Effect of Iron Concentration ......................................................................... 16
Effect of H2O2 concentration ........................................................................ 17
Effect of Reaction Time ................................................................................ 18
Chelating Agents Degradation by Various Fenton Processes ................................ 19
CHAPTER 3 RESEARCH METHODOLOGY .......................................................... 25
Derusting Wastewater Characteristics ................................................................... 25
Materials and Chemical Reagents .......................................................................... 25
Experimental Design and Procedure ...................................................................... 27
Determine wastewater characteristics ........................................................... 27
Hydroxide Precipitation of Iron Before Fenton and Fenton-like Processes . 28
Effects of Initial pH on Fenton-like Process ................................................. 28
iii

Effects of H2O2 Concentration on Fenton-like Process ................................ 29
Effects of Reaction Time on Fenton-like Process ......................................... 30
Hydroxide Precipitation of Iron After Fenton-like Process .......................... 31
Effects of Initial pH on Fenton Process ........................................................ 32
Effects of Fe
2+
Concentration on Fenton Process ......................................... 33
Effects of H2O2 Concentration on Fenton Process ....................................... 33
Effects of Reaction Time on Fenton Process ................................................ 34
Hydroxide Precipitation of Iron After Fenton Process ................................. 35
Optimum Conditions .............................................................................................. 36
Analytical Method ................................................................................................. 36
Kinetic Study ......................................................................................................... 37
REFERENCES ............................................................................................................ 39
APPENDICES ............................................................................................................. 44
Appendix A: Activities plan .................................................................................. 44
Appendix B: Chemical Analysis Procedures ......................................................... 45
Appendix C: Fentons Reagent Preparation .......................................................... 50

iv

LIST OF TABLES
Table 2.1 Oxidizing potential for conventional oxidizing agents ................................. 6
Table 2.2 Summary of Fenton process for various wastewater treatments ................ 23

v

LIST OF FIGURES
Figure 2.1 Classification of advanced oxidation processes (AOPs). ............................ 8

vi

ABBREVIATION
AOPs : Advanced Oxidation Processes
EDTA : ethylenediamine tetraacetic acid
COD : chemical oxygen demand
BOD5 : biological oxygen demand in 5 day
1

CHAPTER 1
INTRODUCTION
This chapter covers the fundamental background of research and problems in
consideration of Advanced Oxidation Processes (AOPs) based on Fenton and Fenton-
like processes for derusting wastewater; then, the research objectives and research
hypothesis are formulated accordingly. Finally, significance and scope of the study are
also provided.
Statements and Significant of Problems
Chemical cleaning of pipes, tanks, boilers, and power plants has been operated
to remove the deposits and scales for reactivation and reuse of them. There are various
types of chemicals that have been used for cleaning depending on the equipment
including inorganic acids, organic acids, chelating agents, alkali agents and aids agents.
The inorganic acids include hydrochloric acid, sulfuric acid and nitric acid. The
hydrochloric acid is the most widely used for chemical cleaning. The examples of
organic acids are citric acid, glycolic acid, and formic acid. The organic acids are used
extensively for cleaning of recent new boilers. The most widely used chelating agent is
ethylenediamine tetraacetic acid (EDTA). The ammonia, which is alkali agent, is used
to clean the scale containing large quantities of copper. The aids agents such as acid
inhibitors and reducing agents are used to reduce and to prevent the corrosion of the
materials, respectively. The sodium nitrite can be used as inhibitor for protection of
carbon steel in salt solution (Hayyan, et al., 2012). During the cleaning operation, two
methods for dissolving encrustation or rust are applied. First method is a two-step
process: first stage uses inhibited hydrochloric acid solution for iron oxide dissolution
followed by the second stage of dissolving the metallic copper by ammonia and
oxidizing agents. Another method involves a single cleaning stage. In this method, iron
oxide and metallic copper are dissolved simultaneously by using hydrochloric acid in
the presence of chelating agents and citric acid. Consequently, the cleaning wastewater
often contains large amounts of iron and copper including high concentration of
chelating agents (Huang et al., 2000; Bansal, 2012). Iron (Fe
3+
) is the most prevalent
cation, generally present at a concentration of 1000-10000 mg/L. Copper is the second
2

most abundant metal with minor level of nickel, chromium, and zinc, typically, present
at the concentration less than 100 mg/L (Huang et al., 2000; Kim et al., 2010).
The EDTA and citric acid are used at the concentrations of 2-5% and up to
10% by weight, respectively, in cleaning process (Huang et al., 2000; Kim et al., 2010).
Chelating heavy mental wastewater must be treated not only for the toxic heavy mental,
but also the chelating agents. Heavy metals are considered toxic to human being and
aquatic life. Furthermore, the EDTA causes the complexation and immobilization of
heavy metals. The EDTA complexation is biologically persistent and cannot be readily
degraded by conventional biological treatment processes (Ghiselli et al., 2004; Citra et
al., 2011). The presence of chelated complex causes constraints and ineffective
application of lime or caustic treatment, chemical precipitation, ion exchange as
reported in the literatures (Citra et al., 2011; Lan et al., 2012; Fu et al, 2009). Metal
chelated wastewater can be treated by electrochemical reduction (Huang et al., 2000)
and interior microelectrolysis (Lan et al., 2012). Both processes can successfully
remove metal; however, interior microelectrolysis cannot remove or degrade chelating
EDTA and electrochemical reduction can achieve EDTA recovery for reuse. To
remove metal and mineralize the metal-EDTA complexes, there is an urgent need to
search for a feasible, efficient, economical, and eco-friendly approach (Bautista et al.,
2008; Bianco et al., 2011).
For last few decades, advanced oxidation processes (AOPs) are known for
their capability to mineralize, decompose, and degrade non-biodegradable organic
compounds (Poyatos et al., 2010; Ameta et al., 2012). Particularly, Fenton and Fenton-
like processes are adopted for wastewaters treatment in terms of organic pollutant
destruction, toxicity reduction, biodegradability improvement, COD removal, odor and
color removal, and heavy metal removal due to the economic advantages, ease of
application, and effectiveness (Matthew Tarr, 2003; Bautista et al., 2008; Lucas &
Peres, 2009; Bianco et al., 2011). Fenton is one of the AOPs that has been commonly
applied for industrial wastewater including textile effluent (Kang et al., 2002;
Karthikeyan et al., 2011), olive oil effluent (Lucas & Peres, 2009; Kiril Mert et al.,
2010), pulp and paper mill effluent (Pirkanniemi et al., 2007), cosmetic wastewater
(Bautista et al., 2007), bleaching effluent (Wang et al., 2011), highly polluted industrial
wastewater (San Sebastin Martinez et al., 2003), complex industrial wastewater
3

(Bianco et al., 2011). However, application of Fenton and Fenton-like reactions for
boilers chemical cleaning wastewater is not extensively documented. An integration of
Fenton oxidation with other conventional treatment methods have been conducted to
degrade EDTA complex and to removal metals from the waste stream. Synthetic
NiEDTA was successfully removed using Fenton and Fenton-like reactions followed
by precipitation (Fu et al., 2009, 2012). The degradation of Cu-EDTA complex can
also achieved (Lan, et al., 2012) with interior microelectrolysis and Fenton oxidation
coagulation. However, Fe-EDTA complex has not been conducted yet. To our
knowledge; Therefore, Fe-EDTA removal by Fenton and Fenton-like is important since
their applications are limited.
As mentioned above, chemical cleaning wastewater contains high iron species
including Fe2O3,/Fe3O4 (rust) and Fe
2+
or Fe
3+
depending on the pH, which can reach
up to hundreds of mg/L. It is assumed that Fenton or Fenton-like reactions should take
place to generate hydroxyl radicals (OH
) when H2O2 is added to the iron-rich

wastewater because the rust (Fe2O3/Fe3O4) particles and iron (Fe
2+
/Fe
3+
), which have
already presented in wastewater, could be effective catalysts in the generation of strong
oxidant (Kitis & Kaplan, 2007; Kim et al., 2010; Lan et al., 2012).
Objectives
The overall objective of this study is to evaluate the feasibility and efficiency
of Fenton and Fenton-like oxidations for removals of organic pollutants measured as
COD and inorganic pollutants including various iron species concentrations as the main
parameters and chemicals in derusting wastewater. Following specific objectives are
included:
1. To determine the optimum initial parameters of Fenton and Fenton-like
reactions including pH, Fe
2+
concentration, H2O2 concentration for the
treatment of derusting industrial wastewater.
2. To determine the optimum reaction time and reaction kinetics for the treatment
of derusting industrial wastewater
3. To determine the optimum precipitation pH for Fenton and Fenton-like
reactions for the treatment of derusting industrial wastewater.
4

4. To investigate the effects of Fenton and Fenton-like reactions on the ammonia
and nitrite removals in the treatment of derusting industrial wastewater.
Research Hypothesis
1. The presence of chelating agent, EDTA, can inhibit the precipitation of iron in
the derusting wastewater.
2. Utilization of existing Fe (III)/Fe (II) and additional iron can be beneficial for
Fenton and Fenton-like oxidation for degradation of EDTA complex in term
of COD reduction and total Fe removal.
Scope of the Study
This study is limited with following conditions.
1. Treatment performance evaluation is conducted using Jar test apparatus under
normal laboratory room temperature at Department of Chemical Engineering,
Faculty of Engineering, Burapha University.
2. Real wastewater taken from Kation Power Ltd (Thailand) is used throughout
the experiments
3. Organic degradation will measured in COD value.
4. Oxidation products are not investigated in this study
Significance of the Study
The results of this study can provide the following contributions:
Firstly, this study demonstrates the fessibility of Fenton and Fenton-like
process applications as methods to solve the encountered derusting wastewater
treatment problem as practiced in accordance with standard effluent stipulated in
national regulation.
Secondly, even though Fenton oxidation have been applied extensively and
enormously in many differrent types of wastewater, its application for derusting
wastewater was not well documented in literatures. Thus, this study will contribute to
comprehensive and extensive knowlegde and discussion on real wastewater treatment
which is known to be contiminated with chelating organic compounds and high metal
concentration.
5

Finally, it is probably advantageous for Fenton and Fenton-like process to
utilize iron metals (ferric and ferrous ions) that have already existed in cleaning
wastewater. If they do, there will be economical and cost-effective for reagents usages
for the treatment of this wastewater.
6

CHAPTER 2
LITERATURE REVIEW
This chapter provides a comprehensive review on advanced oxidation
technologies (AOTs). Next, theoretical and empirical reviews on Fenton and Fenton-
like reaction mechanisms influencing factors and their applications are conducted.
Finally, the applications of Fenton oxidation for chelating agent, EDTA, are also
reviewed.
Advanced Oxidation Processes (AOPs)
The development of cost-effective technical solutions is needed to deal with
the increasingly complex problems arising in the field of industrial wastewater.
Recently, advanced oxidation processes (AOPs) have been applied successfully for the
removal or degradation of recalcitrant pollutants based on the high oxidative power of
the hydroxyl radical (HO
). It has electrochemical oxidation potential (EOP) o f2.8 V,

which is comparatively be second to fluorine as shown in Table 2.1 (Poyatos et al.,
2010).

Table 2.1 Oxidizing potential for conventional oxidizing agents
Oxidizing agent Oxidation Potential (EOP), V EOP relative to
Chlorine (V)
Fluorine
Hydroxyl radical (HO
)
Oxygen (atomic)
Ozone
Hydrogen peroxide
Hypochlorite
Chlorine
Chlorine dioxide
Oxygen (molecular)
3.06
2.80
2.42
2.08
1.78
1.49
1.36
1.27
1.23
2.25
2.05
1.78
1.52
1.30
1.10
1.00
0.93
0.90
Source: Poyatos et al., 2010.
7

A chemical wastewater treatment using AOPs can produce the complete
mineralization of pollutants to CO2, water, and inorganic compounds, or at least their
transformation into more harmless products. Furthermore, the partial decomposition of
non-biodegradable organic pollutants can lead to biodegradable intermediates;
therefore, AOPs are commonly applied as pre-treatments processes, followed by
biological or chemical processes (Poyatos et al., 2010). AOPs represent the newest
methods in H2O2 technology which include photochemical degradation processes
(UV/O3, UV/ H2O2), photocatalysis (TiO2/UV, photo-Fenton reaction), and chemical
oxidation processes (O3, O3/ H2O2, H2O2/Fe
2+
). Although advanced oxidation processes
(AOPs) have employed different reagent systems, they all produce hydroxyl radicals.
These radicals are very reactive and they can attack most organic compounds
nonselectively (Kalra et al., 2011; Lucas & Peres, 2009; Poyatos et al., 2010).
Advanced oxidation processes (AOPs) can be classified either as homogeneous or
heterogeneous. Homogeneous processes can be further subdivided into energy-
activated and non-energy activated processes as shown in Figure. 2.1. The following
sections describe a wide range of advanced oxidation systems that are currently being
studied for their possible use in wastewater treatment (Poyatos et al., 2010).
Among advanced oxidation technologies, Fenton oxidation has been
frequently involved in many different industrial wastewater treatment processes for
degrading and remediating of a wide range of contaminants, predominately toxic,
recalcitrant, and persistent organic pollutants (POPs). It is also due to economic
advantages, ease of application, and effectiveness in the contaminant reduction and
mineralization (Matthew Tarr, 2003). It was also considered that Fenton oxidation
presents one of the best methods for clean and safe processes for the degradation of
organics even at higher initial organic content (Bianco et al., 2011; Lucas & Peres,
2009).

8

Figure 2.1 Classification of advanced oxidation processes (AOPs).

Fentons Reagent and Reaction Mechanism
Basic Principle
The term Fentons reagent refers to the aqueous mixture of Fe (II) and
hydrogen peroxide. The Fentons reagent was first discovered and used by H. J. H.
Fenton in 1894 when he observed that the rate of oxidation of tartaric acid increased
dramatically when dilute hydrogen peroxide with the solution containing dissolved Fe
2+

ions. Forty years later, after a controversial history about the reaction mechanism of
Fentons reaction, its reaction mechanism was interpreted by Haber and Weiss in 1934
that Fentons chemistry is a reaction between hydrogen peroxide (H2O2) and Fe
2+
ions
forming hydroxyl radicals, which is the main oxidizing agent. However the hydroxyl
radical mechanism of the Fentons reaction for toxic organics degradation was not
Advanced Oxidation Processes
Homogeneuos
process
Using Energy
Ultraviolet
Radiation
- O
3
/UV
- H
2
O
2
/UV
- H
2
O
2
/O
3
/UV
- Photo-
Fenton(Fe
2+
/
H
2
O
2
/UV)
Ultrasound
Energy
- O
3
/US
- O
3
/US
Electrical
Energy
- Anodic
Oxidation
- Electro-Fenton
Without Energy
- O
3
in alkaline
Medium
- O
3
/ H
2
O
2
- Fenton Process
Fe
2+
/ H
2
O
2
- Fentton-like
Fe
3+
/H
2
O
2
Fe
0
/H
2
O
2
Heterogeneuos
process
- Catalytic
Ozonization
- Photocatalytic
Ozonization
-Heterogeneous
Photo-catalysis
9

applied until the late 1960s (Ciambelli et al., 2008; Matthew Tarr, 2003; Neyens &
Baeyens, 2003).
Fenton Reaction
The oxidation mechanism in the Fenton process involves using ferrous ions to
react with hydrogen peroxide, producing hydroxyl radicals with powerful oxidizing
ability to degrade organic pollutants. The oxidation mechanism of Fenton reaction is
very complex, but the widely accepted major chemical reactions are summarized as
shown below (Ameta et al., 2012; Bianco et al., 2011; Jiang et al., 2010; Lee & Shoda,
2008; Lucas & Peres, 2009; Matthew Tarr, 2003; Neyens & Baeyens, 2003; Munter,
2001).

Fe
2+
+ H2 O2 Fe
3+
+ OH
+ OH
k1 = 70 M
-1
s
-1
(2.1)
RH + OH
+ H2O k2 =10
7
-10
10
M
-1
s
-1
(2.2)
R
+ Fe
3+
R
+
+ Fe
2+
N/A (2.3)
Fe
2+
+ OH
Fe
3+
+ OH

k4 = 3.2 10
8
M
-1
s
-1
(2.4)
H2 O2 + OH
HO2

+ H2O k5 =3.3 10
7
M
-1
s
-1
(2.5)

As shown in equation (2.1), the ferrous iron (Fe
2+
) initiates and catalyses the
decomposition of hydrogen peroxide (H2O2) to generate the hydroxyl radicals (OH
).
The reaction (2.1) is commonly known as the main reaction of Fenton process (Neyens
& Baeyens, 2003). The generated hydroxyl radical reacts immediately with organic
substances (RH) resulting in a free organic radicals (R
). These radicals are

subsequently oxidized by ferric ion to generate other oxidation products (Matthew Tarr,
2003). In addition to the main reaction, various additional competitives or scavenging
reactions are also possible involving ferrous ions (Fe
2+
)

, hydroxyl radicals (OH
), and
hydrogen peroxide (H2O2) as listed in reactions (2.4)-(2.5). During the reaction, the
newly formed ferric ions (Fe
3+
) may continuously catalyze hydrogen peroxide to
produce ferrous ions and superoxide (HO2
). The reaction of hydrogen peroxide with

ferric ions is referred to Fenton-like reaction (Ameta et al., 2012; Bianco et al., 2011;
Matthew Tarr, 2003; Neyens & Baeyens, 2003). Fenton-like reactions are listed as
below:

10

Fe
3+
+ H2O2 Fe
2+
+ H
+
+ HO2
k6 = 0.001-0.01 M
-1
s
-1
(2.6)
Fe
3+
+ HO2
Fe
2+
+ H
+
+ O2 k7 = 1.2 10
6
M
-1
s
-1
(2.7)
Fe
2+
+ H2O2 Fe
3+
+ OH
+ OH
k8 = 70 M
-1
s
-1
(2.8)
RH + OH
+ H2O K8 = 10
7
-10
10
M
-1
s
-1
(2.9)

In the presence of organic substrates (RH), highly reactive hydroxyl radical
which is species with a relatively short life-span (rate constants in the range 10
7
-10
10
M
-1
s
-1
), undergoes oxidation generating a new radical (R
) as shown in reaction (2.9).

The possible organic compounds present in reaction mixture can suffer an abstraction
of a hydrogen atom (proton abstraction) or addition of hydroxyl radical (OH
) with the
production of organic radicals (R
) which can subsequently be oxidized by ferric ions

(Fe
3+
) as indicated in reaction (2.3). Indeed, the reaction (2.3) regenerates ferrous ions
(Fe
2+
) which ensure the continuity of the chain reaction. As long as the concentration
of reactants are not limited or available in the system, the iron species continually cycle
between Fe
2+
and Fe
3+
unless additional reaction result in formation of insoluble iron
oxides and hydroxides. This can lead ultimately to the decomposition of organic
substrate in carbon dioxide (CO2) and water inorganic salts (Lucas & Peres, 2009;
Matthew Tarr, 2003; Neyens & Baeyens, 2003).
Fenton-like Reaction
The conventional Fenton has been modified to improve treatment efficiency
with the reduced inorganic sludge production and prevention of inhibition reaction of
some ions. Those modified Fenton technologies includes photo-Fenton, electro-Fenton,
electro-photo Fenton and Fenton-like reaction. Fenton-like process uses other
transition metal catalyst other than Fe
2+
(Fu et al., 2009). The conventional Fenton has
been applied numerously while Fenton-like is not well elucidated. The introduction of
lower cost Fe
3+
in Fenton-like process may overcome the drawback of conventional
Fenton (S. Wang, 2008).
Recent applications of other transition metals in addition to Fe
2+
including Fe-
containing zeolites, soluble manganese (II) and amorphous and crystalline manganese
(IV) oxide, soluble iron (III), mixture of Fe
2+
/Cu
2+
and Fe
3+
/Cu
2+
, suspended iron
powder, clay-based Fe nanocomposite and zero valent iron (ZVI) were investigated.
However, ZVI and Fe
3+
have been commonly used as catalysts in Fenton-like reaction
11

due to their comparable efficiency and capacity (Fu et al., 2009 & 2013; Hodaifa et al.,
2013; Jiang et al., 2010 & 2013). Since the Fenton-like reaction can be applied
interchangeably and comparatively with Fenton reaction, it was recently selected for
wastewater treatment application in term of cost-effectiveness, efficiency, and easy of
application (Fu et al., 2009; Hodaifa et al., 2013; Jiang et al., 2010, 2013; Kim et al.,
2010; Kiril Mert et al., 2010; Li et al., 2013). Other investigations of Fenton and
Fenton-like process by using iron originated in wastewater still remain questionable
even though iron waste existed in the wastewater was feasibly use as catalyst for Fenton
reaction (Lan et al., (2012).
Jaing et al. (2013) has indicated the interconversion of Fe(III)/Fe(II) in Fenton
and Fenton-like reaction that they are co-occurring or coexisting. A Fenton-like
reaction involves a classical Fenton reaction, and Fenton reaction may also involve a
Fenton-like reaction step. However, Jaing et al. (2010) and Neyens & Baeyens (2003)
demonstrated conventional Fenton reaction was referred to the Fe
2+
/H2O2 system,
whereas Fenton-like reaction was included in the Fe
3+
/H2O2 system. Therefore, the
reaction mechanisms are similar in both systems, but are different in terms of catalysts
that are utilized to initiate the reaction.
Hydroxyl Radical Reaction with Organic Compounds
For the reaction of hydroxyl radical with organic species, there are three
common reaction pathways: (a) hydroxyl radical addition to an unsaturated compound
(aromatic or aliphatic) to form the free radical products, (b) hydrogen abstraction where
an organic free radical and water are formed (c) electron transfer, where ions of higher
valence state are formed reducing hydroxyl radical to hydroxide ions (Matthew Tarr,
2003; Munter, 2001; Neyens & Baeyens, 2003). Reaction pathways are shown below:

RH + OH
(OH)RH

C6H6 + OH
(OH) C6H6

(Hydroxyl Radical
Addition)
(2.10)

RH + OH
+ H2O
CH3OH + OH
CH2OH

+ H2O

(Hydrogen Abstraction)

(2.11)
12

RH + OH
(RH)
+
+

OH

[Fe(CH)6]
4
+ OH
[Fe(CH)6]
3
+ OH

(Direct Electron Transfer) (2.12)

Additional reactants including Fe
2+
, Fe
3+
, H2O, O2, H
+
, OH
, other metals,
other organics, and other radicals present in the system are necessary to complete these
subsequent reactions. Further oxidation processes continuously occur and
dimerizeation can also occur if the initially formed radical species reacts with another
identical radical. Other possible reactions including radical interaction where the
hydroxyl radical reacts with other hydroxyl radical to combine or to disproportionate
to form the stable products (Munter, 2001; Neyens & Baeyens, 2003). They are shown
as following:

OH
+ OH
H2O2 (dimerization of OH
) (2.13)
R
+ H2O2 ROH + OH
(2.14)
R
+ O2 ROO
(2.15)
ROO

+ RH ROOH + R
(2.16)

The organic free radical produced in the above reactions may then be oxidized
by Fe
3+
reduced by Fe
2+
, or dimerized according to the following reactions.

R
+ Fe
3+
-oxidation R
+
+ Fe
2+
(2.17)
R
+ Fe
2+
-reduction R

+ Fe
3+
(2.18)
R
+ R
-dimerization RR (2.19)

By applying Fentons Reagent for industrial waste treatment, the predominant
reaction are hydrogen abstraction and oxygen addition. Typical rates of reaction
between the hydroxyl radical and organic materials are 10
9
10
10
k (M
-1
s
-1
) (Matthew
Tarr, 2003).
13

Iron Ligand, Chelators and Coordination
Chelating agents still remained contradicted for Fenton reaction. Addition or
presence of resolubilizing chelators or chelating agents cause an increase in the
occurrence of reaction in the catalytic Fenton process. In contrast, chelating agents can
interfere the Fenton process by scavenging ability of the chelator. A good scavenger
may appear to have a lower production rate of hyrdoxyl radical due to rapid trapping of
the radical by the chelator. In addition, very strong iron chelators inhibit the formation
of hydroxyl radical. Iron ligands can also act as hydroxyl radical scavengers. Ligands
are more likely to react with hydroxyl radical than pollutants that are not in close
proximity to the iron because radical is always formed in close proximity to these
ligands. Such coordination will alter the kinetics of hydroxyl radical formation as well
as the dynamics of hydroxyl radical interaction with pollutants. Matthew Tarr (2003)
concluded that the inability of hydroxyl radical to reach sorbed or sequestered
pollutants is one of the major drawback to the application of Fenton degradation
method. However, it is suggested that aggressive conditions including high H2O2
concentration could make possibility for direct degradation of sorbed species.
Several studies have been investigated for the effect of chelators on Fenton
reaction. Addition of chelators to Fe(III)-H2O2 systems (Fenton-like reaction) allows
for effective degradation at near neutral pH values. The influence of the iron chelators
form increased solubility of iron species at higher pH value. Iron chelators improved
the Fenton oxidation of pollutant by increasing iron solubility and increases the rate
constant for hydroxyl radical formation from peroxide. The chelators also act as
hydroxyl radical scavengers from potential interaction with pollutants. Earlier studies
indicated that at pH 7.3, each EDTA-Fe complex was able to produce more than 50
hydroxyl radical before being degraded (Eckenfelder, 2000). The relative efficiencies
of the chelators for hydroxyl radical formation determine whether the added chelators
will have a positive or negative effect on radical formation. The complexation of EDTA
with iron minimized free ions for Fentons oxidation, resulting in a slow generation of
OH radical (Sillanp et al., 2011). However, the chelating agent may activate H2O2
oxidation at a neutral pH range. This pH ranges might affect the Fentons process due
to iron precipitation (Ghiselli et al., 2004). It reaches to a conclusion that the presence
14

of iron ligands and coordination could bring both positive and negative influences on
Fenton process depending on specific property of iron-coordinating complex.
Factors Affecting Fenton and Fenton-like Process
The significant factors affecting both processes are both H2O2 and Iron
concentrations, pH, reaction time, temperature, and initial pollutant concentration.
Effect of pH
The optimal pH for Fenton process is also determined to be between pH 3 and
pH 6. The application of the Fenton process at high pH value will result into the
inhibition of Fenton reaction since the Fe
2+
ions will form the colloidal Fe
3+
ions.
Likewise, the application of Fenton at very low pH value would result into the
decomposition of hydrogen peroxide into water and oxygen by iron without forming
hydroxyl radical (Neyens & Baeyens, 2003). Furthermore, Fenton oxidation presented
the maximum catalytic activity at pH 2.8-3.0. At very low pH, H2O2 is stabilized as
H3O2
+
(Wang et al., 2011). The reaction between OH
and H
+
also occurs. Fe
2+
regeneration by the reaction of Fe
3+
with H2O2 is inhibited at more acidic pH value. On
the other hand, at the pH higher than 3, Fe
3+
can precipitate as Fe(OH)3 and decompose
of H2O2 into O2 and H2O without
OH production (Bautista et al., 2007, 2008). A study

on EDTA degradation by Fenton process with pH ranged from 2 to 7 found that
degradation of EDTA decreased from 80.3% to 27.5% over the reaction time of 10 min
(Lou & Huang, 2009). This result indicated that the pH value significantly influenced
the removal of EDTA by directly affecting the generation of
OH which found that the

optimum range for Fenton oxidation was 2-4 (San Sebastin Martinez et al., 2003;
Bautista et al., 2007; Z. Wang et al., 2011; Jiang et al., 2013). At high pH, oxidation
yield of the process decreases due to the precipitation of Fe
3+
as Fe (OH)3 which
hindered the reaction between Fe
3+
and H2O2 and thus influenced the regeneration of
Fe
2+
. Moreover, Fe(OH)3 functionally catalyzed the decomposition of H2O2 into O2 and
H2O which decrease the production of hydroxyl radical (OH
). Therefore, pH of 2 was
the optimum condition for Fenton method in removal of EDTA. Similarly, Fu et al.
(2009 and 2012) and Lan et al. (2012) found the optimal pH of 3 and 2-5, accordingly,
for metal-EDTA complex wastewater treatment.
15

A second aspect of pH deals with its shift as the reaction progresses. During
the Fenton reaction, an initial wastewater pH typically degreases. This pH decrease is
caused by the addition of FeSO4 catalyst, which typically contains residual H2SO4. A
second, more pronounced drop in pH occurs as the H2O2 is added, and continues
gradually at a rate which is largely dependent on catalyst concentration. This drop in
pH is attributed to the fragmenting of organic material into organic acids. This pH
change is often monitored to ensure that the reaction is progressing as planned. The
absence of such a pH decrease may mean that the reaction is inhibited and that a
potentially hazardous build-up of H2O2 is occurring within the reaction mixture. In
highly concentrated waste streams (COD >10 g/L), it may be necessary to perform the
oxidation in steps, readjusting the pH upwards to pH 4-5 after each step in order to
prevent low pH from inhibiting the reaction (www.usperoxide.com)
Effect of Temperature
The effect of temperature on the rate of reaction of the Fenton process
increases as the solution temperature increases. The application of temperature greater
than 40 C, the treatment efficiency declined due to the decomposition of H2O2 into
oxygen and water. Fenton process has been normally conducted at temperature of 20 to
40 C (Bautista et al., 2008). A comparative study of Fenton and Fenton-like reaction
kinetics in decolorization of wastewater. The result has been indicated that temperature
had little influence on overall dye degradation in the range 15-45 C (Wang, 2008).
Dye degradation rate decreased when the temperature greater than 30 C due to
decomposition of H2O2 at higher temperature. Similarly, San Sebastin Martinez et al.,
(2003) found that temperature showed only a mild positive effect on COD removal.
The significance of temperature influencing the Fenton and Fenton-like oxidation was
clear that the increase of temperature could increase the removal efficiency in the
system because higher temperature increases the reaction between hydrogen peroxide
and Fe
2+
/Fe
3+
, and improve the generation rate of hydroxyl radicals. The increase
temperature from 25 to 50 C, the removal efficiency of Ni increased from 72.1 to
97.2% for Fenton and from 74.3 to 96.7% for Fenton-like after 20 min (Fu et al. 2009).
Since Fenton reaction is exothermic (optimal temperature varied from 20 to 30 C), it
allow an industrial treatment of OMW without temperature control (Nieto, Hodaifa,
Rodrguez, Gimnez, & Ochando, 2011). Consequently, temperature was not
16

considered in the optimization of Fentons reaction in highly polluted industrial
wastewater. This leads to a conclusion that temperature is important but not necessary
for Fenton reactions because of exothermic effects of reaction leading to increase of
temperature in a suitable of range as found in the works of Bautista et al (2008); Wang
(2008); Fe et al. (2009, 2012);and Lan et al.(2012).
Effect of Iron Concentration
Iron concentration plays a vital role treatment efficiency of Fenton and Fenton-
like reactions because the production rate of OH
is proportional to the concentration of

iron and hydrogen peroxide. However, iron content is the determining factors in sludge
production as a challenge for Fenton reaction (Wang et al., 2011). In the absence of
iron, there is no evidence that OH
is produced in wastewater. Inadequate concentration

of iron in the operating condition will lead to insufficient production of OH
, whereas
overdosing of iron can favor the scavenging reaction which prevents the reaction of
OH
with contaminants resulting in poor treatment efficiency (Matthew Tarr, 2003;

Neyens & Baeyens, 2003). The influence of ferrous concentration on EDTA
degradation have been indicated that increase of ferrous concentration from 10
-4
M to
10
-2
M resulting in the degradation of EDTA from 29.8% to 98.5% at a reaction time of
10 min., respectively. However, increasing Fe
2+
concentration from 10
-2
M to 10
-1
M
decreased EDTA degradation from 98.5% to 44.9%, accordingly. A higher Fe
2+
dose
provided the scavenging reaction between Fe
2+
and OH
(Lou & Huang, 2009). Another

study found that the increase of initial Fe
2+
or Fe
3+
from 0 to 1.0 mM resulting in the
increasing of removal efficiency remarkably. When Fe
2+
or Fe
3+
concentration was 1.0
mM, Fenton and Fenton-like systems achieved 92.8% and 94.7% of Ni removal
efficiencies after 60 min. of reaction time, accordingly. However, further increase of
Fe
2+
and Fe
3+
concentration did not achieve the improvement in Ni removal (Fu et al.,
2009). This indicated that the use of much Fe
2+
concentration could lead to the self-
scavenging of OH
by Fe
2+
as explained in the literatures (Matthew Tarr, 2003; Neyens
& Baeyens, 2003). A minimal threshold concentration of 3-15 mg/L Fe which allows
the reaction to proceed within a reasonable period regardless of the concentration of
organic materials. A constant ratio of Fe:substrate above the minimal threshold,
typically 1 part Fe per 10-50 parts substrate, which produces the desired end products.
The ratio of Fe:substrate may affect the distribution of reaction products. A
17

supplemental aliquot of Fe which saturates the chelating properties in the wastewater;
thereby, availing unsequestered iron to catalyze the formation of hydroxyl radicals.
Iron dose may also be expressed as a ratio to H2O2 dose. Typical ranges are 1 part Fe
per 5-25 parts H2O2 (wt/wt) (www. usperoxide.com).
Effect of H
2
O
2
concentration
The amount of H2O2 is considered one of the most important factors in Fenton
and Fenton-like reaction owing to its economic cost, sources of OH
generation,
improvement of treatment efficiency and side effects in overdosing. The H2O2 dose
has to be fixed according to the initial pollutant concentration (Matthew Tarr, 2003).
It is frequent to use an amount of H2O2 corresponding to the theoretical
stoichiometric H2O2 to chemical oxygen demand (COD) ratio, although it depends on
the response of the specific contaminants to oxidation and on the objective pursued in
term of reduction of the contaminant load (Neyens & Baeyens, 2003; Bautista et al.,
2007; Lan et al.,2012). Effect of H2O2 on the removal of COD was indicated that
increase in [H2O2]/[COD] from 0.5 to 2.0, the COD removal increased remarkably from
73.6% to 89.4%. However, the further increase in [H2O2]/[COD] from 2.0 to 6.0, the
removal of COD was negligible or unchanged (Lan et al., 2012; Wang et al., 2011).
The marginal improvement of COD removal may be explained by the scavenging effect
of excessive H2O2 to OH
and recombination of OH
which were supported in literatures

(Neyens & Baeyens, 2003; Matthew Tarr, 2003; Bautista et al., 2007, 2008; Wang,
2008; Wang et al., 2011; Lucas & Peres, 2009). Therefore, stoichiometric relation
between COD and H2O2 are significant for Fenton reaction and acceptable
[H2O2]/[COD] weight ratio should in the range of 2-4.
For most applications, it is important to optimize the molar ratio of [Fe
2+/3+
]/
[H2O2] for estimation of reagent requirement and convenience of experiments
(Matthew Tarr, 2003; Neyens & Baeyens, 2003). The presence of Fe
2+
or Fe
3+
salts not
only functions as catalytic reagents to decompose H2O2 for
OH generation, but also

reduces the scavenging effect of OH
radical from H2O2. The role of Fe

3+
plays an
important role in oxidizing the target organic compound and producing OH
radical
through Fe
2+
reaction (Kim et al., 2010). The [Fe
2+/3+
]/[H2O2] ratio is difficult to specify
and is varied according to the degradation of different pollutants covering the range
from 1:1 to 1:400 for a complete oxidation as reported in De Souza et al. (2006).
18

Effects of [Fe
2+
]/[H2O2] molar ratios of 1:50, 1:20, 1:10, 3:4 were conducted
for removal of initial COD of 300 mg/L by applying [H2O2]/[COD] of 4. Greater than
55% of COD removal was achieved in the first 10 min at higher [Fe
2+
]/[H2O2] molar
ratio. This results from higher generation of OH
radical according to reaction (2.1) as

shown previously. However, COD removal tended to decline in molar ratio of
[Fe
2+
]/[H2O2] greater than 1:20 due to quenching or scavenging effects of OH
radical
by excessive Fe
2+
according to reaction (2.2). [Fe
2+
]/[H2O2] ratio of 1:20 attained
highest performance for greater than 85% of COD removal (Wang et al., 2011). To
achieve 90% removal of 362000 mg/L COD, it was required to maintain the optimal
[Fe
2+
]/[H2O2] molar ratio of 1:10, while [H2O2] was 3M (San Sebastin Martinez et al.,
2003). This molar ratio was comparatively found to be lower than that of [Fe
2+
]/ [H2O2]
molar ratio at 1:15 resulting in the study of Lucas and Peres (2009). It is clear that
[Fe
2+
]/[H2O2] molar ratio varies according to type and concentration of organic
pollutant existing in the wastewater. The typical range of Fe
2+
]/ [H2O2] ratios are 1:5-
25 as reported in Bautista et al. (2008) and www.usperoxide.com.
Effect of Reaction Time
The time needed to complete a Fenton reaction depends on many variables
discussed above, most notably catalyst dose and wastewater strength. Typical reaction
times are 30-60 minutes for low strength wastewater. For more complex or more
concentrated wastes, the reaction may take several hours. Determination of reaction
completion prove troublesome (Matthew Tarr, 2003). A study on Fenton and Fenton-
like reactions from 20120 min. was conducted. Reaction time of 60 min for both
processes was determined for reduction of Ni concentration from 50 mg/L to 1 mg/L
and COD decreased from 252 mg/L to 53.3 mg/L, indicating about 78.8% COD
removal. After 60 min of reaction, the removal efficiency was marginal or almost
unchanged (Fu et al. 2009, 2012). This reaction time for Fenton oxidation is consistent
with Lan et al. (2012), who found optimum reaction time at 60-80 min. However, with
heterogeneous and complicated characteristics of wastewater, it was required 120 min
for reduction of COD from 300 mg/L to 40 mg/L (Wang et al., 2011).
The reaction time for a completion of Fenton reaction also depends on the its
reagents (Fe
2+
and H2O2 ) because the contaminant degradation rate is proportional to
the hydroxyl radical produced (Matthew Tarr, 2003). San Sebastin Martinez et al.
19

(2003) and Jiang et al. (2013) achieved optimum efficiencies in the first 10 min of
Fenton reaction due to the fast reaction in the first stage of Fenton oxidation, while
prolonging the reaction time remained efficiency insignificantly changed. However, it
was required longer than 1 hour reaction time for metal-complex wastewater treatment
due the persistency of organic compounds (Pirkanniemi et al., 2003). Therefore, the
application of Fenton oxidation to industrial wastewater treatment typically varies from
1 to 4 hours for optimal reaction time as reviewed in Bautista et al., (2008).
Chelating Agents Degradation by Various Fenton Processes
There were a number of studies of advanced oxidation processes based on
Fenton oxidation to degrade or mineralize the chelating agents particularly EDTA. Due
to mineralizing ability of H2O2 for organic pollutants, H2O2 is considered as eco-
friendly and safe reagent (Bautista et al., 2008). Without Fe
2+
activation, excessive
concentration H2O2 in alkaline environment (pH=10) was unable to degrade 0.04 mM
EDTA. It was recommended that the use of an effective catalyst might increase the
conversion rate into more biodegradable decomposition products (Rm & Sillanp,
2001). However, with the presence of transition metals (Fe
2+
), treatment of waste
containing EDTA by chemical oxidation obtained 90% of EDTA was degraded at the
initial concentration of 70 mM in 45 min (Tucker et al., 1999).
A study on Fentons oxidation to degrade EDTA from bleaching wastewater
reported that an almost complete removal of EDTA was achieved at the H2O2
concentrations of 74 mM, the pH of 4, and the H2O2:Fe
2+
:EDTA ratio of 70:2:1
(Pirkanniemi et al., 2007). This result was comparatively higher than whose previously
accomplished by Tucker et al. (1999), indicating 90% of EDTA at an initial
concentration of 70 mM as provided in Table 2.2. Further study is needed to check the
applicability of this method for the treatment of real wastewater and to develop
heterogeneous catalysts for this process. In addition, conventional Fenton process has
been modified to Fenton-like, electro-Fenton and photo-Fenton processes by using iron-
supported catalyst like Fe(III) and zero-valent iron (ZVI) to improve efficiency and
sludge associated problem caused by conventional Fenton process (Neyens & Baeyens,
2003; Bautista et al., 2008; Jiang et al., 2013; Zhou et al.,2009 & 2010). To degrade 1
mM EDTA, oxygen activation scheme applied in zero-valent iron system attained 95%
20

of EDTA degradation at an initial concentration of 1 mM at pH 6.5 within 2.5 h
(Noradoun & Cheang, 2005). In another study, Zhou et al. (2009) applied an oxidative
treatment by using heterogeneous ZVI and ultrasound to facilitate reduction of O2 to
H2O2. While being oxidized to Fe
2+
, ZVI induced series of Fenton-like oxidation and
degraded EDTA. In the system, EDTA acts as a complexing agent with the dissolved
Fe
2+
and generates H2O2. The result indicated that a lower EDTA degradation (81%) at
its concentration of 0.32 mM at pH 7.5 due to excessive iron catalyst added in solution
that prevented the formation of O
-
2-Fe
II/III
EDTA, slowing down EDTA degradation by
Fenton-like oxidation.
The application of heterogeneous metallophthalocyanine (FePcS) in Fenton-
like oxidation to degrade five different chelating agents including EDTA from
bleaching effluent was conducted. The rate of EDTA degradation was found to be
dependent on the concentration of Fe
2+
, H2O2, its molar ratio to the Fentons reagent,
pH, and temperature. Almost complete degradation of iron complexes of chelating
agents studied was remarkably obtained between 60% to 100% under pH 1.5 and initial
chelants concentration of 0.1M within a reaction time of 1 h. In addition, the most
relevant iron, manganese, sodium, copper and calcium EDTA complexes can be
successfully eliminated, the conversions being 93, 76, 68, 62 and 49%, respectively,
after 3h of reaction (Pirkanniemi et al., 2003). More description is detailed in Table 2.2.
Application Fenton and Fenton-like reactions under UV-A irradiation to
degrade the 5 mM EDTA achieved 80% of EDTA removal with EDTA:Fe
2+
and
EDTA:Fe
3+
ratio of 1:1 with the initial peroxide concentration of 100 mM in 4 hours.
However, in both cases the reaction rates were increased after 4 hours irradiation with
the total EDTA mineralization of 92 % (Fe
2+
, Fe
3+
, Fe
3+
+Cu
2+
system). The photolysis
of Fe(III)-EDTA complex in EDTA destruction can make use of high peroxide
concentration unnecessary. Photo-Fenton reaction was suitable for the treatment of
wastewater from cleaning and decontamination of nuclear power plant because this
wastewater contained small amount of Fe
2+
and Fe
3+
coming from corrosion process
(Ghiselli et al., 2004). For high iron content and organic citric acid (8 % synthetic citric
acid solution) in the derusting wastewater, UV photo-Fenton-like oxidation was used
because excessive amount of iron caused Fenton reaction occur automatically when
H2O2 was added. It was indicated that UV/H2O2/Fe
3+
could decomposed citric acid
21

better than UV/H2O2 and Fe
2+
/H2O2. This is apparently due to the important role of UV
in allowing Fe
3+
and H2O2 to function as strong oxidant in producing radical chain
reaction. In Fe
2+
/H2O2 system without UV, only 10% of complex removed due
chelating effects and precipitation. 93% COD reduction was achieved for
UV/H2O2/Fe
3+
(Kim et al., 2010). Photo-Fenton oxidation with the application of
visible radiation, UV radiation, and sunlight achieved a complete degradation of 20000
mg/L EDTA. within 31, 6 and 3 hours, respectively. The kinetics of photodegradation
using solar-Fenton reaction follow the order of solar-Fenton > UV (254 nm)- Fenton >
Visible-Fenton. The pH changes from acidic to alkaline range during the photo-Fenton
process indicated loss of chelating ability of EDTA and formation of amide was
confirmed. Therefore, the design and treatment of large volume of decontamination
waste containing EDTA using a solar Fenton process is easy, cost effective, and safe to
operate (Chitra et al., 2011). Mechanism of UV induced destruction, OH radical
induced destruction, and ferric ion induced destruction were implied for EDTA (Kim
et al., 2010).
Metal chelating complexes are not be easily removed or degraded by a single
process. Therefore, a number of studies have incorporated Fenton reaction with other
treatment methods to improve its efficiency (Bautista et al., 2008). The application of
Fenton, Fenton-like, and advanced Fenton reactions followed by hydroxide
precipitation in removal of Ni from NiEDTA wastewater were conducted. The
complete disappearance of NiEDTA and 92% of Ni (II) removal were obtained. Fenton
and Fenton-like reactions were effective to degrade EDTA and the fragmentation of
NiEDTA freed up Ni(II) ion which was removed by precipitation. Fenton-like process
representing higher Ni(II) removal efficiency than Fenton process can be attributed to
the mechanism of ligand exchange. However, advanced Fenton process (Fe
0
+ H2O2)
shows higher removal efficiency of Ni (98.2%) and requires lower H2O2 amount than
Fenton or Fenton-like processes. COD decreased from 252 mg/L to 53.3 mg/L;
indicating about 78.8% COD reduction. Lower percentage of COD removal may be
attributed to the formation of intermediates of acetate and formate. Less than 0.03 mg/L
of residue iron concentration was identified after Fenton type processes, which required
no further treatment options. This leads to a conclusion that Fenton type processes
seems to be an economically and environmentally friendly process for remediation of
22

strong stability chalated heavy metal wastewater (Fu et al., 2009, 2012). The optimum
operating parameters are also provided in Table 2.2
23

Table 2.2 Summary of Fenton process for various wastewater treatments
Wastewater
Type
Pollutant
Concentration
Optimum Conditions Efficiency Reference
EDTA 70 mM pH=4, T= 20 C, [Fe
2+
]= 5 mM, [H2O2]= 100 mM, RT= 30 min, EDTA=90% Tucker et al. (1999)
Fe-EDTA 200 mM pH=1.5, T= 40 C, [Fe
2+
]= 0.03 mM, [H2O2]= 0.88 mM,
RT= 180 min
EDTA=90% Pirkanniemi et al. (2003)
EDTA 76 mM pH=3, T= 40 C, [Fe
2+
]= 0.5 mM, [H2O2]= 18.5 mM, RT= 3 min EDTA=98% Pirkanniemi et al.(2007)
EDTA 68.5 mM pH=3, T= 40 C, [Fe
2+
]= 0.04 mM, [H2O2]= 0.88 mM,
RT= 720 min
EDTA=99% Chitra et al. (2004)
EDTA 5 mM pH=3, [Fe
2+
]= 200 mM, [H2O2]= 0.55 mM, RT= 240 min EDTA=80% Ghiselli et al. (2004)
Ni-EDTA Ni=25 mg/L pH=3, T= 40-50C , [Fe
2+/3+
]= 1 mM, [H2O2]= 141 mM,
precipitation pH= 11, RT= 60 min
Ni=92%
EDTA=100%
Fu et al. (2009)
Ni-EDTA Ni=25 mg/L
COD= 252 mg/L
pH=3, T= 40-50C , [ZVI]= 2 g/L, [H2O2]= 35 mM, precipitation
pH= 11.5, RT= 60 min
Ni=98.2%
COD=79%
Fu et al. (2012)
Cu-EDTA Cu=225.3 mg/L;
COD=1096 mg/L
pH=2-5, T= 40-50C , [Fe
2+
]/[H2O2] molar ratio = 2 ,
[H2O2]:[COD]=0.2-0.3, RT= 60-80 min
Cu=100%
COD=87%
Lan et al.(2012)
Olive oil Phenol = 66.2 mg/L;
COD=4017 mg/L
pH=3, Fe
3+
= 0.35-0.4 g/L, FeCl3/H2O2 = 0.026-0.058 w/w, COD=97%
Phenol=92%
Hodaifa et al. (2013)
Note: T : temperature, RT: reaction time
24

The treatment of metal chelating complex wastewater is not only for metals removal
but also for organic compound degradation. Another study combined interior
microelectrolysis (IM) and Fenton oxidation-coagulation (IM-FOC) to treat EDTA-
Cu(II) containing wastewater. COD was used indirectly to determine the concentration
of EDTA species in the wastewater. IM process provide nearly complete Cu(II)
removal and yielded 336.1 mg/L Fe(II) concentration at very low pH (pH=1.39) in
accordance with IM reaction mechanism as reported in reviews (Ju et al., 2011; Ju &
Hu, 2011). The poor treatment performance of COD by IM, indicating that EDTA
species cannot be effectively decomposed into small biodegradable organic molecules
by IM process. The Fe(II)-rich effluent of IM was suitable for direct treatment in a
subsequent Fenton oxidation without Fe(II) addition or pH adjustment. Under the
optimal operating condition, Cu(II) and COD decrease from 225.3 mg/L and 1096.6
mg/L to 0 mg/L and 142.6 mg/L with overall removal efficiency of 100% and 87%,
respectively by IM-FOC process. After treatment, the BOD5/COD ratio of wastewater
was enhanced from 0 to 0.42, indicating that EDTA was effectively oxidized in the
combined system (Lan et al., 2012).

25

CHAPTER 3
RESEARCH METHODOLOGY
This chapter provides methodology, materials, and reagents required for this
study. Experimental variables are also determined. Experimental procedures,
analytical methods, and kinetic modeling are described as follows:
Derusting Wastewater Characteristics
The derusting wastewater used in this study was obtained from the Kation
Power company, a cleaning service company, located in Rayong Province, Thailand.
This cleaning service company produces varying amount of wastewater according to
the numbers and types of cleaning processes. According to Huang et al. (2000), the
average cleaning wastewater is about 2300 m
3
during each boiler cleaning. However,
the approximate amount of wastewater ranges from 15 to 600 m
3
/week. The wastewater
is originally produced from cleaning processes of pipes or boilers. The wastewater
taken from the company is stored temporarily in a storage tank for further experiments.
During the cleaning processes, various chemicals and chelating agent (EDTA) are
applied to remove rusts and to protect pipe and boiler from corrosion. Furthermore, the
derusting wastewater is in the dark red color due to high iron content, which will form
a complex with the EDTA.
Materials and Chemical Reagents
The reagents used in this study are the analytical grade reagents and will be
used without any further purification. Deionized or distilled water will be used in all
experiments. Chemical reagents for Fenton and Fenton-like processes and chemical
reagents for wastewater parameters analysis are included as described and listed below:
1. Chemicals for Fenton and Fenton-like Processes
1.1 Hydrogen Peroxide (H2O2 -35% w/w),
1.2 Sodium Hydroxide (NaOH, 10N)
1.3 Sulfuric Acid (H2SO4, 5N)
1.4 Ferrous Sulfate (FeSO47H2O) for Fenton reaction
1.5 Manganese Dioxide (MnO2)
26

2. Chemicals for Parameters Analysis
2.1 COD
2.1.1 Standard Potassium Dichromate Digestion Solution
2.1.2 Sulfuric Acid reagent
2.1.3 Ferroin Indicator
2.1.4 Standard Ferrous Ammonium Sulfate (FAS) Titrant
2.2 Total Iron/Soluble Iron/Ferric/Ferrous Iron
2.2.1 Hydrochloric Acid (HCl) conc,
2.2.2 Hydroxylamine solution, AR Grade
2.2.3 Ammonium Acetate buffer solution
2.2.4 Sodium Acetate solution, AR Grade
2.2.5 Phenanthroline solution, AR Grade
2.2.6 Potassium Permanganate (KMnO4)
2.2.7 Stock Iron solution
3. Equipment and Materials
3.1 Jar Test apparatus (six paddles and six beakers with volume of 1L)
3.2 pH meter (EUTECH)
3.3 Multiparameter Photometer (Hana Instruments HI 83205-2008)
3.4 Analytical balance (OHAUS)
3.5 UV-Vis Spectrophotometer (Varian)
3.6 Turbidity meter (EUTECH)
3.7 Drying oven
3.8 Evaporating dishes
3.9 Suction flask
3.10 Desiccator
3.11 0.45m filter paper (GF/C )
3.12 Burette stand
3.13 Separatory funnel
3.14 Centrifugal machine (Harmonic Series)
3.15 Other glass wares (pipettes, burette, measuring cylinder, volumetric
flash, small beakers...)
27

Experimental Design and Procedure
Treatment efficiency of Fenton and Fenton-like reactions are the function of
the operating parameters including dosage of [H2O2], [Fe
2+
] and [Fe
3+
], initial pH, and
reaction time. Therefore, the variables of the experiment are classified and described
as follows:
a. Independent Variables
- Initial pH values: 2, 3, 4, 5, 6, 7
- [Fe
2+
] concentrations: 0.005, 0.01, 0.05, 0.08, 0.1 and 0.15 M
- [H2O2] concentrations indicated as Fe
2+
:H2O2 molar ratios:1:10,
1:20, 1:30, 1:40, 1:50, 1:60
- Precipitation pH values: 6, 7, 8, 9, 10, 11.
- Reaction time: 20, 40, 60, 80, 100, and 120 min.
b. Dependent Variables
- Total COD (TCOD), Soluble COD (SCOD), Total Iron, Soluble Iron,
Fe
2+
, Fe
3+
, Ammonium Nitrogen, Nitrite Nitrogen, Nitrate Nitrogen,
TSS, conductivity, and TDS as objective parameters
c. Control Variables
- Room temperature (28C) corresponding to the wastewater
temperature during Fenton and Fenton-like processes.
- Rapid mixing at 150 rpm for 2 min followed by slow mixing at 50
rpm.
- Homogenous wastewater characteristic in all experiments.

The proposed experimental design is divided into 2 sets of experiments. First
set of experiment is referred as the Fenton-like reaction (addition of H2O2 only) by
utilizing existing iron in the wastewater as catalyst. The second set of experiment is
referred as Fenton reaction (additions of both H2O2 and Fe
2+
). The detail experimental
design and procedures are provided in following steps and figure 3.1.

Determine wastewater characteristics
For each experiment, the wastewater stored in the storage tank is
poured in a large tank and is then mixed thoroughly so that the homogeneous
28

mixture will be achieved. The sample will be randomly collected for analyses
of wastewater characteristics. Various water quality parameters including
Total COD, Soluble COD, Total Iron, Soluble Iron, Fe
2+
, Fe
3+
, Ammonium
Nitrogen, Nitrite Nitrogen, Nitrate Nitrogen, conductivity, TSS and TDS.

Hydroxide Precipitation of Iron Before Fenton and Fenton-like
Processes
1. Prepare a Jar Test apparatus equipped with 6 beakers (size 1000-L
each). Fill every beaker with 500 mL of wastewater sample taken
from the large tank and then start mixing at 50 rpm for a few minutes
to have homogenous characteristic of wastewater
2. Adjust the pH of wastewater with H2SO4 or NaOH to pH values of 6,
7, 8, 9, 10, 11 in beaker No. 1, 2, 3, 4, 5, 6, respectively.
3. Keep mixing the solution in each beaker at the mixing speed of 50
rpm for 15 min.
4. At the end of mixing period, measure the parameters such as pH,
TDS, conductivity in the beaker and then collect the samples for
additional analyses including TCOD, SCOD, Total Iron, Soluble
Iron, Fe
2+
, Fe
3+
, Ammonium Nitrogen, Nitrite Nitrogen, and Nitrate
Nitrogen.
5. Stop mixing and allow the precipitates to settle for 30 minutes.
6. Collect the supernatant for sample analyses. The supernatant will be
centrifuged at 2000 rpm and filtrated by 0.45m filter paper for
analyses of TCOD, SCOD, Total Iron, Soluble Iron, Fe
2+
, Fe
3+
,
Ammonium Nitrogen, Nitrite Nitrogen, and Nitrate Nitrogen.
Effects of Initial pH on Fenton-like Process
29

4, 6, 8, 10, 12 in beaker No. 1, 2, 3, 4, 5, 6, respectively. Keep mixing
the solution in each beaker at the mixing speed of 50 rpm for a few
minutes. Then, measure the parameters such as pH, TDS,
conductivity in the beaker and then collect the samples for additional
analyses including TCOD, SCOD, Total Iron, Soluble Iron, Fe
2+
,
Fe
3+
, Ammonium Nitrogen, Nitrite Nitrogen, and Nitrate Nitrogen.
7. Gradually add H2O2 at the concentration of 2.0 M into each beaker.
Keep mixing at the same speed for 60 minutes.
Iron, Fe
2+
, Fe
3+
Nitrogen.
9. After collecting the samples, adjust the pH to 8 to stop the fenton-like
reaction. Continue mixing for another 15 minutes, and then stop
mixing and allow the precipitates to settle for 30 minutes.
2+
, Fe
3+
,
11. Repeat steps 1-10 with various pH values around the optimum pH
determined previously to obtain the best pH value.
Effects of H
2
O
2
Concentration on Fenton-like Process
each). Adjust the pH of wastewater in the large tank with H2SO4 or
NaOH to the optimum pH value determined from the previous study.
Fill every beaker with 500 mL of wastewater sample taken from the
large tank and then start mixing at 50 rpm for a few minutes to have
homogenous characteristic of wastewater
30

2. Gradually add H2O2 with six different concentrations of 1.0, 1.5, 2.0,
2.5, 3.0, and 3.5 M into each beaker. Keep mixing at the same speed
for 60 minutes.
Iron, Fe
2+
, Fe
3+
Nitrogen.
2+
, Fe
3+
,
Effects of Reaction Time on Fenton-like Process
2. Gradually add H2O2 at the optimum concentration determined from
previous study into each beaker. Keep mixing at the same speed for
20, 40, 60, 80, and 120 minutes of beaker No.1, 2, 3, 4, 5, and 6,
respectively.
3. After each mixing period of each beaker, measure the parameters
such as pH, TDS, conductivity in the beaker and then collect the
samples for additional analyses including TCOD, SCOD, Total Iron,
Soluble Iron, Fe
2+
, Fe
3+
, Ammonium Nitrogen, Nitrite Nitrogen, and
Nitrate Nitrogen.
31

2+
, Fe
3+
,
Hydroxide Precipitation of Iron After Fenton-like Process
each). Adjust the pH of wastewater in the large tank to the optimum
pH value determined from the previous study and then Fill every
beaker with 500 mL of wastewater sample taken from the large tank
and then start mixing at 50 rpm for a few minutes to have
2. Gradually add H2O2 at the optimum concentration determined from
previous study into each beaker. Keep mixing at the same speed for a
period of the optimum reaction time.
3. After ending the mixing perioid, adjust the pH of wastewater with
H2SO4 or NaOH to pH values of 6, 7, 8, 9, 10, 11 in beaker No. 1, 2,
3, 4, 5, 6, respectively.
rpm for 15 min.
2+
, Fe
3+
,

32

Effects of Initial pH on Fenton Process
3, 4, 5, 6, 7 in beaker No. 1, 2, 3, 4, 5, 6, respectively. Keep mixing
the solution in each beaker at the mixing speed of 50 rpm for a few
minutes. Then, measure the parameters such as pH, TDS,
conductivity in the beaker and then collect the samples for additional
analyses including TCOD, SCOD, Total Iron, Soluble Iron, Fe
2+
,
Fe
3+
, Ammonium Nitrogen, Nitrite Nitrogen, and Nitrate Nitrogen.
3. Adjust the mixing speed to 150 rpm, and then add Fe
2+
with a
concentration of 0.05 M. Maintain the mixing speed for 10 minutes
to distribute the ferrous thoroughly in the beaker.
4. After 10 minutes, gradually add H2O2 at the concentration of 2.0 M
into each beaker. Keep mixing at the same speed for 60 minutes.
Iron, Fe
2+
, Fe
3+
Nitrogen.
2+
, Fe
3+
,
8. Repeat steps 1-10 with various pH values around the optimum pH
determined previously to obtain the best pH value.
33

Effects of Fe
2+
Concentration on Fenton Process
2+
with six
different concentrations of 0.005, 0.01, 0.05, 0.08, 0.1 and 0.15 M
into beaker No.1, 2, 3, 4, 5, and 6, respectively. Maintain the mixing
speed for 10 minutes to distribute the ferrous thoroughly in the
beaker.
3. After 10 minutes, gradually add H2O2 at the concentration of 2.0 M
into each beaker. Keep mixing at the same speed for 60 minutes.
Iron, Fe
2+
, Fe
3+
Nitrogen.
2+
, Fe
3+
,
Effects of H
2
O
2
Concentration on Fenton Process
34

2+
with the
optimum concentration determined from previous study. Maintain
the mixing speed for 10 minutes to distribute the ferrous thoroughly
in the beaker.
3. After 10 minutes, gradually add H2O2 with six different
concentrations of 1.0, 1.5, 2.0, 2.5, 3.0, and 3.5 M into each beaker.
Keep mixing at the same speed for 60 minutes.
Iron, Fe
2+
, Fe
3+
Nitrogen.
2+
, Fe
3+
,
Effects of Reaction Time on Fenton Process
2+
with the
35

in the beaker.
3. After 10 minutes, gradually add H2O2 at the optimum concentration
determined from previous study into each beaker. Keep mixing at the
same speed for 20, 40, 60, 80, and 120 minutes of beaker No.1, 2, 3,
4, 5, and 6, respectively.
4. After each mixing period of each beaker, measure the parameters
such as pH, TDS, conductivity in the beaker and then collect the
samples for additional analyses including TCOD, SCOD, Total Iron,
Soluble Iron, Fe
2+
, Fe
3+
, Ammonium Nitrogen, Nitrite Nitrogen, and
Nitrate Nitrogen.
2+
, Fe
3+
,
Hydroxide Precipitation of Iron After Fenton Process
each). Adjust the pH of wastewater in the large tank to the optimum
pH value determined from the previous study and then Fill every
beaker with 500 mL of wastewater sample taken from the large tank
and then start mixing at 50 rpm for a few minutes to have
homogenous characteristic of wastewater.
2+
with the
in the beaker.
36

3. After 10 minutes, gradually add H2O2 at the optimum concentration
determined from previous study into each beaker. Keep mixing at the
same speed for a period of optimum reaction time.
4. After ending the mixing perioid, adjust the pH of wastewater with
H2SO4 or NaOH to pH values of 6, 7, 8, 9, 10, 11 in beaker No. 1, 2,
3, 4, 5, 6, respectively.
rpm for 15 min.
2+
, Fe
3+
,
Optimum Conditions
The optimum condition is determined for each ferrous and hydrogen peroxide
concentration by computing the removal efficiencies of pollutants at different varying
concentration of reagent used in Fenton and Fenton-like oxidations. The removal
efficiency (R) is calculated by the following equation:
Removal Efficiency (R) =
A- B
A
100
where, A represents the initial characteristic of the objective parameters; B represents
the final characteristics of the objective parameters. The objective parameters include
the TCOD, SCOD, Total Iron, Soluble Iron, Fe
2+
, Fe
3+
, Ammonium Nitrogen, Nitrite
Nitrogen, and Nitrate Nitrogen..
Analytical Method
The analytical methods for each parameters will be analyzed according to the
Standard Method for the Examination of Water and Wastewater (APHA, 2005). They
are briefly described as following:
1. The TCOD and SCOD of treated water is determined by the close reflux
titrimetric method (Method 5520).
37

2. The pH of solution will be measured with a EUTECH pH meter.
3. Total iron, soluble iron, ferric and ferrous concentrations will be analyzed by
Phenanthroline Method (Standard Method 3500).
4. Total suspended solid (TSS) determined by standard method (Method 2540).
Total solid and total dissolved solids (TDS) dried at 103-105C are
determined according to Standard Method (Method 2540)
5. Total dissolved solid (TDS) is determined by portable TDS meter (STARTER
300C)
The detail description of each parameter analytical method is referred to
Appendix B.
Kinetic Study
Due to the complexity of the organic pollutant in the derusting wastewater and
intermediates formed in the Fenton and Fenton-like reactions, it is impossible to
conduct a detailed kinetic study with the different individual reactions that take place
during the reaction. However, it is possible to conduct an approximated kinetic study
for organic compound degradation measured in COD removal (Wang et al., 2011;
Lucas & Peres , 2007). The complete oxidation reaction of Fenton and Fenton-like
reactions in removal of COD can be represented as below:

Organic matter (COD) + OH

Oxidized product (P) + CO2 + H2O (3.1)

The kinetic removal of COD removal by Fenton and Fenton-like reaction can
be represented by the following nth-order reaction kinetics as described in Skoog and
West (2004), Bautista et al. (2007) and Wang (2008).

-
dCOD
dt
=kCOD
n

where n is the order of the reaction, k is the reaction rate constant and t is the
time.
According to the equation (19), the kinetic removal of COD can be written in
second order reaction according to the study of Samet et al.,(2011) as provided below:
38

-
dCOD
dt
=k[OH
]COD (second order reaction)

However, Lucas & Peres (2007) & Samet et al.,(2011) assume that the
hydrogen peroxide (H2O2) during the reaction is far excess and
OH concentration is
constant during the reaction. Therefore, the kinetic removal of COD during Fenton and
Fenton-like reactions can be simplified to a pseudo-first order reaction as follow:

-
dCOD
dt
=k
upp
COD ( pseudo-first order reaction)

which can be integrated between t=0 and t=t, yielding:

C
t
= C
0
exp(-k
app
t) or ln
COD
0
COD
t
= -k
app
t

where kapp is the pseudo-first order apparent rate constant (kapp = k[OH
]).

The kapp constants are obtained from the slope of the straight lines by plotting
ln (Ct /C0) as a function of time t. The data is fitted using the first order and second
order rate equation. The best fit is chosen when the coefficient of linearity is nearly
equal to the value of 1 (Skoog and West, 2004; Samet et al., 2011).

39

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44

APPENDICES
Appendix A: Activities plan
Activities
2013 2014
Jan Feb Mar Apr Ma
y
Jun Jul Aug Sep Oct Nov Dec Jan Feb Mar Apr May
Topic Selection
Literature Review
Pre-test Method
Proposal Defense
Proposal Revision
Experiment
Data Analysis
Thesis Reporting
Thesis
submission and
Revision

Thesis Defense
Publication
45

Appendix B: Chemical Analysis Procedures
1. CHEMICAL OXYGEN DEMAND (COD) (5220 B. Close Reflux Method)
1.1. Principle
Chemical oxygen demand (COD) is used as a measure of oxygen requirement of a sample
that is susceptible to oxidation by strong chemical oxidant. The dichromate reflux method is
preferred over procedures using other oxidants (eg potassium dichromate) because of its
superior oxidizing ability, applicability to a wide variety of samples and ease of
manipulation. Most types of organic matter are oxidized by a boiling mixture of chromic
and sulfuric acids. A sample is refluxed in strongly acid solution with a known excess of
potassium dichromate (K2Cr2O7). After digestion, the remaining unreduced K2Cr2O7 is
titrated with ferrous ammonium sulfate to determine the amount of K2Cr2O7 consumed and
the oxidizable matter is calculated in terms of oxygen equivalent.
1.2. Apparatus
a. Test tube or digestion vessels
b. Heating oven (150 C)
c. Micropipettes
d. Beakers (250 mL)
e. Volumetric pipettes (10 mL)
f. Burette and burette stand
g. Test tube rack
1.3. Reagents
a. Sulfuric acid reagent (H2SO4) for COD: Add 22g of reagent grade silver sulphate to a 4-
kg bottle of concentrated sulphuric acid (H2SO4) and mix until the silver sulphate goes
into solution.
b. Potassium dichromate (K2Cr2O7) 0.25N, Dissolve 12.259 g K2Cr2O7, primary standard
grade, previously dried at 150C for 2 h, in distilled water and dilute to 1000 mL.
c. Ferroin indicator solution: Dissolve 1.485 g 1,10-phenanthroline monohydrate and 695
mg FeSO47H2O in distilled water and dilute to 100 mL.
d. Standard ferrous ammonium sulfate (FAS) titrant, 0.25M: Dissolve 98 g
Fe(NH4 )2(SO4)26H2O in distilled water. Add 20 mL conc H2SO4, cool, and dilute to
1000 mL. Standardize this solution daily against standard K2Cr2O7 solution as follows:
46

Dilute 25.00 mL standard K2Cr2O7 to about 100 mL. Add 30 mL conc H2SO4 and cool.
Titrate with FAS titrant using 0.10 to 0.15 mL (2 to 3 drops) ferroin indicator.
Morality of FAS solution=
volume K
2
Cr
2
O
7
solution titrated, mL
Volume FAS used in Titration, mL
0.1
1.4. Procedure
a. Prepare COD test tubes for sample, hot blank and cold blank
b. Pipette 1 mL of sample and 5 mL of water into sample tube
c. Add 3 mL potassium dichromate
d. Add 7 ml of sulfuric acid reagent
e. Heat in the oven at 150 C for 2 hours then cool down the test tube
f. Add 2-3 drops of ferroin indicator
g. Start to titrate the FAS solution until sample color turn to mild pink and record its
volume used
(Hot and cold blank tubes are done the same as sample tube processes)
1.5. Calculation
COD as mg O
2
/L=
(A-B)M8000
mL of sample

where:
A = mL FAS used for blank,
B = mL FAS used for sample,
M = molarity of FAS, and
8000 = milliequivalent weight of oxygen X 1000 mL/L.

2. Determination of Iron concentration (3500-Fe B. Phenanthroline Method)
2.1. Principle
Any solution which is colored or can be made colored by adding a complexing agent can be
analyzed using a visible spectrophotometer. Solutions containing iron ions are colorless, but
upon addition of, the iron (II) ions in the sample react immediately to produce a complex ion,
which is orange-red in color. This follows the Beer-Lambert Law of spectroscopy. From data
obtained from a series of iron (II) standards, it is possible to be able to determine the amount
of iron in an unknown sample.
2.2. Apparatus
47

a. Spectrophotometer Instrument with its kit; (Varian)
b. Pipette (10 mL) and Micropipette
c. Volumetric Flask (100, 500 mL)
d. Acid-washed glassware
e. Erlenmeyer flasks
f. Hot plate
g. Glass beats
2.3. Reagents
a. Hydrochloric acid (HCl) conc, containing less than 0.5 ppm
b. Hydroxylamine solution: Dissolve NH2OH-HCl in 100 mL water
c. Ammonium acetate buffer solution: Dissolve 250 g of NH4C2H3O2 in 150 mL water. Add
700 mL glacial acetic acid. Sodium acetate solution.
d. Sodium acetate solution: Dissolve 200 g NaC2H3O23H2O in 800 mL water
e. Phenanthroline solution: Dissolve 100 mg 1,10-pehnanthroline monohydrate,
C12H8N23H2O in 100 mL water by stirring and heating to 80 C. Heating is unnecessary
if 2 drops of HCL are added.
f. Potassium permanganate (KMnO4), 0.02M: Dissolve 0.316 g KMnO4 in reagent water and
dilute to 100 mL.
g. Stock iron solution: slowly add 20 mL conc H2SO4 to 50 mL water and dissolve 1.404 g
Fe(NH4)2(SO4)23H2O. Then slowly add potassium permanganate solution until fain pink
color persists. Add few milliliters dropwise. Dilute to 1000 mL with water.
h. Standard iron solution: pipette 50 mL stock solution into a 1000 mL volumetric flash and
dilute to mark with water; 1 mL =10 g Fe.
2.4. Sample preparation before analysis (Sample containing organic interferences)
2.4.1. Digestion with (HNO3) to digest organic interferences
a. Transfer 50 mL of sample into a 125 mL conical flash
b. Add 5 mL of HNO3 conc.
c. Heating on hotplate to evaporate sample to 15-20 mL
d. Heat to remove all HNO3 before continuing treatment (HNO3 removed if solution
is clear or no browndish fume is evident
e. Cool down and transfer sample to a 100-mL volumetric flask dilute to mark and
mix thoroughly. Take 1 portions of this solution for required metal determinations.
2.4.2. Extraction to eliminate the other metal ions interferences
48

a. Pipette 10 ml or other suitable portion containing 20-500 g Fe of digested sample
into 125-mL separatory funnel (if volume taken is less than 10 mL, add water to
make up to 10 mL)
b. Add 15 mL conc HCl for 10-mL sample. Then mix and cool down the solution
c. Add 25 mL of isopropyl ether and mixing for 30 seconds then wait for layer
separation
d. Drain off acid layer to second separatory funnel and extract acid solution again
with 25 mL isopropyl ether then drain acid layer into a clean beaker
e. Transfer ether layer in second separatory funnel into the first separatory funnel
f. Pour acid layer back into second separatory funnel and re-extract with 25 mL
isopropyl ether.
g. Withdraw and discard acid layer and return ether layer again into first separatory
funnel
h. Shake combined ether and add 25 mL of DI water to return iron to aqueous phase
and transfer lower layer(water layer) into a 100- ml volumetric flask
i. Repeat the addition of 25 mL of DI water and transfer water layer in 100 mL
volumetric flask
2.5. Determination Procedure
5.2.1. Total iron ( for digested and extracted sample)
a. Take extracted sample (50 mL in a 100-mL volumetric flask) and add 1 mL of
hydroxylamine
b. Add 10 ml phenanthroline
c. Add 10 ml Sodium Acetate buffer solution (NaC2H2O2)
d. Dilute to 100 mL then mix and stand for 10 min for color development
e. Measure absorbance in spectrophotometer and read it concentration in calibration
curve (figure 1)
f. Calibration curve of ferrous iron is formulated by pipetting 50 mL of standard
solution (1mL = 10 g Fe) in a 100 mL volumetric flask then follow step a-c
(Series dilutions are used to get ferrous iron concentration of 31.25, 62.5, 125, 250,
and 500 g in final 100-volume)
49

Figure 1: Calibration curve for total iron

5.2.2. Dissolved iron
a. Immediately collect filter sample through a 0.45 m filter paper into a vacuum
flask containing 1 mL conc HCl/100 mL sample. Analyze filtrate for total
dissolved iron (according to step 5.2.1) or ferrous iron( according to step 5.2.4)
Suspended Iron = Total Iron- Dissolved Iron
5.2.3. Ferrous iron:
a. Acidify the sample by pipetting 50 mL into 125-mL Erlenmeyer flask (if Fe >200
g, the sample needs to be diluted) and add 1 mL conc HCl
b. Add 20 mL phenanthroline solution and 10 mL NH4C2H3O then Dilute to 100 mL
c. Measure color intensity within 5 to 10 min in spectrophotometer at 510 nm and
concentration of ferrous from calibration curve as provided in figure 1
d. Ferric iron can be determined by
Ferric Iron = Total Iron-Ferrous Iron

5.3. Calculation
mg FeL=
g Fe (in 1uu mL final volume)
mL sample

1uu
ml poition

y = 0.002x - 0.0005
R = 1
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0 50 100 150 200 250 300 350 400 450 500
A
b
s
o
r
b
a
n
c
e
Fe (g in 100 mL)
50

Appendix C: Fentons Reagent Preparation

1. Preparation of 300 mL of Fe
2+
solution (0.1M) from FeSO
4
.7H
2
O
a. Calculate the amount of Fe
2+
in form of FeSO4.7H2O by
SuumL u.1
mol Fe
2+
L

1 mol FeS0
4
. 7B
2
0
1mol Fe
2+

278.u2g
1 mol FeS0
4
. 7B
2
0
L
1uuumL

1uu
99.S
(%Assay) = 8.S8 g
b. Weight 8.38 g of FeSO4.7H2O using analytical balance
c. Prepare 300 mL of distilled water and adjust pH to 3-4 in order to avoid the precipitation of iron
d. Dissolve 8.38 g of FeSO4.7H2O and transfer to 300 mL volumetric flash then keep it in
refrigerator for the next experiment
2. Preparation of 300 mL of Fe
3+
solution (0.1M) from FeCl
3
.6H
2
O
a. Calculate required amount of Fe
3+

SuumL u.1
mol Fe
3+
L

1 mol FeCl
3
. 6B
2
0
1mol Fe
3+

27u.S2g
1 mol FeCl
3
. 6B
2
0
L
1uuumL

1uu
99.u
(%Assay) = 8.191S g
b. Weight 8.1915 g of FeCl3 and dissolved in 300 mL distilled water that pH is adjusted to 3-4 to
prevent the precipitation of ferric
c. Transfer into a 300 mL volumetric flash and store in refrigerator for the next experiments
3. Calculation of H2O2 molar concentration
2.5 L of H2O2 with assay 35 % (v/v) is used in the experiment. Density of 35% H2O2 = 1.14 g/mL
and MW of H2O2 = 34.01 g/mol

Bensity % of B
2
0
2

1 mol
NW of B
2
0
2

1uuu mL
1 L

1.14
g
mI

SS
1uu

1 mol
S4.u1 g

1uuu mI
1 I
= 11.7S H

4. Preparation of 10 N NaOH Solution
a. Calculate the amount of NaOH required
1u eq
L

mol
1 eq

4u g
mol
= 4uu gL
51

b. If solution volume is required 500 mL, mass of NaOH required is 200 g
c. Dissolve 200 g with distilled water then dilute to 500 mL
5. Preparation of 5 N H2SO4 Solution
a. Calculate the concentration of H2SO4 ( density= 1.84 g/cm
3
or 1.84 g/mL, purity= 98%,
MW=98.08 g/mol)
Bensity % of B
2
S0
4

1 mol
NW of B
2
S0
4

1uuu mL
1 L

1.84 g
mL

98
1uu
1 mol
98.u8 g
1uuu mL
L
= 18.S8 N
Normality (N) of H2SO4 is given by
18.S8 mol
L

2 eq
1 mol
= S6.76 N
b. Calculate the volume of H2SO4 for 500 mL of H2SO4 5N
According to dilution rule: N1V1= N2V2
36.76N V1 = 5N 0.5L
The required volume of H2SO4 = 0.068 L or 68 mL
c. Prepare 432 mL of distilled water in a 1000 mL beaker
d. Pipette 68 mL of con. H2SO4 and add slowly into beaker
e. Cool down and ready to use for pH adjustmen

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APPLICATIONS OF FENTON AND FENTON-LIKE REACTIONS WITH

SUBSEQUENT HYDROXIDE PRECIPITATION FOR DERUSTING

) when H2O2 is added to the iron-rich

). It has electrochemical oxidation potential (EOP) o f2.8 V,

). These radicals are

). The reaction of hydrogen peroxide with

) as shown in reaction (2.9).

) which can subsequently be oxidized by ferric ions

OH production (Bautista et al., 2007, 2008). A study

OH which found that the

is proportional to the concentration of

is produced in wastewater. Inadequate concentration

with contaminants resulting in poor treatment efficiency (Matthew Tarr, 2003;

(Lou & Huang, 2009). Another

which were supported in literatures

OH generation, but also

radical from H2O2. The role of Fe

radical according to reaction (2.1) as

]COD (second order reaction)

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