INTERNATIONAL JOURNAL OF DESIGN AND MANUFACTURING TECHNOLOGY (IJDMT) · 2014-03-05 ·...

International Journal of Design and Manufacturing Technology (IJDMT), ISSN 0976 –

6995(Print), ISSN 0976 – 7002(Online) Volume 4, Issue 2, May - August (2013), © IAEME

21

MEMBRANE ASSISTED ELECTRO CHEMICAL DEGRADATION

FOR QUINOLINE YELLOW, EOSIN B AND ROSE BENGAL DYES

DEGRADATION

B. Chirsabesan and M.Vijay*

Department of Chemical Engineering, Annamalai University, Annamalai Nagar,

Chidambaram -608002, India

ABSTRACT

Industrial waste often contains a mixture of organic and inorganic compounds, in

addition to solid or soluble material, and because of this diverse feature no universal

strategy of remediation is feasible. In the present study, Quinoline Yellow, Eosin B and Rose

Bengal model dye were chosen and its characterization was done by measuring pH, EC, TDS,

COD, and Color etc. Degradation studies of Quinoline Yellow, Eosin B and Rose Bengal

model dye was carried out with Membrane assisted electro chemical degradation cell in

specially designed reaction vessel in the electro membrane reactor equipped with poly

electrolyte membranes. Experiments were performed in four poly electrolyte membranes

(PEM) such SPES, SPSf, SPEEK and Nafion at optimized condition. The SPES, SPSf,

SPEEK were prepared with different ion exchange capacity. The dyes degradation were

compared with commercial Nafion commercial PEM membranes.

Key words: Quinoline Yellow, Eosin B, Rose Bengal Quinoline Yellow, Membrane assisted

electro chemical degradation, decolourization of dye.

1. INTRODUCTION

Industrial waste often contains a mixture of organic and inorganic compounds, in

addition to solid or soluble material, and because of this diverse feature no universal

strategy of remediation is feasible. As to the treatment of effluents polluted with organic

compounds, biological oxidation is the cheapest process, but the presence of toxic or bio-

refractory molecules may hinder this approach. It is important to design (or select) an

electrochemical reactor for a specific process, and it is clear that reactors for energy

conversion and electrochemical synthesis will have different drivers to those used in the

INTERNATIONAL JOURNAL OF DESIGN AND MANUFACTURING

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ISSN 0976 – 6995 (Print) ISSN 0976 – 7002 (Online)

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destruction of electrolyte-based contaminants. Adequate attention must be paid to the form of

the electrode, its geometry and motion, together with the need for cell division or a thin

electrolyte gap. However, some limitations are there in electrochemical technology such as

relatively few “showcases” for the technology, shortage of experienced electrochemical

engineers, Chemical reactions, corrosion, adsorption, etc., at electrode surfaces can cause

complications, Damage to electrodes via, e.g., corrosion and fouling, can restrict performance

and longevity. Ion-exchange membranes can play a critical role in electrochemical reactors, it

provides high surface area electrodes, acceptable cost, lifetime, and practicality of electrodes

and membranes, low potential drop over electrodes and membranes, membranes that are

selective to a particular ion and low solvent transport rate through membranes.

Textile Printing and dyeing processes include pretreatment, dyeing / printing, finishing and

other technologies. Pre-treatment includes desizing, scouring, washing, and other processes.

Dyeing mainly aims at dissolving the dye in water, which will be transferred to the fabric to

produce colored fabric under certain conditions. Printing is a branch of dyeing which

generally is defined as ‘localized dyeing’ i.e. dyeing that is confirmed to a certain portion of

the fabric that constitutes the design.

Table 1 The scope for electrochemical technology in environmental treatment

� Avoidance of pollution

clean electro

synthesis

� Recycling of valuable materials

precious metal deposition

� Remediation of polluted sites

soil remediation by electrodialysis

� Monitoring and sensors

in the gas and liquid phase

� Efficient energy conversion

fuel cells and redox flow cells

� Avoidance of corrosion

choice of materials/protective coatings

� Removal of contaminants

metal ion, organics, and inorganics removal from water and process

liquors

� Disinfection of water

chlorination, peroxy species, or ozone

Effluent from textile mills also contains chromium, which has a cumulative effect,

andhigher possibilities for entering into the food chain. The scope of electrochemical

technology in environmental treatment is shown in Table 1. Due to usage of dyes and

chemicals,effluents are dark in color, which increases the turbidity of water body (Joseph and

Egli, 2007). Adsorption techniques have recently gained a considerable importance due to their efficiency in the removal of pollutants too stable for conventional methods (Robinson et

al. 2001, Aksu 2005). Most adsorbents are not equally effective towards different types of

dyes (van der Zee 2002). Membrane technology has emerged as a feasible alternative to

conventional treatment processes of dye wastewater and has proven to save operation costs

and water consumptions by water recycling. Usually this technique is applied as a



23

tertiary/final treatment after biological and/or physical-chemical treatments (Ciardelliet al.

2000, Marcucciet al. 2002). Electro oxidation of organic compounds in aqueous solution can

be obtained without electrode fouling by performing electrolysis at high anodic potentials in

the region of water discharge due to the participation of intermediates of oxygen evolution.

This process results in partly conversion or full mineralization of the organics, does not need

to add oxidation catalysts to the solution and does in principle not produce any by-products.

The decontaminated solutions showed no mutagenicity towards Salmonella

typhimurium(Lunn and Sansone, 1991). In literature, it is reported that AOP using Fenton’s

reagent can reduce the eosin concentration of 678 mg/l by 20% in 1hwhen treated with 278

mg/l FeSO4·7H2O and 3400 mg/l hydrogen peroxide. The results showed that anionic

surfactants performed significantly better than a cationic one during the desorption of

anionic dyes Eosin (Purkait et al).Quinoline yellow (QY) is also another food colorant.

Different techniques such as adsorption, oxidation, reduction, electrochemical and membrane

filtration are applied to remove these pollutants from the industrial effluents. Oxidation

processes are widely used both in industrial preparations and in environmental treatments.

Karacakaya and colleagues (2009) investigated the removal capabilities of Synechocystis sp.

And Phormidium sp. The pseudo-second order kinetic model (PSOM) is widely used because

of the simplicity of applying its linear form and the general applicability to adsorption kinetic

data (Ho and McKay 1999). However, the models with simple expressions are more favored

(Levenspiel 2002; Gonzo and Gonzo 2005). Among all the models used in adsorption kinetic

studies, pseudo-first order model (PFOM) and PSOM were frequently applied (Ho and

McKay 1999). However, as yet, there has not been a method employing the electrochemical

oxidation process combined with the membrane filtration process for the treatment and reuse

of textile dyehouse wastewater. The goal of this research is to study the performance of the

arc-shaped transfer-flow membrane module, at the same time, to demonstrate these processes

and to develop a potential dye wastewater treatment system for reuse.

2. MATERIALS AND METHODS

Textile dye Quinoline Yellow, obtained from pollution control division, Central

Electrochemical research Institute, Karaikudi, Tamilnadu.PES (3500) was received from

Udel. Eosin B dye (4´,5´-Dibromo- 2´,7´dinitrofluorescein di sodium salt, colour index:

45400), chloroform, chlorosulfonic acid,methanol, and dimethylformamide (AR grade) were

obtained from S.D fine Chemicals, India, and were used without any further purification. The

Characteristics of organic dyes are shown Table 2. Fungal strain Corialusversicalor ((MTCC-

138)wasobtained from microbiology laboratory, Bharathidasan University, Trichy and used

for the study.

2.1. Dye Effluent Preparation

Dye concentration selected for experiments was 200 mg/L. This value is included in

the range of real dye concentration found in textile effluents. Synthetic Quinoline Yellowand

Eosin B dye bath effluent used in the present study was prepared according to the

composition commonly used in cotton dyeing. In order to dye 0.1kg of fabric, 0.004 kg of

dye is used. It is dissolved in 1 L of double distilled water along with the auxiliary chemicals

such as 0.003 kg Na2CO3, 1 mL of NaOH 38°Bé (441×10-3

kgm-3

NaOH solution)and0.01kg

of NaCl.



24

2.2 Electrochemical process

The electric current induces redox reactions resulting in the transformation and

destruction of the organic compounds and almost complete oxidation to CO2 and H2O.

Table 2: Characteristics of organic dyes

The oxidation of pollutants in an electrolytic cell can occur through the following

processes:

Anodic oxidation: This refers to processes in which an electron transfer reaction of the

desired pollutant occurs at the surface of the anode. The electrode reactions involving the

degradation of organic compounds are given by Equations 2.1 and 2.2. The potential required

for the oxidation of organic compounds is usually high and collateral reactions such as water

electrolysis are inevitable.

M + H2O→M (HO•) + H

++ e

− (2.1)

M (HO•) + R→M + CO2 + H2O + H

++ e

− (2.2)

where M is the electrode and R is the organic compound.

Cathodic reduction: Electro reduction of textile wastewater with azo dyes was also

reported. The reductive cleavage of the azochromogene leads to a decrease in the specific

absorbance of the dye without the addition of chemicals or formation of sludge.

Indirect oxidation: This process relies on the electrolytic generation of strong

oxidising agents. The action of these oxidizing species leads to total or partial

decontamination, respectively. When NaCl is used, the electrode reactions to indirect

degradation of organic compound proceeds as follows:

2Cl−−→Cl2 + 2e

− (2.3)

Cl2 + H2O→H++ Cl

− + HOCl (2.4)

HOCl→H++ OCl

− (2.5)

R + OCl−−→CO2 + H2O + Cl

− (2.6)

where: R is the organic compound.

Name of Dyes Class of dye

(ionic type)

Mwt

gm/gmol

Chemical

structure ��max

(nm)

Quinoline Yellow

Colour Index No.:

47005

Quinoline

(anionic)

375.3 C19H11N1Na2O8S2 411

Eosin B

(disodium salt)

CI Number:

45400

Xanthene

(anionic)

580.09 C20H6N2Na2O9Br2 514



25

The main advantages of using these electrochemical methods include that they do not

consume a significant amount of chemicals, nor do they produce sludge. Additionally, the

processes are commonly performed at room temperature and atmospheric pressure, thus

avoiding the undesirable volatilization and discharge of untreated residues.

By means of electrochemical oxidation, pollutants in wastewater can be completely

mineralised by electrolysis using high oxygen over-voltage anodes such as PbO2 and boron-

doped diamond. Polcaro et al. (1999) studied the performance of the Ti/PbO2 anode during

electrolysis of 2-cholorophenol in terms of faradic yield and fraction of toxic intermediates

removed.

2.3. Membrane Separation Process

Membrane-wet oxidation, an integrated process, has been demonstrated by Dhale and

Mahajani (2000) to treat the disperse dye bath waste. On the other hand, these techniques do

not eliminate definitively the dyes but only separate and concentrate them. The destruction of

the concentrated pollutants requires an additional operation as incineration. However,

electrochemical processes that use hydroxyl radicals, a very strong oxidant to destroy

compound that cannot be oxidized by conventional oxidant. An advanced oxidation method

is a result of their high potential. The chain mechanism of oxidation, which involves hydroxyl

and hydroperoxide radicals guarantees efficiency and quick rate of the process. The high

reactivity and low selectivity of the reaction enable the method to be applied to a large

number of organic compounds present in the wastewater. Further advantages include a lack

of by-products, which can produce secondary pollution of the environment and thus risk over

dosage of the oxidizing agents

2.4. Membrane assisted electrochemical oxidation techniques for degradation of dye

effluents

Electrochemical oxidation has a high COD removal efficiency (89.8%) of the textile

wastewater while membrane filtration can almost totally remove TSS (nearly 100%

reduction) and turbidity (98.3% elimination) in it. The traditional single-chamber

electrochemical method used in the wastewater treatment mainly focuses on anodic

oxidation, but hydrogen is produced on the cathode, which also consumes much energy, is

often ignored. The simultaneous production of evolved hydrogen at a cathode as a

byproduct, along with high power requirements is the main disadvantage for electro-

oxidation of organics. In this work, an innovative two-chamber electrolytic cell, connected

with an anion exchange membrane, was developed. In this new reactor, indirect oxidation at

anode, indirect oxidation by hydrogen peroxide and UV/H2O2 at cathode can occur

simultaneously. Therefore “dual electrodes oxidation” in one electrochemical reactor was

achieved successfully. Compared to a traditional one cell reactor, this reactor considerably

reduces the energy cost by 25–40%, and thus the present work becomes significant in

wastewater treatment for dye effluents.

Electrochemical oxidation of dye solution was carried out in electrochemical cell.

Anode and cathode were Fisher platinum electrodes. The volume of solution to be treated

was 400 mL and the effective electrode area was 25 cm2. The homogeneous nature of the

medium during the electrolysis was maintained using magnetic stirring. The electrolysis cell

used in the present study consists of a glass beaker of 500 ml capacity closed with a PVC lid

having provision to fit a cathode and an anode (surface area of the electrode19.5 cm2). Anode

was ruthenium coated on titanium metal (RuOx–TiOx) (expanded mesh type) and cathode

International Journal of Design and Manufacturing Technology (IJDMT), ISSN 0976

6995(Print), ISSN 0976 – 7002(Online) Volume 4, Issue 2, May

was stainless steelplate. The current was supplied by multi

source (with ammeter and voltmeter).

Figure 1: Schematic diagram of electrochemical reactor employed for dye degradation

Schematic diagram of electrochemical reactor

in Figure 1. Electrochemical reactor was made of PTFE and divided into an anode

compartment (AC) and cathode compartment (CC) by PEM (8.0×10

pumps were used to move each stream, while an adjustable dc power supply (model L 1285,

Aplab, Mumbai, India) was used to apply constant potential gradient. NaOH concentration in

the CC was also monitored regularly. In all cases, equal v

study the feasibility of the separation process. Build

determined by acid-base titration using phenolphathalein indicator.

were analyzed by UV-Vis spectrometry at m

calibration curve (Figure1) and dyes removal was obtained following equation

Dyes removal (%) = 1-

2.5. Preparation of Polymer Electrolyte Membrane

2.5.1. Preparation of sulfonated poly

Polyethersulfone (Gadone TM 3400 was sulfonated as per the procedure developed

by Chen et al., (1996). Poly ether sulfone 40g was dissolved in 1,2

the solution at a temperature of 85

and 5 ml of chlorosulfonic acid was added drop wise to the solution for about 15 minutes. This

reaction mixture was maintained at 4

sulfone obtained was precipitated

dried in vacuum for 1-2 h at 40°C.

al Journal of Design and Manufacturing Technology (IJDMT), ISSN 0976

7002(Online) Volume 4, Issue 2, May - August (2013), © IAEME

26

inless steelplate. The current was supplied by multi-output 2 A and 30 V, DC power

source (with ammeter and voltmeter).

Schematic diagram of electrochemical reactor employed for dye degradation

Schematic diagram of electrochemical reactor employed for dye degradation is depicted


compartment (AC) and cathode compartment (CC) by PEM (8.0×10-3

m2). Two peristaltic



the CC was also monitored regularly. In all cases, equal volumes of AC and CC were taken to

study the feasibility of the separation process. Build-up of NaOH concentration in CC was

base titration using phenolphathalein indicator. The dye concentrations

Vis spectrometry at maximum wavelength (λmax = 517 nm) using

calibration curve (Figure1) and dyes removal was obtained following equation

(C1/C0) × 100

Preparation of Polymer Electrolyte Membrane

Preparation of sulfonated poly (ether sulfone)


by Chen et al., (1996). Poly ether sulfone 40g was dissolved in 1,2-dichloroethane by heating

the solution at a temperature of 85°C ± 5°C, for 2-3 h. The solution was then cooled to 4


reaction mixture was maintained at 4°C for 2 h. The solid sodium salt of sulfonated poly ether

sulfone obtained was precipitated in ice cold water followed by treatment with methanol and

C.

al Journal of Design and Manufacturing Technology (IJDMT), ISSN 0976 –

August (2013), © IAEME

output 2 A and 30 V, DC power

Schematic diagram of electrochemical reactor employed for dye degradation

employed for dye degradation is depicted


). Two peristaltic



olumes of AC and CC were taken to

up of NaOH concentration in CC was

The dye concentrations

max = 517 nm) using

(4.1)


dichloroethane by heating

solution was then cooled to 4°C


C for 2 h. The solid sodium salt of sulfonated poly ether

in ice cold water followed by treatment with methanol and



27

Figure 2: Sulfonation process sequence

2.6. Membrane Formulations

The polymers of SPSf, SPES and SPEEK were prepared by individually at 17.5 wt% in

presence polar solvent, DMF (82.5 wt%), under constant mechanical stirring in a round bottom

flask for 3 h at 40°C. The homogeneous solution was allowed to stand for 1 h in airtight

condition to get rid off the air bubbles. The compositions and casting conditions of PEM

membranes is displayed in Table 3.

2.6.1. Preparation of Membranes

All membranes were prepared by the “diffusion induced phase separation”

method, namely, casting a thin film of the polymeric solution on a glass plate and, after

allowing the solvent to evaporate for a predetermined period at the desired humidity and

temperature conditions, immersing it into a bath of non-solvent (water, solvent, surfactant)

for final precipitation. Prior to membrane casting, a gelation bath of 2L of distilled water

(non-solvent), containing 2% DMF (Solvent) and 0.2% SLS (Surfactant) was prepared and

cooled to 10°C.

Table 3: Compositions and casting conditions of PEM membranes

Name of Polymer Polymer

composition (%)

Solvent, DMF

(%)

SPSf 17.5 82.5

SPEEK 17.5 82.5

SPES 17.5 82.5

Nafion® 117 - -

Total weight percentage of polymer = 17.5 wt %. Casting solution temperature = 85 ± 2°C,

Casting temperature = 34 ± 2°C Casting relative humidity = 20 ± 2 %, Solvent evaporation

time = 30 s.

Poly Sulfone +Chloroform

(PSU)

Dissolved + Sulfonating agent

PSU (TMSCS)

Sulfonating

Polysulfone (PSU)

Silylsulfonate PSU

+

Sodium methoxide

[A]

[C]

[B]

[A] = reaction at ambient temperature

[B] = continuous stirring for 24 h

[C] = stir for 1 hour, then added drop wise into methanol bath

(TMSCS) = trimethylsilylchlorosulfonate

Note: The solution were contiuously stirred under N2 atmosphere during the



28

Figure 3. PEM membranes

2.6.2. Membrane properties and stability

The sulfonated sample was characterized for functional group determination by FT-IR

Spectroscopy. FT-IR spectra were recorded on a Perkin-Elmer, model-Spectrum RX1 Fourier

transform spectrometer either with powder samples inside a diamond cell or by using KBr

pellets composed of 50 mg of IR spectroscopic grade KBr and 1mg polymer sample.

2.7. Estimation of water content, ion-exchange capacity (IEC) and counter-ion transport

number

Membrane thickness was measured by a digital micrometer with 0.1 µm accuracy.

The membrane water content was determined by weight of membrane in wet and dry

conditions. Membrane was dried in vacuum oven at 60 °C for 24 h and recorded its weight.

Further the dry membrane was kept in distilled water for same period of time and their wet

weight was recorded. The water content was finally calculated using the following equation:

(4.2)

Where Ww and Wdare the weight of the wet and dry membrane, respectively.

For the estimation of ion exchange capacity (IEC), desired pieces of ion-exchange

membranes were conditioned in 1.0 M HCl solution for 12 h to convert them into H+ form.

The excess HCl was removed by washing with distilled water. The membranes were then

equilibrated in 50 ml of 0.5 M NaCl solution. The amount of H+ ions liberated from SPS

membrane was determined by acid–base titration.

Nafion® 117 SPSf SPEEK SPES



29

Counter-ion transport number across the membranes was estimated by membrane

potential measurement in 0.01 and 0.10 M NaCl solutions, according to equation 4.3 reported

previously using TMS (Teorell, Meyer, and Sievers) approach.

�� 2�� 1�

�

��

��

�� (4.3)

Where a1 and a2 are the activities of electrolyte solutions contacting two surfaces of the

membrane, R is the gas constant, T is the absolute temperature, and F is the Faraday constant.

2.8. Membrane conductivity The membrane conductivities were recorded in equilibrium with eosin and NaCl

solution of different concentrations. The specific membrane conductivity (κm) was estimated

by:

�� ∆�

�� (4.4)

Where ∆x is the thickness of equilibrated membrane, A is the membrane area.

2.9. Analytical methods

2.9.1. Chemical Oxygen Demand(COD)

In order to determine the extent of degradation of the effluent Chemical Oxygen

Demand (COD) was measured. The COD as the name implies is the oxygen requirement of a

sample for oxidation of organic and inorganic matter. COD is generally considered as the

oxygen equivalent of the amount of organic matter oxidizable by potassium dichromate. The

organic matter of the sample is oxidized with a known excess of potassium dichromate in a

50% sulfuric acid solution. The excess dichromate is titrated with a standard solution of

ferrous ammonium sulfate. COD of all samples were determined by the dichromate closed

reflux method using thermo reactor TR620-Merck.In COD measurement, 3 samples are

subjected to analysis for one COD data. From that, any two same values or the average of any

two nearer values is considered as the measured data.

2.9.2. Spectral analysis using UV-visible spectrophotometer

For UV-Visible spectral analysis, 5 mL of treated and untreated samples were taken and

centrifuged at 12,000 rpm for 10 min. The supernatant of untreated and treated samples were

analyzed by monitoring the changes in its absorption spectrum using UV–visible

spectrophotometer with a cell having 1 cm optical path length.

3. RESULTS AND DISCUSSION

3.1. Characterization of sulfonated poly (ether sulfone)

FTIR spectra were also used to confirm the pendant SO3H group on the polymer

chain. Figure 4 shows the spectra of SPES. The presence of the sulfonic group can be

visualized by the presence of the absorption bands. On the spectra of SPES, the new

absorbance at 1020 cm-1

and 1250 cm-1

are contributed separately by symmetric and

asymmetric O=S=O vibration. The peak at the peak at 1770 cm-1

to the ester cardo group of

sulfonated poly (ether sulfone).It has been known that the asymmetrical stretching vibrations



of sulfonic acid groups appear at

overlapping absorbance. However, it still can getconclusion that the sulfonic acid groups has

been introduced into the polymer chains

Figure

Table 4: Physicochemical and electrochemical properties

Property

Thickness (µm)

Water content (%)

Ion-exchange capacity

(mequiv./g of dry membrane)

Counter ion transport number

Membrane conductivityb(mScm

a(tm) was estimated from membrane potential measurements in

solutions of 0.1M and 0.01M concentrations.bMembrane conductivity was measured in equilibration with 1.0MNaCl solution



30

of sulfonic acid groups appear at ∼1180 cm−1

, but we could not readily observe it due to near


ntroduced into the polymer chains

Figure 4. The spectra of SPES

Physicochemical and electrochemical properties of the cation exchange membrane

SPSf SPES Nafion® 117

150 150 150

12 23 38

(mequiv./g of dry membrane)

1.40 0.80 0.90

Counter ion transport numbera(tm) 0.94 0.99 1.05

(mScm−1

) 20.2 41.4 94.6

(tm) was estimated from membrane potential measurements in equilibrium with NaCl

solutions of 0.1M and 0.01M concentrations.

Membrane conductivity was measured in equilibration with 1.0MNaCl solution



, but we could not readily observe it due to near


of the cation exchange membrane

SPEEK

150

35

1.10

0.98

99.5

equilibrium with NaCl

Membrane conductivity was measured in equilibration with 1.0MNaCl solution



31

For EMR, knowledge on membrane conductivity in equilibration with actual

operating conditions is an essential parameter. Membrane conductivity data (km) for SPS

membrane inequilibration with eosin B and NaCl solutions of different concentrations (10-

100 ppm) is presented in Figure 5. km values depended on ionic strength of equilibrating

solution, and increased initially with concentration (eosin B and NaCl) before attending

limiting value (beyond 30 ppm). This observation may be attributed to comparatively low

dissociation and ionic strength of eosin B solution. However, comparable membrane

conductivities under both operating conditions (eosin B or NaCl) revealed the membrane

suitability for an EMR.

Figure 5. Membrane potential measurements in equilibrium

3.2. Membrane Morphology

The top face shows non-uniformaggregates that might have formed due to solvent

removal fromthe top as mentioned earlier and the bottom face appears smooth. Dense

membranes with reproducible thickness could beobtained by using a sufficient quantity of

polymer solution.The pore structure of the PEM membranes were sensitively changed for

SPSf, SPES, SPEEK and Nafion membranes (Figure 6). The average pore size of SPES

membrane clearly increased with respective IEC. In this comparison of morphology, dyes

mass transport driving forcesknown for flows of dye molecules through microporous,

diffusion driven by activity gradients, migrationof protons in the electric field, pressure-

driven convective flow, and electro-osmotic flow of uncharged species, dueto forces exerted

on them by the migrating protons. Therefore it is necessary to analyse morphology of

membranes for dyes transport mechanisms

0

1

2

3

4

5

6

Nacl Eosin B Rose bengal

Km

(m

S c

m-1)



SPSf Membrane

SPEEK Membrane

Figure 6.

3.3. Chlorine tolerant of SPS, SPES and SPEEK and Nafion® 117 membranes

The chlorine tolerant nature of prepared SPS, SPES and SPEEK membrane was

assessed in comparison with Nafion® 117 membrane in terms of percentage in weight loss

and IEC loss for definite time intervals. Formation of oxy radicals during electrochemical

water splitting in the presence of halide ion occurred AC, which may attack on hydrogen

containing bonds of PEM. Thus, developed PEM should be highly chlorine tolerant in nature.

Resultant image are presented in Figure

It is obvious that prepared membranes

after 24 h treatment when compared with Nafion® 117 membrane. Progressively, loss in IEC

and weight attained limiting values. Furthermore, for SPEEK membrane, weight loss was

slightly higher than Nafion® 117 membra

loss.



32

SPSf Membrane SPES Membrane

SPEEK Membrane Nafion Membrane

6. SEM image of all PEM membranes

hlorine tolerant of SPS, SPES and SPEEK and Nafion® 117 membranes




r splitting in the presence of halide ion occurred AC, which may attack on hydrogen


Resultant image are presented in Figure 7.

It is obvious that prepared membranes (SPS, SPES and SPEEK) lost about 5



slightly higher than Nafion® 117 membrane, while latter showed comparatively high IEC



hlorine tolerant of SPS, SPES and SPEEK and Nafion® 117 membranes




r splitting in the presence of halide ion occurred AC, which may attack on hydrogen


(SPS, SPES and SPEEK) lost about 5-6% IEC



ne, while latter showed comparatively high IEC



33

Figure 7. Comparison of percentage loss in weight for SPS, SPES and SPEEK and

Nafion® 117 membranes

The membrane degradation occurred chemically as a result of oxy-chloride free

radical (•OCl) attack on the polymer chain in the vicinity of hydrophilic domains. IEC is

measure of functional group concentration in the membrane matrix, and high for SPS

membrane (1.40 mequiv./g) in comparison with membrane Table 4. Thus, because of more

hydrophilic nature of SPS membrane than other three membranes, IEC loss was

comparatively high under chlorine stability test (Figure 8). Moreover, chlorine tolerant nature

for all (SPS, SPES and SPEEK and Nafion® 117) was same and these membranes showed

their potential applications under chlorine environment.

Figure 8. Comparison of IEC for SPS, SPES and SPEEK and Nafion® 117 membranes

0

1

2

3

4

5

6

7

8

9

0 10 20 30 40 50 60 70 80 90 100 110

% W

eig

ht

loss

Time allowed for NaoCl treatment (h)

SPSf

SPES

Nafion

SPEEK

0

1

2

3

4

5

6

7

8

0 10 20 30 40 50 60 70 80 90 100 110

% I

EC

lo

ss

Time allowed for NaoCl treatment (h)

SPSf

SPES

Nafion

SPEEK



This result means that SPEEK membrane is highly chlorine

other PEM membranes. In addition, there is no degradation moiety in this polymerbackbone

which is composed ketone and ether linkage,unlike poly(ether sulfone) backbone structu

which consists of thebenzene ring, ether and sulfone linkage (Figure

theall membranes under5% aq. NaOClsolution, time requirement with the weight loss

increased, whichmeans that the potassium ion was exchanged with sodium ionun

solution.

Figure 9. Comparison of percentage loss in weight for SPS, SPES and SPEEK and

However, for SPEEK membranes the overall values reduced after the chlorine

treatment. On the contrary, commercial Nafionmembrane

5% aq. NaOCl solution at 80◦C for different time intervalswas lesser when compared with

SPES and SPSf respectively, after exposure to NaOCl solution.

The IEC loss of membraneswas main factor to measure hydrophilicity on t

of membranes. The increase of the IEC loss with time of NaoCl treatment shown in Figure

.The increase of hydrophilicity may correspondto % of IEC loss of membranes, which

indicates that theNafionmembrane is unstable under the chlorine condition at

solution at 80◦Cas reported in other literatures.However, the % of IEC loss of SPS

membranes exhibit change after the treatment under wild acidic condition. From Figure

data give quite reliable informationon the hydrophobic/hydrophilic separation in the

amorphouspart of the ionomer. The typical dye separation and distributionis read

from % of IEC loss of membranes andits dependenton the water volume fraction

3.4.Investigations on membrane electrochemical properties

3.4.1 Electro-membrane reactor with PEM for separation dye solution

The physicochemical and electrochemical

investigation arepresented in Table

exchange capacity, and counter

specific membraneconductivity. Furthermore,

comparable with the best-known ion



34

This result means that SPEEK membrane is highly chlorine-resistant membrane than


which is composed ketone and ether linkage,unlike poly(ether sulfone) backbone structu

which consists of thebenzene ring, ether and sulfone linkage (Figure 9).After the treatment of


increased, whichmeans that the potassium ion was exchanged with sodium ionun

Comparison of percentage loss in weight for SPS, SPES and SPEEK and

Nafion® 117 membranes


treatment. On the contrary, commercial Nafionmembrane displays the chlorine resistant at

C for different time intervalswas lesser when compared with

SPES and SPSf respectively, after exposure to NaOCl solution.

The IEC loss of membraneswas main factor to measure hydrophilicity on t

of membranes. The increase of the IEC loss with time of NaoCl treatment shown in Figure


indicates that theNafionmembrane is unstable under the chlorine condition at 5% aq. NaOCl

as reported in other literatures.However, the % of IEC loss of SPS

membranes exhibit change after the treatment under wild acidic condition. From Figure


amorphouspart of the ionomer. The typical dye separation and distributionis read


Investigations on membrane electrochemical properties

membrane reactor with PEM for separation dye solution

The physicochemical and electrochemical properties of PEM prepared and used in the

Table 4. All membranes exhibited good watercontent, ion

exchange capacity, and counter-ion transportnumbers in the membrane phase and high

specific membraneconductivity. Furthermore, all properties of these membranesare

known ion-exchange membranein the world.The chemical (chlorine



resistant membrane than


which is composed ketone and ether linkage,unlike poly(ether sulfone) backbone structure

).After the treatment of


increased, whichmeans that the potassium ion was exchanged with sodium ionunder NaOCl

Comparison of percentage loss in weight for SPS, SPES and SPEEK and


displays the chlorine resistant at

C for different time intervalswas lesser when compared with

The IEC loss of membraneswas main factor to measure hydrophilicity on the surface

of membranes. The increase of the IEC loss with time of NaoCl treatment shown in Figure 9


5% aq. NaOCl

as reported in other literatures.However, the % of IEC loss of SPSf

membranes exhibit change after the treatment under wild acidic condition. From Figure 9,


amorphouspart of the ionomer. The typical dye separation and distributionis readily obtained


properties of PEM prepared and used in the

. All membranes exhibited good watercontent, ion-

ion transportnumbers in the membrane phase and high

all properties of these membranesare

exchange membranein the world.The chemical (chlorine



35

resistance) stabilities of these membranes are attractive features for theirapplicability in the

electro-membrane processes. For developingelectrochemical membrane reactor, knowledge

on membraneconductivity in equilibration with actual operating conditionsis an essential

parameter.

Most dye contains NaCl as the major constituent, thus electrochemicaldegradation is

easy in absence of supporting electrolytes. Principle of EMR used for dye degradation

wasbased on electro-membrane electrodialysis as presented in Figure 10.Generally, dye

molecule is electrochemically inactive andanode changes occurred because oxidation of

water/Cl−to O2/Cl2.Chlorine gas is robust oxidizing agent and dissolves in water

(HOCl),which is instable in acidic solution (pKa = 7.4). HOClimmediatelydissociates and

formation of OCl−is responsible for dye degradation.Thus, basic or neural pH conditions are

more favorable for dyedegradation.

Figure 10. Cyclic voltammetric responses of 0.1M NaCl: Scan rate in all cases was

50mVs−1

The above diagram describes the basic electrochemical principles by which

Electrosep's cell works. As the stream to be treated passes through the anolyte chamber,

sodium (Na+) ions are transferred through the membrane to the catholyte chamber to

combine with available hydroxyl (OH-) ions and produce caustic (sodium hydroxide).

Organics are oxidized or acidified at the anode, allowing them to be removed from the treated

stream. Hydrogen gas (H2) is liberated at the cathode, and may be recovered for fuel.pH of

the solution was monitored by using a digit al desktop,pH Meter (CP901) from Century

Instrument Company and pH was adjusted with the help of 0.1MNaOH and 0.1M HCl batch

mode. Constant stirring of the solution was ensured using magnetic stirrers. In AC, eosin B

degraded in AC by chloride/hypochlorite mediatedoxidation. Degradation was effected by

O2/OCl−

generationat anode, and migration H+/Na

+ from AC through SPS membrane(CEM)

towards cathode. This leads formation of NaOH in CC usingOH−formed due to reductive

water splitting Moreover,eosin B degradation process depends on the initial eosin B

dyeconcentration and oxidizing strength of anode (active species concentration).Electro-

active species produced at electrodes exhibited peaktyperesponses in cyclic voltammetry

because exchange of electronduring anodic- and cathodic-potential scans.

-20

-17.5

-15

-12.5

-10

-7.5

-5

-2.5

0

2.5

5

7.5

10

12.5

15

-1.5 -1 -0.5 0 0.5 1 1.5

I/A

E/V vs SCE

with addition of dye solution

Without dye solution



36

40

50

60

70

80

90

100

20 40 60 80 100 120 140 160 180Qu

ino

lin

e Y

ello

w d

ye r

em

ov

al

(% )

Time (min)

100 ppm50 ppm30 ppm10 ppm

3.5. Effect of operating conditions on Quinoline Yellowdegradation in EMR

Rate of dye degradation was affected applied potential, dye concentration and feed of

flow rate. Variation of Quinoline Yellow removal under different applied potential are

presented in Figure 11 for 50 ppm Quinoline Yellow in feed at 40 ml/min. Quinoline

Yellowconcentration was monitored by absorbance spectra before and after degradation at

411 nm band. With time and applied potential, dye removal was enhanced during electrolysis.

About 95% Quinoline Yellowdegradation was achieved for it 50 ppm concentration in AC

(40 ml/min flow rate) after 180 min electrochemical treatment at 12.0V applied potential.

Figure 11. Variation of Quinoline Yellow removal under different applied potentials

Figure12. Rate of change of dye concentration was relatively fast at high concentration

under similar experimental conditions

70

75

80

85

90

95

100

25 45 65 85 105 125 145 165 185Qu

ino

lin

e Y

ell

ow

d

ye

rem

ov

al

(%)

Time (min)

12V

10V

8V



37

40

50

60

70

80

90

100

20 40 60 80 100 120 140 160 180

Qu

ino

lin

e Y

ello

w d

ye d

ye r

em

ov

al

(% )

Time (min)

100 ppm

50 ppm

30 ppm

10 ppm

Rate ofchange of dye concentration was relatively fast at high concentrationunder

similar experimental conditions. It revealed about95% degradation of eosin B (40 ml/min

flow rate) after 180 min at12.0 V.

From Figure12, It is observed for the minimum dye concentration (100 ppm) when

reduced color in EMR using SPEEK membrane for the maximum time of 180 min. When the

highest dye concentration (100 ppm) was observed SPEEK membrane for time 30 min, only

66.5% of Quinoline Yellowdye removal in the dye concentration was detected in the samples.

The effects of reaction time and dye concentration were significant at the 180 min. The

interaction between the dye concentration and reaction time was significant in the removal

ofQuinoline Yellowdye (Figure 13).These results also showed that removal efficiency

SPEEK membrane at all the concentration levels. Similarly, all the times were also

significantly different from each other at the different concentration.Figure 14 showed

influence of time on concentration of Quinoline Yellowduring oxidative degradation of eosin.

These data revealedthat high applied potential, dye concentration and low feed flowrate are

required for fast and efficient degradation process.

Figure 13. The interaction between the dye concentration and reaction time was

significant in the removal ofQuinoline Yellowdye

Further,these parameters also depended on EMR flow pattern andmembrane as well

as electrode area. Thus complete optimizationof these parameters is essential for an efficient

process.



38

Figure 14. Influence of feed flow rate or turbulence (AC) during oxidative degradation

of eosin

Under optimumconditions about 95–98% degradation was observed during180 min,

which can be further enhanced with increase in appliedpotential or membrane area.The dye

removal percentages when the dye was treated with 25 ml/min was higher than that observed

when 50 ml/min and 75 ml/minusing SPEEK membrane. A maximum dye removal efficiency

of 97% was obtained after 180 min of time.

Figure 15. Effect of operating conditions on Eosin B degradation in EMR

70

75

80

85

90

95

100

25 45 65 85 105 125 145 165 185

Qu

ino

lin

e Y

ello

w

dye r

em

ov

al (%

)

Time (min)

25 ml/min

50 ml/min

75 ml/min

65

70

75

80

85

90

95

100

25 45 65 85 105 125 145 165 185

Eo

sin

B d

ye r

em

ov

al

(% )

Time (min)

12V

10V

8V



39

3.6. Effect of operating conditions on Eosin B degradation in EMR

The result of the Eosin Bdye color removal on time for electro membrane oxidation is

shown in Figure 15. The final color removal ratio at 10V isabout 88 % which is higher than

that at 8V. If the potential was up to 12V, the color was increased 95%,which was about 2

times of that at 8 V.Furtherincrease in the potential leads to increase in the color

removalto95%. The result is consistent with the quasi-steadystatecurves on EMR for the

Eosin B dye solution. It was supposed thatthe functional group on SO3-H underwent some

reactionswhen polarized at a certain potential and could enhance the degradation for electro

membrane.

Figure 16. The influence of concentration of the Eosin Bdye solution

The pollutant concentration is very important parameter in wastewater treatment. The

influence of concentration of the Eosin Bdyesolution has been investigated on the electro

membrane degradation with SPEEK membrane after the optimization of pH. In order to

optimize the % removal the initial dye concentrations was varied during the EMR treatment

from 10 to 100 ppm, at constant pH of 4.0. It has been observed from the graph Figure 16 that

increasing concentration of dye solution from 10 to 100 ppm decreases the percentage Eosin

Bdyeremoval and it was found that at 10 ppm dye concentration, % removal was 43% and at

100 ppm dye concentration, percentage removal was increased to 76%. The reason behind

this behavior may be due to the increase in the extent of pore size, permeation and mass

transfer through membranes at necessary dye concentration which increases the migration of

dye. The increases in the dye concentration also increase the transfer ions form dye solution

in to respective poles.

40

50

60

70

80

90

100

20 40 60 80 100 120 140 160 180

Eo

sin

B d

ye

rem

ov

al

(% )

Time (min)

100 ppm50 ppm30 ppm10 ppm



40

Figure17. Effect of timefor various concentrations of eosin dye

Experiment carried out at different contact times for various concentrations of eosin

dye showed that the percentage removal increases rapidly with increasing contact time for the

first 60 min (Figure17). With increase in reaction time, the external mass transfer coefficient

increases, resulting in movement of eosin dye molecules through membrane. However, the

membrane morphology was affecting the transfer of eosin dye molecules. At 75ml/min, the

highest % removal of eosin dye was observed, hence an indication of the influence of

molecular weight of eosin dye. The percentage of eosin dye removal influenced the chemistry

of both the eosin dye molecule and dipoles in aqueous solutions. Eosin is a dipolar molecule

and chemical structure at low pH, as shown in Figure 17. PEM contains oxygen donor sites

on its surface, e.g. hydroxyl groups and sulfonic groups.

CONCLUSION

Membrane assisted electro chemical degradation (MAEO) process showed 97%

degradation of eosin B against 92% CEand 4.97 kWh/kg of eosin B removed energy

consumption, with SPES, SPSf, SPEEK membranes. While for Nafion® 117showed 76.6%

CE and 3.94 kWh/kgof eosin B removed energy consumption for same extent of eosin B

degradation (97%) under optimum operating conditions. Depending on polymer stabilities

and properties, SPEEK membrane also can be tailored for specific separation purposes by

electro dialysis, because of its high chlorine tolerance, stabilities, conductivity and counter-

ion transport number. The studies presented using MAEO exhibit that the removal of Rose

Bengal from its aqueous solutions can be efficiently achieved through SPES, SPSf, SPEEK.

It was also found that increase in reaction time, the external mass transfer coefficient

increases, resulting in movement of Rose Bengal dye molecules through membrane.

However, the membrane morphology was affecting the transfer of Rose Bengal dye

molecules. The percentage of Rose Bengal dye removal influenced the chemistry of both the

Rose Bengal dye molecule and dipoles in aqueous solutions.

70

75

80

85

90

95

100

25 45 65 85 105 125 145 165 185

Eo

sin

B d

ye

rem

ov

al

(% )

Time (min)

25 ml/min

50 ml/min

75 ml/min



41

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