23

CHAPTER 2

LITERATURE REVIEW

This chapter covers extensive literature collection on tannery

industry, treatment methods of organic effluent, rotating disk electrode and
residence time distribution.

2.1 TANNERY INDUSTRY

Tanning industry contributes significantly towards exports,

employment generation and occupies an important role in Indian economy on
the other hand; tannery wastes are ranked as the highest pollutants among all
the industrial wastes. Tannery industries use a large number of chemicals (i.e.,
natural and synthetic tanning agents, surfactants, salts, etc.) for the treatment
of skins and consequently produce large quantities of effluents (about 10m3 of
waste per tonne of leather) which have to be purified before being discharged
into the environment. Since tannery wastewater contains both organic
compounds, mainly tannins that are polyphenolic molecules, and inorganic
compounds such as ammonia, sulfides, and chlorides, the combination of
conventional methods of physiochemical and biological methods do not
always meet the legal limits for waste discharge (Marcopanizza et al 2004,
Balakrishnan et al 2002, Iaconi et al 2002, Jochimsen et al 1997, Rao et al
2001, Dima et al 2006, Balakrishnan et al 2002, Lefebvrea et al 2005).
Physico-chemical treatment of tannery effluents consists of chemical
 24

precipitation, adsorption, coagulation, flocculation, sedimentation, filtration,

ion exchange and chemical oxidation (Ramesh et al 2007, Kyung-Sok et al
2004, 2007, Lefebvre et al 2006, Metes et al 2004, EPA, 2004, UNEP, 2004,
Linda and Peter 1999).

Advanced Oxidation Processes (AOPs) have been developed to

overcome the problem of treating high refractory pollutants (Preethi et al
2009a,b, Lech Kos et al 2003, Giusy Lofrano et al 2009).

2.2 TREATMENT METHODS

2.2.1 Conventional Methods

Various treatment processes, such as sedimentation, coagulation–

flocculation, adsorption, chemical oxidation, and membrane processes, as
well as biological (both aerobic and anaerobic) processes and fungal
treatment, have been studied for the treatment of tannery wastewaters. The
conventional method includes Membrane filtration (Justina et al 2009),
Precipitation (Kabdasli et al 2003, Esmaeili et al 2005) and Coagulation
(Jing-Wei et al 2007, Haydar et al 2009, Zhi et al 2009, Espinoza-Quinones
et al 2009, Sengil et al 2009). Adsorption (Santosa et al 2008, Covarrubias
et al 2008), Ion exchange (Tiravanti et al 1997, Kabir and Ogbeide 2008) and
Biological methods studied by Martinez et al (2003), Farabegoli et al (2004),
Murat et al (2006), Lefebvre et al (2006), Banu and Kaliappan (2007), Munz
et al (2008), Zupancic and Jemec (2010). Schrank et al (2004) has reported
that many organic compounds contained in the effluent are resistant to
conventional chemical and/or biological treatment. The degradation of
inhibitor substance such as tannin during the anaerobic digestion was
investigated by Banu and Kaliappan (2007). Lombardo et al (1997) reported
a marginal increase in COD reduction and a substantial improvement in floc
 25

settling when bentonite or organic flocculants were used together with ferric
chloride or polyaluminium salts.

In biological method, microorganisms are utilized to treat

wastewater because they can uptake organic matter and nutrients (nitrogen
and phosphorus) for energy source, metabolism and for building blocks
(cell synthesis) (Pittier and Chudoba 1990, Wiesmann et al 2007). Typical
biological treatment processes make use of trickling filters, activated sludge,
Sequencing Batch Reactor (SBR) and wetland as polishing system. Organic
pollutants and colloidal organics from wastewater can successfully be
removed by biological treatments (Benefield and Randall 1985, Seabloom and
Buchanan 2005). In this treatment technique, micro-organisms utilize the
organic matter for metabolism processes (Bashaar 2004, Wiesmann et al
2007, Seabloom and Buchanan 2005). Biodegradation of organic matter
during wastewater treatments occur either in the presence of oxygen
(aerobically) or in anoxic conditions by denitrification (Jeyaseelan 1997,
Nicholas 1996, USEPA 2004). Many investigators have reported the use of
biological treatments, specifically, sequencing batch reactors (SBR) in
tannery wastewater as an efficient way for the removal of organic matter
(Ganesh and Ramanujam 2009, Farabegoli et al 2004, Murt et al 2002,
Lefebvre et al 2006).

Even though the conventional methodologies are technically

feasible, on lab scale operations they are questionable for their technical and
economic feasibility in large scale operations. Thus, it can be observed that
the problem involving the proper management of the tannery effluent has not
been solved. Hence the evolution of AOP was originated as an alternative
method of treating this kind of problems.
 26

2.2.2 Advanced Oxidation Process (AOP)

Tannery effluents are oxidized by four different reagents like

ozone, hydrogen peroxide, Fenton oxygen, and air, in precise,
pre-programmed dosages, sequences UV radiation. These procedures may
also be combined with any one of oxidation process or agents are known as
advanced oxidation process (AOP). Advanced oxidation processes (AOPs)
may become the most widely used water treatment technologies for organic
pollutants, which cannot be treated by conventional technologies due to the
high chemical stability and/or low biodegradability. Depending on the
operating temperature, the type of used oxidant, and the concentration of the
pollutants in the wastewater, the possible partial oxidation step can be
classified into three main categories: Incineration, Wet air oxidation process
(WAO) and Oxidation with strong oxidants. These processes involve
generation and subsequent reaction of hydroxyl radicals (·OH).

Schrank et al (2004) studied the various oxidation techniques (UV,

TiO2/UV, O3, H2O2/UV and O3/UV) to degrade tannery wastewater.
Degradation of xenobiotics originating from the textile preparation, dyeing,
and finishing industry using ozonation and advanced oxidation was reported
to be very effective (Arslan-Alaton et al 2004). The UV/O3 process is
expected to improve the treatment efficiency due to the activation of ozone
molecules by UV photons and thereby facilitating the formation of hydroxyl
radicals.

Awan et al (2003) was analysed that the recovery of chromium

from tannery wastewater by H2O2, sodium hypochlorite and calcium
hypochlorite oxidants to soluble chromate. H2O2 was potentially a suitable
oxidant as it could oxidize a suspension of Cr (OH)3 to chromate to 98% and
 27

88% in the synthetic and real wastewater. Dantas et al (2003) was evaluated
that the efficiency of Fenton and Photo-Fenton processes for the treatment of
wastewater from leather industry, in a 4 hr time period 90% of COD removal
was achieved. The concentration of hydroxyl radicals (•OH) increases
removal efficiency also increased.

However, all these methods have some major drawbacks. For

example, in conventional treatment, filtration and adsorption are not always
sufficient to achieve the discharge limits; coagulation and flotation generate a
large amount of sludge; chemical oxidations have low capacity rates and need
transportation and storage of dangerous reactants; and advanced oxidation
processes require high investment costs. In this context, oxidative
electrochemical technologies offer an alternative solution to many
environmental problems (Marco Panizza and Giacomo Cerisola 2009).

2.3 ELECTROCHEMICAL TREATMENT

Electrochemical technologies have gained importance in waste

water treatment during the past two decades (Lin et al 1998). There are
different companies supplying facilities for metal recoveries, treating drinking
water or process water, treating various wastewaters resulting from tannery,
electroplating, dairy, textile processing, oil – in – water emulsion, etc. at the
present time, electrochemical technologies have reached such a state that they
are not only comparable with other technologies in terms of cost, but also
more efficient and compact. The development, design and application of
electrochemical technologies in water and wastewater treatment have been
focused particularly to electro oxidation, electro deposition, electro
coagulation and electro flocculation (Kobya et al 2003). An extensive
research has been done by many researchers in treating various wastewaters
by using electrochemical technologies. These techniques will be explained in
 28

brief, being the electrochemical oxidation ours central point. Technical

feasibility for the treatment of various industrial effluents such as
electroplating waste water (Adhoum et al 2004b); oil mill wastewater
(Apostolos et al 2007); heavy metal laden wastewater (Lai et al 2003); nitrite
effluent (Koparal et al 2002); de-fluoridation (Zhu et al 2007); arsenic
removal (Balasubramanian et al 2009a, 2009b); textile dyes
(Saravanathamizhan et al 2007, Chithra et al 2008, Mohan et al 2007); landfill
leachate (Tsai et al 1997); restaurant wastewater (Chen et al 2000a, 2000b);
laundry wastewater (Ge et al 2004); surfactants (Ebru et al 2007); agro
industry wastewater (Patrick et al 2008) etc has been studied extensively.

2.3.1 ELECTRO OXIDATION

Electro oxidation of organic and inorganic compounds takes place

via two principle pathways direct oxidation and indirect oxidation. The direct
oxidation occurs at the anode in which the pollutants discharge its electron to
the anode electrode in order to maintain the flow of current in the bulk
solution. The indirect oxidation occurs as a result of the production of
powerful oxidizing agents in the bulk solution such as chlorine, hydrogen
peroxide and ozone. Short-lived intermediates, such as OH.2, O.2 and HO.2
also form during the electro-oxidation and could effectively destroy the
organic and inorganic pollutants.

The electrochemical oxidation of phenolic compounds was studied

using different anodic materials by Comninellis et al 1993, Saracco et al 2000,
2001, Canizares et al 2002, 2004a, 2004b, 2005b, Iniesta et al 2001 and these
authours are reported, electro oxidation gives more removal efficiency. Lidia
et al (2005) studied the ability of the electro oxidation technique in improving
the biodegradability of the tannery wastewater. Extensive research has been
going on for the electro oxidation of wastewater treatment using various
electrodes.
 29

Vijayalakshmi et al (2011) studied the electro-oxidation and

advanced oxidation as tertiary treatment technique for the purification of
tannery wastewater. The results indicated that the TOC removal by advanced
oxidation became sluggish, when the wastewater was processed initially by
electro-oxidation. However, the effluents processed by EO were found to be
completely disinfected.

Raoof et al (2011) investigated the electrochemical oxidation of

methanol on the surface of a new modified carbon paste electrode which was
prepared by incorporation of Ni (II)–zeolite in the carbon paste matrix. It was
found that methanol was oxidized by NiOOH generated with further
electrochemical oxidation of nickel hydroxide on the surface of this modified
electrode during the anodic potential sweep.

Xiuping Zhu et al (2011) studied the electrochemical oxidation of

biologically-pretreated dye wastewater which was performed in a boron
doped diamond (BDD) anode system. After electrolysis of 12 h, the COD was
decreased from 532 to 99 mg L 1. The performance of BDD anode system in
degradation of large molecular organics such as humic substances makes it
very promising in practical applications as an advanced treatment of
biologically-pretreated wastewaters.

Hongbin Zhao et al (2011) synthesized ordered mesoporous carbon

(OMC) supported nanosized Pt and Pt Co alloy electro catalysts by ethylene
glycol hydrothermal reduction route and their electrochemical oxidation
activity toward several typical small organic molecules (SOMs) was
investigated. Electrochemical measurements confirmed that electrochemical
oxidation behaviors of SOMs on synthesized Pt/OMC and Pt Co/OMC
catalysts were complicated and the carbon chain length of SOMs and the
intermediates, especially COads oxidation behaviors on Pt active sites are two
main factors which affect the SOMs oxidation.
 30

Nigel Bunce et al (2011) studied the electrochemical oxidation of

ammonia in alkaline solution at platinized platinum. Elemental nitrogen is
formed at mildly positive potentials with near quantitative current efficiency
through dimerization of partly dehydrogenated ammonia molecules NHx(ads).
The major intermediate, NH2(ads), is formed at Pt(1 0 0) domains on the
metal surface, where it dimerizes to hydrazine, and rapidly oxidizes to N2. At
somewhat more positive potentials, the formation of adsorbed nitrogen atoms
poisons the anode, and nitrogen evolution ceases. At potentials where water is
oxidized, the Pt anode is modified by a surface oxide. Under these conditions,
nitrogen evolution is accompanied by nitrogen oxides and oxy anions.

Elisabetta Turro et al (2011) studied the electrochemical oxidation

of stabilized landfill leachate with high COD value of 2960 mg L 1, using
Ti/IrO2–RuO2 anode in the presence of supporting electrolyte (HClO4). The
important parameters of electrolysis time, temperature, current density, initial
effluent's pH and electrolyte concentration addition of NaCl or Na2SO4 were
studied. The performance was evaluated by COD, total carbon, total phenols
and color removal and anode properties were studied by scanning electron
microscopy and cyclic voltammeter. The author’s concluded that the main
parameters affecting the process were the effluent's pH and the addition of
salts.

Arseto et al (2011), electrochemical oxidation was investigated for

the treatment of reverse osmosis concentrate generated during the reclamation
of municipal wastewater effluent. Five different anodes (titanium coated with
IrO2–Ta2O5, RuO2–IrO2, Pt–IrO2, PbO2, and SnO2–Sb) were evaluated for the
electrochemical oxidation of reverse osmosis concentrate in a batch reactor.
Concluded that the highest formation of trihalomethanes (THMs) and
haloacetic acids (HAAs) was observed for Ti/Pt–IrO2 and Ti/SnO2–Sb. Also,
 31

indirect oxidation by chlorine was a dominant oxidation mechanism for all

anodes.

Ilje Pikaar et al (2011) compared the performance of five different

mixed metal oxide (MMO) coated titanium electrode materials (Ta/Ir, Ru/Ir,
Pt/Ir, SnO2 and PbO2) for the electrochemical removal of sulfide from
domestic wastewater. All electrode materials performed similarly in terms of
sulfide removal (with ± 1% difference) at a constant current density. It
concluded that all the MMO coated titanium electrode materials studied are
suitable anodic materials for sulfide removal from wastewater.

Costa et al (2010) studied the electrochemical treatment of a

synthetic tannery wastewater with different type of anodes Si/BDD,
Ti/SnO(2)-Sb, and Ti/SnO(2)-Sb-Ir were evaluated. The level of organic
contaminant such as total phenols, COD, TOC and absorbance were measured
with the influence of pH and current density. Results showed different rate of
completion of process with anode type. The increase in current density
resulted in faster wastewater oxidation, with lower current efficiency and
higher energy consumption. In this aspect, Si/BBD proved to be the best
electrodic material for the direct electro oxidation of tannery wastewaters.

Sundarapandian et al (2010) studied the electrochemical treatment

of saline wastewater with organic load. The influence of the parameters such
as pH, period, salt concentration and current density on the reduction of
organic load was studied using graphite electrodes. It was found that current
density of 0.024 A/cm2 for a period of 2 h at pH 9.0 rendered best results in
terms of reduction in COD and TKN. The energy requirement for the
reduction of 1 kg of TKN and 1 kg of COD are 22.45 kWh and 0.80 kWh
respectively at pH 9 and 0.024 A/cm2. These experiments were reused at
commercial scale, on pickling process in leather manufacturing. The
 32

characteristics of the waste stream and the quality of the leathers indicate that
the reuse of saline streams with intermittent electrochemical treatment is
feasible.

Ahmed Basha et al (2009) investigated the electrochemical

degradation of various process stages such as soak liquor, tanning effluent,
and post-tanning effluent using Ti/RuOx-TiOx-coated titanium substrate
insoluble anode (TSIA). The treatment was found to be effective for the soak
liquor in almost complete mineralizing the organic part. A high percentage of
sodium chloride makes the process effective by improving the rate,
completion, and energy efficiency of the process. The optimal operating point
giving maximum COD removal (94.8%) was found using RSM at a
circulation flow rate of 142.8 L h-1, a current density of 5.8 A dm-2, and a time
of 7.05 h. The remaining salt in the process was further used in the post –
tanning stage.

Rameshraja et al (2009) reviewed the various oxidations and

combined processes in the treatment of tannery wastewater such as
UV/H2O2/Hypochlorites, Fenton and Electro-oxidation, photo-chemical,
photo-catalytic, electro-catalytic oxidation, wet air oxidation, ozonation,
biological followed by ozone/UV/ H2O2, coagulation or electro-coagulation
and catalytic treatments. For the tannery effluent with sulphide as main
sources of pollutant, electro-coagulation is the best removal process whereas
for chromium, photo catalytic oxidation process using nano-TiO2 and wet air
oxidation in the presence of manganese sulphate and activated carbon as a
catalyst are efficient processes.

Davood Nematollahi and Leila Mohammadi-Behzad (2009) studied

the electrochemical oxidation of catechol in the presence of 1, 10, diaza-18-
crown, 1,7-diaza-15-crown-5 and aza-15-crown-5 and also, in the presence of
some transition metal ions (Zn+2, Ni+2 and Cd+2) in acetonitrile containing
 33

tetra-n-butyl ammonium perchlorate as supporting electrolyte, by means of

cyclic voltammetry. The cyclic voltammetric data were analyzed by digital
simulation to confirm and to measure the homogeneous parameters for the
suggested electrode mechanism.

Dominguez et al (2008) described the electrochemical oxidation

using boron-doped diamond electrodes as an efficient alternative in the
treatment of biorefractory effluents. Total organic carbon (TOC) removal was
reported higher than 80 % under the selected experimental conditions, where
COD was in the range of 500- 1500 mg/l, current density was between 3 and
6 A/dm2, and the concentrations of sodium sulfate and sodium chloride
supporting electrolytes were 2500 and 5000 mg/l respectively. Experimental
conditions were selected to evaluate the technical suitability of the process
and to establish a kinetic model and parameters. A first-order kinetic model
and kinetic parameters are found out.

Saravanathamizhan et al (2008), attempted to study electrochemical

oxidation of formaldehyde at lower concentrations. Experiments were carried
out in a batch electrochemical reactor using commercially available RuO2
coated titanium and SS as anode and cathode respectively and covering a
wide range in operating conditions. It was observed from the statistical tool
(RSM) that the model predictions match well with experimental values with a
R2 value of 0.999.

Mohan and Balasubramanian (2006) experimented electrochemical

oxidation of textile dye wastewater using RuO2/Ti anode in batch
electrochemical reactor. The authors reported more than 90% COD removal
under optimum conditions. Later the authors (2007) attempted to reuse the
electrochemically treated textile effluent for dyeing application and reported
that the electrochemically treated wastewater can be effectively reused for
industrial application.
 34

Lidia Szpyrkowicz et al (2005) studied the influence of anode

materials Ti/Pt–Ir, Ti/PbO2, Ti/PdO–Co3O4 and Ti/RhOx–TiO2 on
electrochemical oxidation for the treatment of tannery wastewater. The
decrease in time of chemical oxygen demand, nitrogen (TKN and ammonia),
Cr and sulphides was monitored. The study showed that the rate of pollutant
removal was significantly influenced by the type of anode material and
electrochemical parameters. Electrochemical oxidation can be applied as a
post-treatment after the conventional biological process in order to remove the
residual ammonia with low energy consumption of 0.4kWhm-3 with rate of
0.75 min-1.

Marco Panizza et al (2004) investigated the electrochemical

oxidation of vegetable tannery wastewater as a tertiary treatment by using
lead dioxide (Ti/PbO2) and mixed titanium and ruthenium oxide (Ti/TiRuO2)
as anodes under different experimental conditions. In Ti/TiRuO2 anode, the
rate of tannery wastewater oxidation increased with operating parameters. The
results strongly indicate that electrochemical methods can be applied
effectively as a final treatment of vegetable tannery wastewater allowing the
complete removal of pollutant. Also, Ti/TiRuO2 was more stable and did not
release toxic ions, so it was the best candidate for industrial applications.

Canizares (2004) studied electro oxidation of 2, 4-dinitro phenol

using boron doped diamond electrode. The use of new anodic materials like
boron doped diamond electrode allowed to achieving higher efficiencies in
the use of electric energy and as a consequences to decrease the operating
cost.

Rao et al (2001) investigated the electrochemical treatment of

tannery wastewater using Ti/Pt, Ti/PbO2 and Ti/MnO2 anodes and a
Ti cathode in a two-electrode stirred batch reactor. The changes in color
 35

concentration, chemical oxygen demand (COD), ammonia (NH4+), sulfide and

total chromium were determined as a function of treatment time and applied
current density. The efficiency of Ti/Pt was 0.802kg COD h 1A 1m 2 and
0.270kgNH4+h 1A 1m 2, and the energy consumption was 5.77kWhkg 1 COD
and 16.63kWhkg 1 of NH4+. The order of efficiency of anodes was found to
be Ti/Pt Ti/PbO2>Ti/MnO2. The results indicate that the electro-oxidation
method could be used for effective oxidation of tannery wastewater and a
final effluent with substantially reduced pollution load can be obtained.

Juttner et al (2000) reported in their work that formation of active

chlorine is responsible for the oxidation of azo dyes. Azo dyes are commonly
encountered in leather and textile wastewaters.

Anna et al (1997) investigated the electrochemical removal of

2-chlorophenol and 2,6-dichlorophenol from aqueous solutions using porous
carbon felt anodes. Operating variables including current input, ratio of
electrode and solution volumes, and initial pollutant concentration were
considered in order to determine their influence on the faradic efficiency of
the process. The by-products of the oxidation reaction were identified, and
their concentration was determined during the electrolysis. The experimental
results showed a satisfactory detoxification, consisting of removal of cyclic
chlorinated compounds, could be accomplished by means of this
electrochemical method with a faradic efficiency of 30 % under optimized
conditions. A mathematical model based on the reaction between
chlorophenols adsorbed on the carbon fibers of the electrode and hydroxyl
radicals produced by anodic oxidation of water has been proposed to interpret
the experimental behavior of the system under different operating conditions.

Lidia Szpyrkowicz et al (1995) investigated the treatment of

tannery wastewater by the electrochemical method using Ti/Pt and Ti/Pt/Ir
 36

electrodes. The aim of a satisfactory elimination of NH+4 from wastewaters of

different strength was achieved using both types of electrodes. For both types
of the electrodes NH+4 removal followed pseudo first order kinetics, with the
rate decreasing in function of the presence of organic substances. In
conclusion the electrochemical process can be applied successfully as a final
polishing or an alternative to biological nitrification, but cannot substitute
completely the traditional treatment of tannery wastewater.

Table 2.1 Literature collection on organic effluent, EO, Reactor

configurations

Details of
Reference Inference
Elctrodes /Reactor
Titanium mesh coated with Effluents processed by EO
Vijayalaksmi
oxides of IrO2 , TaO2 and were found to be
et al (2011)
TiO2 was used as electrodes. completely disinfected.
Ahmed Basha Ti/RuOx-TiOx-coated Using Ti/TiRuO2 anode is
et al (2009) titanium anode most effective.

Comparing the overall

performance of basic
Soloman electrochemical reactor
et al (2009) configurations such as batch,
batch recirculation, recycle
and single pass systems
Compare overall
performance of the basic
Ahmed Basha electrochemical reactor
et al (2009) configurations such as batch, configuration, because of its
batch recirculation and
continuous recycle reactors
A recycle reactor was the
best configuration, because
of its flexibility of
operation.
Continuous recycle reactor
is found to be the better
flexibility of operation.
 37

Table 2.1 (Continued)

Details of
Reference Inference
Elctrodes /Reactor
Batch electrochemical It was observed that the
Saravanathamizhan reactor using commercially model predictions match
et al (2008) available RuO2 coated well with experimental
titanium values
Electrochemically treated
Batch electrochemical cell wastewater can be
Mohan et al (2007)
Ti/TiO2, RuO2 coated effectively reused for
dyeing application.
It has been observed from
Undivided electrode cell, the present analysis that
Saravanathamizhan
Different oxide coated the predicted values are in
et al (2007)
titanium metal anode. good agreement with
experimental data
The results indicate that
Ruthenium/lead/tin oxide the electrochemical
Mohan et al (2006)
coated titanium method can be used to treat
dye house effluents.
It is observed from the
present investigation that
Batch electrochemical the organic pollutant
Mohan et al (2001)
Cell, Ti / RuO2. present in the wastewater
can be oxidized by an
electrochemical technique.
 38

2.4 RESIDENCE TIME DISTRIBUTION

The residence time distribution (RTD) analysis of a chemical

process reactor is very useful information on flow characterization. It is
projected for investigation of hydrodynamic flows in chemical apparatuses on
the base of stimulus - response technique. The RTD study gives how long
each element spent inside the reactor, as a quantitative measure of the degree
of back mixing within the system.

The knowledge on RTD plays an important for accurate kinetic

modeling of the system, and help reactor design to achieve the desired flow
pattern. This technique includes the injection of a small amount of the tagged
inert particles (tracer) in the inlet stream and the observation of the
corresponding response in the outlet stream of an apparatus. A flow model is
then selected by matching the experimental RTD curve with that obtained
from the mathematical model. It provides the convenient interface and
powerful tools for: initial experimental data processing, creation model of the
flow in reactor with using the predefined flow patterns as the building blocks,
estimate the flow model parameters, simulate the system for the response to
the input signals of different types and creation of a user-defined flow
patterns. One of the functions in the tool is estimation expert; user can
estimate the best values for hydrodynamic flow models that are nonlinear in
the parameters. Estimation is done in time domain by the least square method.
The convolution approach is used to do that, calculate model output signal at
values of unknown parameters as model transfer function (in time domain)
and experimental input signal. Then it is compared with experimental signal.
Parameter values are changed to reduce the lack of fit and the process is
repeated automatically, if it is necessary.
 39

Egedy et al (2012) presented an algorithm based on qualitative

analysis that can be used to identify a compartment model structure based on
the results of physical experiments performed in a stirred reactor.
Furthermore, based on the compartment structure, dynamic simulation CFD
can be applied to identify and validate the unknown model parameters of the
compartment model. The most important aspect of this study is that a suitable
structure identification algorithm was created, and tested. The author
concluded from the study, the developed algorithm engineers can make
various compartment models which, can be used for on-line control,
engineering design and modeling systems at a more detailed level. Also, in
the future the algorithm will be improved to identify more complex structures,
and the basic compartment models will be extended to handle more
compartment classes such as dead zone.

Bahadori et al (2012) studied full-scale plug-flow reactors, in PFR,

the flow usually is non-ideal because of entrance and exit flow disturbances
and axial dispersion. To facilitate the design of treatment processes authors
have developed an analytical for plug flow reactors with dispersion numbers
varying from complete-mix to ideal plug-flow reactor. Also, a simple-to-use
method which is easier than existing approaches, less complicated with fewer
computations, for accurate and rapid estimation of effluent and influent
concentration ratios in plug flow reactor (percent remaining) as a function of
plug flow dispersion factor (from zero to infinity), first order reaction constant
and hydraulic detention time. The error between model and experimental data
were found to be 1.8%.

Militaru et al (2011) developed a mathematical model for

hydrodynamic behavior in the water treatment pilot plant equipments and it
has been validated by Residence Time Distribution (RTD). The author
combined the well known non–ideal flow models of real mixing
 40

(Cholette-Cloutier) and axial dispersion in order to identify models structure

that gives the best fitting of the experimental data for each unit. Further, the
validated hydrodynamic models used in the evaluation and selection of the
process and optimum operating conditions, in order to improve process
economics and drinking water quality.

Saravanathamizhan et al (2010), Described the electrolyte flow

behaviour in the parallel plate electrochemical reactor by residence time
distribution models. The author used different models include single tank and
two/three tanks in series. The exit age distribution curves obtained under
various operating conditions was analyzed and compared with experimental
observations. Finally, the results predict that single CSTR model closely
matches with three tanks in series model with the volume ratio 1:18:1.

Capela et al (2009) studied the hydrodynamic characteristics of a

full-scale anaerobic contact reactor treating evaporator condensate from a
sulphite pulp mill. The methodology applied was based on the RTD technique
using lithium as a tracer. Different non-ideal hydraulic flow models were
tested and the best model fitting RTD data was the Gamma distribution model
with by-pass. It was concluded that the full-scale bioreactor presents a good
degree of mixing with about 22% of non-effective volume due to the presence
of high amounts of inorganic materials.

Wang et al (2009), recognized from the literature the flow profile

and hydraulic conditions of Membrane Bioreactor (MBR) that predicts the
performance of design was not evolved. The author used a concept of RTD to
characterize the hydraulic conditions in MBR. The technique would be used
as a tool to determine the impact of membrane geometry, orientation and
mixing efficiency on MBR performance. Lithium chloride was used as a
tracer to generate the RTD profile. The ‘‘Tanks-in-Series’’ model was used to
simulate the performance of a pilot plant MBR. However, it was found that
 41

experimental RTD profiles could not be reproduced with this simple model
and conclude that a more fundamental approach, based on computational fluid
dynamics is needed to model the hydraulic behaviour in MBR’s.

Jones et al (2008), Studied the variations in CSTR feed geometry,

impeller speed and inlet flow rate through the residence time distribution.
The measured RTD also used to characterize the degree of plug flow
behaviour and short-circuiting. Using the ratio of the mean residence time to
the batch mode mixing time (t/tM) could not evaluate the performance of a
CSTR. Moreover, this approach can lead to process overdesign and excessive
energy requirements. Instead, it was shown that all process parameters can be
correlated using the ratio of the inlet jet momentum to the impeller discharge
momentum. The prediction of the degree of short circuiting and plug flow in
the CSTR could be used to improve process control. In addition, the results
can be used to identify the design of CSTR (inlet position or diameter) should
be modified to improve process performance.

Saravanathamizhan et al (2008) studied the electrolyte flow

characteristics in a Continuous Stirred Tank Electrochemical Reactor
(CSTER) using RTD. A three-parameter model has been developed to explain
the flow characteristic of electrolyte in a continuous stirred tank
electrochemical reactor and the model simulations are validated with the
experimental observations. From the model simulations, it explains that the
residence time distribution has been increased with increase in the exchange
flow ratio between active and dead zones and increase in the electrolyte flow
rate. Further the experiments were carried out for the effluent color removal
and the values are compared with theoretically calculated value and it is
observed that the values are satisfactorily matching with experimental
observations.
 42

Lifeng Zhang et al (2007), studied the RTDs in a multistage

agitated contactor (MAC) for Newtonian fluids and presented a suitable
Computational Fluid Dynamics (CFD) simulation. The resulting mean
residence times and variances via the CFD simulation were in good
agreement with the experimental data. Various liquids are used to simulate the
RTD under different flow conditions. The simulation results show that a
cascade of stirred tanks with a back flow CTB model is more suitable to
describe the flow behavior in a MAC with few stages than an axial dispersion
model.

Qingfeng Yang et al (2007), used to diagnose the flow

characteristics in spiral wound Reverse Osmosis (RO) modules by RTD
techniques. In usual procedure, the steps (conductivity-concentration
transformation, baseline selection and the use of exit age distribution function
of Et, or dimensionless exit age distribution function of E ) in processing
tracer response conductivity and modeling of RTD curves often involve
complicated steps. In this study author developed a simple and direct method
for processing RTD signals from conductivity data for spiral wound
membrane RO system. Further, the direct method was tested using axial
dispersion (AD) model and Exponentially Modified Gaussian (EMG) model
and it shows that the present method provides a simple, fast and accurate RTD
data reduction.

Andre et al (2007), studied the RTD for industrial indirect Joule

Effect Heaters (JEH), with Smooth (ST) and Modified (MT) tubes to improve
treatment homogeneity in heated vessel used in food industry. Demonstration
and quantification of the efficiency of the geometrical modifications, and
Proposition of a single semi-empirical model including the flow regime (10 <
Re < 2000) and tube diameters (18 and 23 mm). The results obtained confirm
that the simple Dispersed Plug Flow (DPF) model is not adaptable to small
 43

Reynolds numbers. Additional analysis demonstrate that certain geometrical

modification improve the treatment homogeneity by increasing the plug flow
contribution and reducing the value of the reduced variance. These beneficial
effects increase when the Reynolds number is increased, the nominal diameter
is reduced, and modified tubes were used. The proposed model enables the
prediction of the RTD in JEH with an accurate degree of confidence.

Polcaro et al (2007) studied the water disinfection processes in a

stirred tank electrochemical reactor using boron doped diamond electrode and
developed a model for E(t) distribution for a pulse input considering two
CSTRs in parallel

2
Q Q (1 )2 Q (1 )Q
E(t) exp t exp t (2.1)
V V (1 )V (1 )V

represents the fraction of the total flow rate fed to a fraction of the
total volume V. The authors observed deviation from the ideal behavior for
low Reynolds number.

Lidia and Marta (2006), have reported the treatment of textile

effluent of reactive dye Red Procion H-EXGL using electrochemically
generated redox mediator in a filter press cell and developed a model for exit
age distribution E(t) was,

N 1 t M M 1 t
1 NN N t N 1 M t M
E(t) f e t
(1 f) e t
(2.2)
t (N 1)! t t (M 1)! t

where, M, N, f and is a function of flow rate. The authors observed that the
electrolyte flow behavior was close to plug flow and compared the
decolorization of the dye using experimental and exit age distribution model.
 44

Achim Heibel et al (2005) introduced an experimental method and

data analysis procedure to determine the liquid RTD of monoliths based on
the imperfect pulse injection of a dye tracer. Both the experimentally
determined liquid saturations values and predictions of CFD calculations, fits
well. Despite the reasonable agreement for the mean residence time the CFD
model based on uniform liquid distribution over the monolith channels and
the individual channel corners failed to describe the experimentally
determined reduced RTD curves. The authors go for a measured corner-scale
liquid distribution pattern in combination with the CFD model resulted in
good agreement with the experiments. Furthermore, this approach also
improved the agreement between measurement and model for the mean
residence time.

Bang Cheng Xu et al (2005), determined interstage back mixing

rates in an agitated, fully baffled, two-stage, compartmented column. The
back mixing rate was indirectly determined by introducing a tracer into one
stage and then measuring the tracer concentration with time in both
compartments as the tracer migrated from the injected stage to the noninjected
stage. The effect of flow through the column on interstage back mixing was
determined. The data were correlated in dimensionless form, and predictive
methods are presented that allow the prediction of the interstage back mixing
rate as a function of the impeller type, fluid properties, the interstage opening
geometry, and the forward flow rate. The correlations for the effect of the
forward flow rate on back mixing allow the design of a compartmented
column, using a draft tube attached to a center hole opening, which has no
back mixing. Concluded that, a compartmented column can be designed and
operated as a series of continuous stirred reactors (or compartments) in series,
without any interstage back mixing.
 45

Andrade Lima and Hodouin (2005) have reported the residence

time distribution of electrolyte in a gold leaching tank. The author used
lithium chloride as a tracer and modeled the flow behavior in the tank consists
of two parallel streams single perfect mixed reactor and another consisting of
n perfect mixed reactors in series with by-pass.

David Olivet et al (2005), investigated the hydrodynamic behaviour

of a bioreactor treating municipal wastewater, through RTD technique using
lithium (chloride) as tracer. Different non-ideal models (namely axial
dispersion, tanks-in-series and some simple compartment models) were tested
for the modeling of the experimental RTD. The best model fitting RTD data,
tanks in series. The author observed that, the system under study, local RTDs
have been used for the qualitative determination of particular situations of
insufficient mixing, recirculation or channeling and the type of flow (plug,
dispersed or mixed) rather than global RTD. From the study the author
concluded that, local RTDs have permitted a qualitative description of the
hydraulic behaviour of the bioreactor

Olivier Potier et al (2005), performed RTD experiments in a

activated sludge 3000m3 channel reactor aerated by gas diffusion (for
different liquid flow rates under constant aeration rate and constant water
depth) and on a benchscalechannel reactor aerated from the bottom (for
different liquid and gas flow rates and water depths) in order to characterize
their hydrodynamics. Both units can be modeled as plug flow reactors with
axial dispersion. A general correlation has been obtained to predict the axial
dispersion coefficient as a function of the gas and liquid velocities and the
geometrical parameters of the full-scale and bench-scale reactors. Finally, to
facilitate the simulation of biological reactions in transient state, an equivalent
model based on tanks-in-series with variable back-mixing flow rate is
proposed.
 46

Dudukovic (2004), discussed about the many models of non-ideal

reactors, cholette –coultier model are discussed in detail. Effect of dead
space, stagnancy, macromixing etc with impulse response is critically
discussed.

Hardin et al (2001) studied the residence time distribution of a

tracer gas (carbon monoxide) through a rotating drum bioreactor for
solid-state fermentation. The exit concentration profiles expected for plug
flow, plug flow with axial dispersion, and Continuous Stirred Tank Reactor
(CSTR) models. Model parameters were the dispersion coefficient in the
central plug flow region, the volumes of the dead regions, and the exchange
rates between the different regions. The superficial velocity of the gas through
the reactor has a large effect on parameter values. Increased superficial
velocity tends to decrease dead region volumes, inter region transfer rates,
and axial dispersion. The significant deviation from CSTR, plug flow, and
plug flow with axial dispersion of the residence time distribution of gas within
small-scale reactors can lead to underestimation of the calculation of mass
and heat transfer coefficients and hence has implications for reactor design
and scale up. The author’s concluded that, proper estimates of the driving
force will lead to a better understanding of mass transfer in moving beds of
particles with concomitant benefits not only in SSF with RDBs, but also in
non-SSF applications of rotating drums, such as drying and calcining.

Bengoa et al (2000), studied the hydrodynamics behavior in the

laboratory-scale commercial filter-press electrolyzer by flow visualization and
RTD. The direct visualization studied both divided and undivided modes,
with two injection points. The use of foams instead of turbulence promoters
as well as that of electrodes without turbulence promoters is tested. In the
membrane-partitioned mode, radial and axial dispersions are observed.
Dispersion is drastically extended in case of empty channel flow. A flow
 47

distributor helps to high-flow asymmetry. RTD is implemented in the whole

cell and in the reaction area. The reactor working with a plane plate alone
gives a rather constant, low Peclet number, Pe, whatever the tested flow rates.
The low Pe values denote an important axial dispersion. The Pe increasing
significantly with turbulence promoters or foams, giving plug flow character.

Martin (2000) presented an alternative method for interpreting RTD

data, which is relatively easy to use and addresses some of the weaknesses of
more conventional methods. An extension to the tanks in series a concept was
used (ETIS) and combined with the reactor network formulation. The
suitability and appropriateness of the model is discussed and compared with
the closed dispersion model. It gives the model in conjunction with the reactor
network structure to be a versatile method of describing the characteristics of
a small but diverse group of reactors. The ETIS model has been compared
with the conventional tanks in series approach and has been found to be
superior.

Jose Gonza lez-Garc a et al (1998), studied the optimization of the

ratio between felt / compartment thickness of a three-dimensional electrode
by different techniques to get good flow dispersion, and good electrode
conductivity. Nevertheless, the RTD analysis gives information about the
hydrodynamic behavior of the system. This analysis yields an optimum ratio
close to 10/8. In these conditions, a dispersed plug-flow model, with almost
no dead zones, can represent the hydrodynamic behavior obtained. It is also
expected that no accumulation or retention of the liquid or gas phase inside
the reactor, due to its hydrodynamic behavior. The authors in 2002 have
reported the hydrodynamic behaviour of electrochemical reactors by
simulating stimulus–response experiments. The experiments were performed
with a simple experimental arrangement to generate RTD data from
electrolytic conductivity measurements. The multiparametric model proposed
 48

and the Matlab program developed for electrochemical reactors, providing

values of porosity and compressibility parameters. This also permits modeling
of the electrochemical reactions that will be produced during the process.

David Wolf and William Resnick (1963), studied the measurement

and analysis of residence time distribution of continuous flow systems.
A study of available experimental data shows that the usual assumptions of
perfect mixing or plug flow do not correspond to the situation existing in real
flow systems. The residence time distribution for real systems can be
represented by an F-function

t
F(t) 1 exp for t (2.3)
9

F(t) 0for 0 t (2.4)

This equation results for a number of possible flow models that

include the additional possibilities of dead space, short-circuiting, error in
average residence time determination, and lag in response and any
combination of these models. This equation can be used to describe the
experimental results obtained far single as well as multistage systems.

2.5 ELECTROCHEMICAL REACTORS

Different types of electrochemical reactors ranging from conventional

plate and frame cell to advanced electrodes such as three-dimensional electrodes
are used for electrochemical processes (Saravanathamizhan et al 2008). The
design or selection of suitable electrochemical reactor is very important in
electrochemical process as the reactor geometry plays an important role in the
process yield. Extensive work has been reported on the analysis of
performance of various electrochemical reactors. Bengoa et al (1997) studied
 49

the flow behavior of electrolyte in a filter press type electrochemical reactor

and reported residence time distribution using a commercial ElectroSyn cell.

2.5.1 Rotating Disk Electrode

The RDE is an extremely valuable method for characterizing

electrochemical reactions, mass transfer rate. RDE is a hydrodynamic
electrode system. The electrode rotates during experiments enhancing the
mixing of the effluent thereby increasing the rate of mass transfer. The RDE
reactor is an important investigational device because one can study the
effects of both convection and diffusion and its effects on chemical reactions.
This will aid in understanding the physical phenomena involved and
eventually lead to better equipments based on RDE; as a result it finds many
applications in electro synthesis, electro winning, electro oxidation, corrosion
detection etc. Ajith Wijayawardhana et al (1999) find application of RDE in
immune assay experiments. Thus the applications of RDE are practically
limitless.

Antonio Chaparro (2011) recently used rotating disc electrode to

study the electro catalysis. The authour studied the spillover effects of
catalysts on electrochemical reaction. Wojtowicz et al (1967) studied the
construction and operation of rotating disc electrode at high temperature.

Cesar Real-Ramirez et al (2010) said that electrochemical cells with

a rotating disc electrode are the preferred devices to characterize
electrochemical reactions. The three-dimensional numerical simulations of the
cell hydrodynamic behavior presented in this work shows that the fluid flow
pattern inside the cell was erroneously interpreted (Blurton and Riddiford
1965).
 50

Pascal Viel et al (1999) studied the electro polymerization of

methacrylonitrile on a high spinning rotating disc electrode. Also, studied the
convection effects near and away from the electrode and concluded that
polymer film is initiated near the electrode region, rather than in the bulk
solution

Blurton et al (1959) described the shapes of many practical rotating

disc electrodes. Mass transfer and fluid flow in near disc regions were studied
and also opined that fluid flow below the working surface of the disc
electrode shall not interact with that in the upper region.

2.6 RESPONSE SURFACE METHODOLOGY

In conventional multifactor experiments, optimization is usually

carried out by varying a single factor while keeping all other factors fixed at a
specific set of conditions. It is not only time-consuming, but also usually
incapable of reaching the true optimum due to ignoring the interactions
among variables. On the other hand, the RSM has been proposed to determine
the influences of individual factors and their interactive influences. The RSM
is important in designing, formulating, developing, and analyzing new
scientific studying and products. It is also efficient in the improvement of
existing studies and products.

According to Hill and Hunter, RSM method was introduced by

G.E.P. Box and K.B. Wilson in 1951. Box and Wilson suggested to use a
first-degree polynomial model to approximate the response variable. Mead
and Pike stated origin of RSM starts 1930s with use of Response Curves
(Myers et al 1989).
 51

One of the important facts is whether the system contains a

maximum or a minimum or a saddle point, which has a wide interest in
industry. Therefore, RSM is being increasingly used in the industry.

Statistical analysis widely used in various fields, dye removal by

absorbent (Ravikumar et al 2006), Biosorption of dye (Pavan et al 2007),
Fenton’s peroxidation on the removal of organic pollutants from olive oil mill
wastewater (Ahmadi et al 2005), decolorization of dye using enzyme
(Murugesan et al 2007), and nickel plating process (Oraon et al 2006).

Barbara Bianco et al (2011) studied the experimental factorial

analysis on wastewaters samples taken from a real treatment plant in different
periods, were used to construct a model response function to be applied in
operative conditions. The second-order model was modified to include the
initial COD as an independent variable in order to account for the wide range
of initial COD in the treatment plant. The regression gives an excellent
quantitative agreement between the predicted and measured values of COD
for different experimental conditions. For the optimum condition, the removal
of 80% COD was obtained.

Bahadir Korbahti (2007) studied the electrochemical degradation of

Levafix Blue CA, Levafix Red CA and Levafix Yellow CA reactive dyes in
textile dye wastewater using iron electrodes. The effect of operating
parameters on COD removal, dye removal and turbidity removal was
optimized using RSM, and the approximating functions of dye removal were
obtained with satisfactory degrees of fit (R2=0.93).

Arul Murugan et al (2009) studied the electrocoagulation of Acid

Blue 113 textile effluent in a batch electrochemical reactor covering wide
range of operating conditions. Experiments were designed using Response
 52

Surface Method (RSM) to examine the combined effect of operating

parameters on the efficiency of electro coagulation process.

Saravanathamizhan et al (2008) studied electrochemical oxidation

of formaldehyde at lower concentrations. Experiments was carried out in a
batch electrochemical reactor using commercially available RuO2 coated
titanium and SS as anode and cathode respectively and covering a wide range
in operating conditions. Further, the statistical tool Response surface
methodology by Box-Behnken design was used to examine the influence of
individual parameters on electro-oxidation of formaldehyde, and the quadratic
model for formaldehyde removal efficiency was derived. It was observed that
the model predictions match well with experimental values with a R2 value of
0.999. Further, the author in (2007) studied the electrooxidation of textile
effluent using Response Surface Methods, electrochemical technique was
designed and analyzed using the Box-Behnken method. The influence of
individual parameters on electro-oxidation of textile effluent was critically
examined by author using the response surface method (RSM), and a
quadratic model for chemical oxygen demand (COD) reduction was
developed. The authour observed from the analysis that the predicted values
are in good agreement with experimental data with a correlation coefficient of
0.945.

It is observed from the literature that, though there are good amount
of work on electrochemical reactor, very few are on RTD. Hence, it is
proposed to study the RTD of electrolyte in Rotating disc electrochemical
reactor and extend the data for CFD simulation. Further, no literature is
available for RSM tool in RDE reactor. With help of this optimization tool,
lab scale reactor is to be scaled up into a pilot scale reactor. It is strongly
believed that the outcome of the research will have a real social and
commercial value.