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THE DEACIDIFICATION OF PINEAPPLE JUICE USING ELECTRODIALYSIS WITH MONOPOLAR ION EXCHANGE MEMBRANES MASNIZA BINTI SAIRI A thesis submitted in fulfilment of the requirements for the award of the degree of Master of Engineering (Bioprocess) Faculty of Chemical and Natural Resources Engineering Universiti Teknologi Malaysia MAY 2005

THE DEACIDIFICATION OF PINEAPPLE JUICE USING ...eprints.utm.my/id/eprint/4366/1/MasnizaSairiMFChE2005.pdf · vi ABSTRAK Objektif penyelidikan ini adalah mengkaji prestasi elektrodialisis

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THE DEACIDIFICATION OF PINEAPPLE JUICE USING ELECTRODIALYSIS

WITH MONOPOLAR ION EXCHANGE MEMBRANES

MASNIZA BINTI SAIRI

A thesis submitted in fulfilment of the

requirements for the award of the degree of

Master of Engineering (Bioprocess)

Faculty of Chemical and Natural Resources Engineering

Universiti Teknologi Malaysia

MAY 2005

iii

Specially dedicated to my beloved mak, abah, Achik, Abang Dzul, Jojo, Angah,

Abang Chik, Alang, Along and my fiancé, Hadi for all the encouragement and help

during the hard time…

iv

ACKNOWLEDGEMENT

First of all, I wish to express my sincere appreciation to my supervisor,

Professor Dr. Mohamad Roji bin Sarmidi, Research and Development Manager of

Chemical Engineering Pilot Plant, Universiti Teknologi Malaysia for the guidance,

advice, help and encouragement throughout my study.

I would also like to express my gratitude to all staffs of Bioprocess

Engineering Department, Faculty of Chemical and Natural Resources Engineering;

Mr. Yaakop, Mr. Malek, Mr. Nur Muhammad El-Qarni and especially to Mrs. Siti

Zalita for their guidance and assistance. Thanks also to School of Graduate Studies,

Universiti Teknologi Malaysia for funding my master’s study with two years UTM -

Grant Vote 72101 and UTM - PTP scholarship.

Deep thanks and appreciation are also due to all of my friends and colleagues

for their true friendship, help, support and motivation, especially during my hard

times. Thank you so much to Law Jeng Yih, Ting Lee Yu, M. Taher, Mahadevan,

Chua Lee Suan, Cheng Kian Kai, Wan Mohd. Hafizudin, Hanamasayu, Fairuz, Ida

Juliana, Mazatusziha, Sitti Asmah, Siti Khadijah, Suzana, Yap Wei Ney, Wee Chen

Chen, Wong Fui Ling, Faizall, Hadi, Maznah, Norzaliana and Shamsaaiza. My

sincere appreciation also extends to all my colleagues in Mechanisation and

Automation Research Centre, MARDI.

Last but not least, I wish to express my deepest thanks and gratitude to all my

family members; my parents, brothers and sisters for their eternal love, continuous

prayers, moral supports and financial help. Without all of you, this study would not

have been successful.

v

ABSTRACT

The objective of this research was to study the performance of the

electrodialysis using monopolar ion exchange membranes for the deacidification of

pineapple juice. Based on preliminary experimental data using citric acid solution,

AFN monopolar anion exchange membrane was selected for the subsequent study of

the deacidification of pineapple juice. Electrodialysis of pineapple juice resulted in

the reduction of the conductivity and the total acidity in the diluted stream. The

deacidification value was 27.53 %. Deacidification process unexpectedly decreased

the pH value from 4.01 to 3.75. However the Brix values were essentially unchanged

(from 10.50 to 10.17 % Brix). A slight fluctuation in sugar compositions during

electrodialysis was observed after 80 minutes of the processing. The sugar analysis

was carried out using High Performance Liquid Chromatography (HPLC). HPLC

analysis also showed that citric acid and malic acid compositions were always higher

in the concentrated stream as compared to the diluted stream. The elemental analysis

of the pineapple juice indicated that the composition of magnesium, phosphorus and

potassium were reduced in the diluted stream but increased in the concentrated

stream. The results from sensory evaluation test showed a higher overall acceptance

for the electrodialysed pineapple juice compared to the fresh juice. The values of the

overall acceptance were 66.0 % and 56.0 %, respectively. The findings showed that

electrodialysis offer a better processing route and produce a more acceptable product

for the deacidification of pineapple juice.

vi

ABSTRAK

Objektif penyelidikan ini adalah mengkaji prestasi elektrodialisis

menggunakan membran pertukaran ion monopolar bagi penyahasidan jus nanas.

Berdasarkan data eksperimen permulaan menggunakan larutan asid sitrik, membran

pertukaran anion monopolar, AFN dipilih untuk kajian penyahasidan jus nanas.

Elektrodialisis jus nanas menyebabkan pengurangan nilai konduktiviti dan asid

keseluruhan di dalam aliran pencairan. Nilai penyahasidan adalah 27.53 %. Nilai pH

berkurang tanpa dijangka daripada 4.01 kepada 3.75. Walaubagaimanapun, nilai Brix

tidak banyak berubah (daripada 10.50 kepada 10.17 % Brix). Komposisi gula semasa

elektrodialisis menunjukkan sedikit turun naik selepas minit ke-80 pemprosesan.

Analisis gula dijalankan menggunakan Kromatografi Cecair Prestasi Tinggi (HPLC).

Analisis HPLC turut menunjukkan kandungan asid sitrik dan asid malik di dalam

aliran pemekatan sentiasa lebih tinggi daripada aliran pencairan. Analisis elemen jus

nanas menunjukkan komposisi magnesium, fosforus dan kalium berkurang di dalam

aliran pencairan tetapi bertambah di dalam aliran pemekatan. Keputusan ujian

penilaian sensori menunjukkan penerimaan keseluruhan yang lebih tinggi bagi jus

nanas yang diproses menggunakan elektrodialisis berbanding jus segar, di mana nilai

masing-masing adalah 66.0 % dan 56.0 %. Penemuan ini menunjukkan

elektrodialisis menyediakan aliran pemprosesan yang lebih baik dan menghasilkan

produk yang lebih diterima bagi penyahasidan jus nanas.

vii

TABLE OF CONTENTS

CHAPTER TITLE PAGE

TITLE i

DECLARATION ii

DEDICATION iii

ACKNOWLEDGEMENT iv

ABSTRACT v

ABSTRAK vi

TABLE OF CONTENTS vii

LIST OF TABLES xiv

LIST OF FIGURES xvii

LIST OF SYMBOLS xx

LIST OF APPENDICES xxiii

1 INTRODUCTION 1

1.1 Electrodialysis and Ion Exchange Membrane 1

1.2 Deacidification of Pineapple Juice by

Electrodialysis 2

1.3 Objective of the Study 3

1.4 Scopes of the Study 3

1.5 Organization of Thesis 4

2 LITERATURE REVIEW: ELECTRODIALYSIS

AND ION EXCHANGE MEMBRANE 5

viii

2.1 Membrane Separation Technology 5

2.1.1 Types of Membranes 9

2.1.1.1 Microporous Membranes 9

2.1.1.2 Homogeneous Membranes 10

2.1.1.3 Asymmetric Membranes 10

2.2 Ion Exchange Membrane 10

2.2.1 Introduction to Ion Exchange

Membrane 10

2.2.2 Properties of Ion Exchange

Membrane 11

2.2.3 Anion Exchange Membrane 12

2.2.4 Cation Exchange Membrane 13

2.3 Electrodialysis 13

2.3.1 Introduction to Electrodialysis 13

2.3.2 Fundamental of Electrodialysis 14

2.3.3 Electrodialysis Equipment 15

2.4 Industrial Application of Electrodialysis 16

2.4.1 Desalination of Brackish Water 16

2.4.2 Production of Table Salt 16

2.4.3 Electrodialysis in Wastewater

Treatment 16

2.4.4 Acid and Base Production 17

2.4.5 Electrodialysis in the Food Industry 17

2.4.5.1 Special Consideration for Food

and Biotechnology Application 17

2.5 Concentration Polarization and Limiting

Current Density of Electrodialysis Process 18

2.5.1 Concentration Polarization 18

2.5.2 Limiting Current Density 19

2.5.3 Limiting Current Density Determination 19

2.5.4 Derivation of the Limiting Current

Density Equation 20

2.6 Water and Ion Transport in Ion Exchange

Membrane 21

ix

2.6.1 Water Transport in Electrodialysis 21

2.6.2 Ion Transport in Electrodialysis 22

2.6.3 Derivation of the Water Transport

Equation 23

2.6.4 Derivation of the Ion Transport

Equation 25

2.7 Membrane Fouling 26

2.7.1 Process Factors Affecting Fouling 27

2.7.2 Fouling of Electrodialysis Membranes 28

2.7.3 Anti Fouling Technology 28

3 LITERATURE REVIEW: PINEAPPLE AND

DEACIDIFICATION OF FRUIT JUICES

PROCESS 30

3.1 Pineapple 30

3.1.1 Introduction 30

3.1.2 Pineapple and Pineapple Juice

Compositions 31

3.1.3 Pineapple Industry in Malaysia 35

3.2 Membrane for Processing Fruit Juice and

Beverages 35

3.3 Conventional Deacidification of Fruit Juices

Process 36

3.4 Electrodialysis for Deacidification of Fruit

Juices 37

3.5 Electrodialysis Deacidification of Citric Acid 39

4 MATERIALS AND METHODS 40

4.1 Introduction to Experimental Work 40

4.2 Materials 41

4.2.1 Chemicals 41

4.2.2 Equipments 42

x

4.2.3 Membranes 43

4.3 Experimental Set-up 45

4.4 Experimental Procedure to Determine the

Effect of Operating Parameters on

Electrodialysis Membrane Performance 47

4.4.1 Effect of Current Density 48

4.4.2 Effect of Feed Concentration 49

4.4.3 Effect of Anion Exchange

Membrane Types 49

4.5 Experimental Procedure for the Measurement

of Limiting Current Density 50

4.6 Experimental Procedure to Determine Water

Transport 51

4.7 Experimental Procedure to Determine Ion

Transport 52

4.8 Preparation of Experimental Solution 53

4.8.1 Preparation of Citric Acid Solution 53

4.8.2 Preparation of Electrode Rinse

Solution 54

4.9 Experimental Procedure for Deacidification

of Pineapple Juice Using Electrodialysis 54

4.9.1 Preparation of Pineapple Juice 54

4.9.2 The Electrodialysis of Pineapple Juice 55

4.10 Analytical Procedures 56

4.10.1 Titratable Acidity of Pineapple Juice 56

4.10.2 pH of Pineapple Juice 57

4.10.3 Total Soluble Solids in Pineapple

Juice 57

4.10.4 Analysis of Sugar Contents in

Pineapple Juice by HPLC 57

4.10.5 Analysis of Organic Acid Contents in

Pineapple Juice by HPLC 58

4.10.6 Analysis of Elemental Components

in Pineapple Juice by ICP-MS 59

xi

4.11 Sensory Analysis of Pineapple Juice 59

4.11.1 Introduction 59

4.11.2 Organisation of Sensory Evaluation

Test 60

5 RESULTS AND DISCUSSION 65

5.1 Introduction 65

5.2 Effect of Operating Parameters on Membrane

Performance Using Citric Acid Solution 66

5.2.1 Effect of Current Density on

Electrodialysis Membrane Performance 66

5.2.2 Effect of Feed Concentration on

Electrodialysis Membrane Performance 69

5.2.3 Effect of Anion Exchange Membrane

Type on Electrodialysis Membrane

Performance 74

5.3 The Current-Voltage Curve Study of Anion

and Cation Exchange Membranes Using Citric

Acid Solution 76

5.3.1 Introduction to the Limiting Current

Density 76

5.3.2 General Features of Current-Voltage

Curve for Anion and Cation

Exchange Membranes 77

5.3.3 The Characterisation of Current-

Voltage Curve for Anion Exchange

Membranes 78

5.3.4 Comparison of the Limiting Current

Density for the Anion Exchange

Membranes 83

5.4 Water and Ion Transport in Ion Exchange

Membranes for the Deacidification of Citric

Acid Solution 84

xii

5.4.1 Water Transport of Citric Acid in the

1-L Laboratory Scale Electrodialysis

System 85

5.4.2 Comparison of Water Transport Rate

for Ion Exchange Membrane 87

5.4.3 Ion Transport of Citric Acid in the

1-L Laboratory Scale Electrodialysis

System 88

5.5 Limiting Current Density Analysis 91

5.5.1 Limiting Current Density Calculation 91

5.5.2 Determination of the Empirical

Constants m and n of Limiting Current

Density Calculation 91

5.5.3 Comparison between the Measured

and Calculated Limiting Current Density

for Anion Exchange Membranes 92

5.6 Analysis of Water and Ion Transport 95

5.6.1 Water Transport Calculation 95

5.6.2 Ion Transport Calculation 95

5.6.3 Water and Ion Transport Calculation

Reliability Test 96

5.7 Deacidification of Pineapple Juice Using

Electrodialysis 98

5.7.1 Effect of Electrodialysis on Titratable

Acidity 100

5.7.2 Effect of Electrodialysis on pH of

Pineapple Juice 102

5.7.3 Effect of Electrodialysis on Soluble

Solids 103

5.7.4 Effect of Electrodialysis on Sugar

Contents in Pineapple Juice 105

5.7.5 Effect of Electrodialysis on Organic

Acid Contents in Pineapple Juice 109

5.7.6 Effect of Electrodialysis on Elemental

xiii

Components in Pineapple Juice 113

5.8 Sensory Analyses of Pineapple Juice 115

6 CONCLUSION AND RECOMMENDATIONS 118

6.1 Conclusion 118

6.2 Recommendations for Future Work 120

REFERENCES 121

APPENDICES 129

Appendix A 129

Appendix B 130

Appendix C 136

Appendix D 143

Appendix E 152

Appendix F 157

Appendix G 162

Appendix H 165

xiv

LIST OF TABLES

TABLE NO. TITLE PAGE

2.1 The characteristics of membrane used in different

membrane separation process, process driving

forces and applications of such processes 6

2.2 Membrane separation technologies 8

3.1 The composition of pineapple juice 33

3.2 The composition and nutritive value of pineapple 34

4.1 Measured anion exchange membrane (AEM)

properties and data provided by the membrane

manufacturer 44

4.2 Measured cation exchange membrane (CEM)

properties and data provided by the membrane

manufacturer 45

5.1 The data on deacidification values for AFN, AM-1,

AM-3 and AMX anion exchange membranes at

different current densities 67

5.2 The data on flux values for AFN, AM-1, AM-3 and

AMX anion exchange membranes at different current

densities 68

5.3 The data on deacidification values for AFN, AM-1,

AM-3 and AMX anion exchange membranes at

different feed concentrations 71

5.4 The data on flux values for AFN, AM-1, AM-3 and

AMX anion exchange membranes at different feed

concentrations 72

xv

5.5 The data on deacidification values through different

types of Neosepta anion exchange membranes 75

5.6 The value of limiting current density for different

types of anion exchange membranes and different

citric acid concentrations 82

5.7 The data on water transport rate for different current

densities applied to AFN, AM-1, AM-3 and AMX

anion exchange membranes 88

5.8 The data on deacidification values between current

density and feed concentration effect 89

5.9 The data on flux values between current density and

feed concentration effect 89

5.10 The empirical constants of m and of limitingn

current density for different type of anion exchange

membranes (AEMs) 92

5.11 The data on phenomenological coefficients of water

transport and ion transport rate constants for 0.2379 M

citric acid solution 96

5.12 Data for titratable acidity 101

5.13 pH value in the diluting stream during electrodialysis 103

5.14 Degree Brix value of pineapple juice samples taken

during electrodialysis processing 104

5.15 Data on Brix-acid ratio in the diluting stream and

concentrating stream during electrodialysis processing 105

5.16 The data on peak areas from HPLC chromatograms

for the determination of sugar contents in the diluting

stream during electrodialysis processing 106

5.17 The data on peak areas from HPLC chromatograms

for the determination of sugar contents in the

concentrating stream during electrodialysis processing 107

5.18 The data on peak heights from HPLC chromatograms

for the determination of organic acid contents in the

diluting stream during electrodialysis processing 110

5.19 The data on peak heights from HPLC chromatograms

xvi

for the determination of organic acid contents in the

concentrating stream during electrodialysis processing 111

5.20 The compositions of fresh pineapple juice and

processed pineapple juice using electrodialysis 114

5.21 Sensory evaluation test results 115

xvii

LIST OF FIGURES

FIGURE NO. TITLE PAGE

2.1 Microstructure of a cation exchange membrane 13

2.2 Principles of electrodialysis process 15

4.1 The experimental flowchart 41

4.2 Schematic flow diagram of electrodialysis system 45

4.2 An overview of 1-L laboratory scale electrodialysis

system 47

4.3 The schematic diagram of membranes arrangement

in the five-compartment electrodialysis system 48

4.4 The schematic diagram of current-voltage

measurement 50

4.5 Apparatus for measuring the volume of water

transport 52

5.1 Comparison of deacidification percentage at different

current densities using AFN, AM-1, AM-3 and AMX

anion exchange membrane 67

5.2 Comparison of flux value at different current densities

using AFN, AM-1, AM-3 and AMX anion exchange

membranes 69

5.3 Variation of citric acid deacidification curves during

electrodialysis processing at different feed

concentrations using AFN anion exchange membrane 70

5.4 Comparison of deacidification percentage at different

feed concentrations using AFN, AM-1, AM-3 and

AMX anion exchange membrane 72

xviii

5.5 The influence of feed concentration on the flux of

citric acid across the AFN, AM-1, AM-3 and AMX

anion exchange membranes at current density of

2.60 mA/cm2 73

5.6 Comparison of different anion exchange membrane

types on deacidification value using 0.5, 1.0, 2.0 and

5.0 (% w/v) citric acid solution 75

5.7 The current-voltage curve for ion exchange

membrane 78

5.8 The current-voltage curve of AFN anion exchange

membrane at 0.5 % (w/v) citric acid solution 79

5.9 The current-voltage curve of AFN anion exchange

membrane at 1.0 % (w/v) citric acid solution 80

5.10 The current-voltage curve of AFN anion exchange

membrane at 2.0 % (w/v) citric acid solution 80

5.11 The current-voltage curve of AFN anion exchange

membrane at 5.0 % (w/v) citric acid solution 81

5.12 The limiting current density for different type of

anion exchange membranes at various citric acid

concentrations 82

5.13 The limiting current density value for different type

of anion exchange membranes at 0.5, 1.0, 2.0 and

5.0 % (w/v) synthetic citric acid solution 83

5.14 The effect of current density on citric acid volume

difference in concentrating stream for AFN, AM-1,

AM-3 and AMX anion exchange membranes 85

5.15 The effect of citric acid feed concentration on volume

difference in concentrating stream for AFN, AM-1,

AM-3 and AMX anion exchange membrane 86

5.16 The relationship between water transport rate with

current density for AFN, AM-1, AM-3 and AMX

anion exchange membranes 88

5.17 The influence of current density and feed concentration

on deacidification value 90

xix

5.18 The influence of current density and feed concentration

on flux value 90

5.19 Measured (Mea.) and calculated (Cal.) result of

limiting current density as a function of citric acid

concentration for AFN anion exchange membrane 93

5.20 Measured (Mea.) and calculated (Cal.) result of

limiting current density as a function of citric acid

concentration for AM-1 anion exchange membrane 93

5.21 Measured (Mea.) and calculated (Cal.) result of

limiting current density as a function of citric acid

concentration for AM-3 anion exchange membrane 94

5.22 Measured (Mea.) and calculated (Cal.) result of

limiting current density as a function of citric acid

concentration for AMX anion exchange membrane 94

5.23 Measured (Mea.) and calculated (Cal.) results of

water transport at different constant current densities 96

5.24 Measured (Mea.) and calculated (Cal.) results of ion

transport rate for 0.2379 M citric acid solution 97

5.25 Deacidification curve of pineapple juice after two

hours of processing using electrodialysis 99

5.26 Comparison of total acidity in the diluting stream

and concentrating stream 102

5.27 Sugars concentrations variation as a function of time

in the diluting stream (DS) and concentrating stream

(CS) 108

5.28 Organic acids concentrations variation as a function

of time in the diluting stream (DS) and concentrating

stream (CS) 112

5.29 Comparison graph on pineapple juice characteristics

in sample M (fresh pineapple juice) and sample H

(processed pineapple juice using electrodialysis) 116

xx

LIST OF SYMBOLS

A - Ion transport rate constant (M/(A.s))

A, AEM - Anion exchange membrane

B - Ion transport rate constant (1/(A.s))

BMED - Bipolar-membrane electrodialysis

C, CEM - Cation exchange membrane

CD - Current density

CDlim - Limiting current density

CE - Current efficiency

CP - Concentration polarization

CS - Concentrating stream

D - Diffusion coefficient

DC - Direct current

DS - Diluting stream

ED - Electrodialysis

ERS - Electrode rinse solution

F - Faraday constant (96500 C.mol-1)

HPLC - High Performance Liquid Chromatography

i - Current density

I - Current, Current intensity

ICP-MS - Inductively Coupled Plasma Mass Spectrometer

IEM - Ion exchange membrane

I-V curve - Current-voltage curve

m, n - Empirical constant

n - Average current efficiency

pK - Dissociation constant

R - Gas constant

xxi

S - Effective membrane area

SS - Soluble solid

t - Time

T - Temperature

TA - Titratable acidity

v - Velocity of convection transport, Feed solution velocity

V - Voltage

x - Direction of coordinate

z - Electrochemical valence

- Phenomenological coefficient (ml/s)

- Phenomenological coefficient (ml.cm2/(A.s))

- Electrical potential

H+ - Hydrogen ion

OH- - Hydroxide ion

C0 - Feed concentration

Jk - Flux of component k

QF - Amount of electrical charges expressed in Faraday

dtdV - Water transport rate

0cC - Concentration at time = 0 in the concentrate stream

tcC - Concentration at time = t in the concentrate stream

0dC - Concentration at time = 0 in the diluate stream

)0(0citricn - Number of moles of citric acid in the concentrating stream at

initial stage

)(tnccitric - Number of moles of citric acid in the concentrating stream at

time t0

cV - Initial volume of the concentrating stream

tcV - Volume of the concentrating stream at time t

n - The difference in the number of moles of citric acid in the

concentrating stream at time t and at initial stage

cV - Volume of water transported from diluting stream to

concentrating stream

xxii

+ - Anode

- - Cathode

(% w/v) - Percent by weight

xxiii

LIST OF APPENDICES

APPENDIX TITLE PAGE

A-1 The Standard Curve of Citric Acid Solution 129

B-1 Effect of Current Density on Electrodialysis

Membrane Performance 130

B-1.1 Experimental Data Worksheet 130

B-2 Effect of Feed Concentration on Electrodialysis

Membrane Performance 132

B-2.1 Experimental Data Worksheet 132

B-2.2 The deacidification curves for AM-1, AM-3 and

AMX anion exchange membranes at various citric

acid concentrations 134

C-1 Current-Voltage Curve of Anion Exchange

Membranes Under the Influence of Different Feed

Citric Acid Concentrations 136

C-1.1 AM-1 Anion Exchange Membrane 136

C-1.2 AM-3 Anion Exchange Membrane 138

C-1.3 AMX Anion Exchange Membrane 140

D-1 Determination of the Empirical Constants m and n

of Limiting Current Density Calculation 143

D-1.1 AFN Anion Exchange Membrane 144

D-1.2 AM-1 Anion Exchange Membrane 146

D-1.3 AM-3 Anion Exchange Membrane 148

D-1.4 AMX Anion Exchange Membrane 150

E-1 Water Transport Analysis of Citric Acid 152

E-2 Ion Transport Analysis of Citric Acid 154

xxiv

F-1 HPLC Chromatogram for Sugar Contents Analysis 157

F-1.1 HPLC Chromatogram for Sugar Standards 157

F-1.2 The Data on Sugars Standard 157

F-1.3 The Standard Curve of Sugars 158

F-2 HPLC Chromatogram for Organic Acid Contents

Analysis 158

F-2.1 HPLC Chromatogram for Organic Acid Standards 158

F-2.2 The Data on Organic Acids Standard 160

F-2.3 The Standard Curve of Organic Acids 161

G-1 Questionnaire for Sensory Taste Panels Selection 162

G-2 Data of Panel Preference on Pineapple Juice Samples 164

H-1 Local and International Conference/Exhibition 165

CHAPTER 1

INTRODUCTION

1.1 Electrodialysis and Ion Exchange Membrane

Electrodialysis is an electrochemical membrane separation process in which

electrically charged membranes and an electrical potential difference used to separate

ionic species from aqueous solution and other uncharged components (Strathmann,

1992; Bazinet et al., 1998). The separation is not based on the size of the particles,

but by their electrical charge (Bazinet et al., 1998).

The interest in electrodialysis as a membrane separation process due to the

developments in new membrane materials that offer better stability and performance,

thus facilitating for new applications (such as bipolar membrane) (Bazinet et al.,

1998). The applications of electrodialysis include the desalination process,

production of table salt from seawater, demineralization of cane sugar, desalination

of cheese whey, deacidification of fruit juices, wines stabilization, production of

acids and bases from a salt stream and to the recovery of concentrated acids

(Strathmann, 1992; Alvarez et al., 1997; Bazinet et al., 1998; Ling, 2002).

The ion exchange membranes are the most important component in the

electrodialysis equipment. Ion exchange membranes are made of polymer matrix

material with fixed charged groups covalently bonded to the polymer matrix

(Strathmann, 1992). The ion exchange membranes are subdivided into two basic

categories, which are the monopolar membranes and the bipolar membranes. The

2

type of fixed charged groups attached to the polymer matrix, determines the

classification of ion exchange membrane (Ling, 2002). Monopolar membranes can

be further classified into anion exchange membrane and cation exchange membrane.

A membrane containing fixed negative charges is called a cation exchange

membrane, while a membrane with fixed positive charges is referred as anion

exchange membrane (Strathmann, 1981).

1.2 Deacidification of Pineapple Juice by Electrodialysis

Pineapple or Ananas comosus is a popular tropical fruit due to its unique

aroma and pleasant flavour. A ripe pineapple is juicy, succulent and has a tangy

sweet-tart flavour. Pineapple juice is obtained by squeezing pineapple fruit.

Pineapple juice contains 12 % - 15 % (w/v) sugars of which two-third is in the form

of sucrose and the rest are glucose and fructose. 0.6 % - 1.2 % (w/v) of pineapple is

acid of which 87 % is citric acid and 13 % is malic acid (Samson, 1986; Adhikary et

al., 1987). The pH of pineapple juice is in the acidic region, which is of around 3.71

and the acidity percentage is 53.5 %. The composition of the juice varies with

geographical, seasonal harvesting and processing.

Several methods have been attempted to reduce the sour taste of pineapple

juice, due to its high acidity. The methods include adding sweetening agents, simple

neutralization by alkali and partially removal of the acid by ion-exchange techniques

(Bhatia et al., 1979; Adhikary et al., 1983; Lue and Chiang, 1989).

At present, there is an increase demand for fruit juices with authentic

characteristics of fresh fruits and free from chemical additives. As a result, the

industry is searching for new technology that could maintain the sensorial and

nutritional quality of the fruit juices (Carneiro et al., 2002). The conventional thermal

processing method reduced the quality of the pineapple juice. An alternative

pineapple juice processing is by using electrodialysis. The advantages of

electrodialysis in relation to the thermal processing are the use of mild temperature

and pressure conditions, which maintain the nutritional quality and the sensorial

3

attributes of the products. Hence a study is warranted to develop pineapple juice with

acceptable acidity level using laboratory scale electrodialyzer equipment.

1.3 Objective of the Study

The objective of this research was to study the performance of monopolar ion

exchange membranes during electrodialysis for the deacidification of pineapple

juice.

1.4 Scope of the Study

In order to achieve the objective, the research is divided into three phases.

The first phase involved the study on the effect of operating parameters on the

performance of electrodialysis equipment using citric acid solution. The operating

parameters studied were the current density, feed concentration and anion exchange

membranes type. The study on limiting current density, water transport and ion

transport were also conducted.

The second phase was to study the reliability of the developed limiting

current density, water transport and ion transport equation to describe the

performance of electrodialysis process using citric acid solution.

The third phase was to study the deacidification of pineapple juice using

electrodialysis. The effect of electrodialysis on the physico-chemical and chemical

characteristics of pineapple juice was investigated. The sensory analysis was also

conducted to determine the acceptability of the processed pineapple juice using

electrodialysis.

4

1.5 Organization of Thesis

The research work in this thesis deals with the application of electrodialysis

with ion exchange membranes for deacidification of pineapple juice. The thesis is

divided into six chapters. Chapter 1 presents the background and overview of the

overall study. An introduction to electrodialysis, ion exchange membrane and its

application in the process of pineapple juice deacidification are presented. The

research objective and scope are also outlined.

The Chapter 2 of this thesis is the comprehensive literature review, including

membrane separation technology, the basic principles of electrodialysis and ion

exchange membranes, the applications of electrodialysis, limiting current density in

electrodialysis process and ion transport in ion exchange membranes.

In Chapter 3, the background of pineapple, the pineapple and pineapple juice

composition and pineapple industry in Malaysia are presented. Besides that,

membrane processing of fruit juices and the conventional methods for fruit juice

deacidification are presented. A review of the previous study on the application of

electrodialysis with ion exchange membrane for deacidification of fruit juices is also

cited.

Chapter 4 listed out the materials and equipments used in this study. The

methods for the experimental work were also described. All the experimental results

and discussion of the performance of electrodialysis to deacidify citric acid solution

and pineapple juice are outlined in Chapter 5. This chapter also includes the analysis

of limiting current density and water and ion transport. Finally, Chapter 6 concludes

the findings from this research and with recommendations for future work.

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