Micellar Enhanced Ultrafiltration: Fundamentals & Applications

MATERIALS SCIENCE

A response to increasingly stringent regulation of pollution and toxicity levels

in industrial waste discharge, Micellar Enhanced Ultrafiltration: Fundamentals

& Applications offers the most complete book available on the benefits and

use of micellar enhanced ultrafiltration (MEUF) to achieve continuous removal of

organic and inorganic pollutants.

An Unparalleled Book That Addresses Both Academic and Industrial

Points of View

Several membrane-based techniques, such as microfiltration, ultrafiltration,

nanofiltration, and reverse osmosis, are currently used in a wide range of

applications throughout the textile, pulp and paper, sugar, chemical,

pharmaceutical, biomedical, biotechnological, and food industries. However,

although reverse osmosis is an effective means of removing contaminants, this

book explains why MEUF is a better substitute, as it is less expensive, less

energy-intensive, and more efficient and practical for a wider range of applications.

Topics covered include:

• Effects of pollution in water and its consequences

• Various treatment processes and membrane technologies

• Fundamentals of ultrafiltration

• Outline of various membrane modules and modeling approaches

• Principles of colloid chemistry

• Theories of micelle formation

• Stability and dynamics of micelles

• Phenomena of counterion binding

• Solubilization of organic pollutants

• Selection criteria for surfactants

• Various flux enhancement techniques

• Recovery of precious metals

This book conveys how, with proper selection of surfactant and membrane, MEUF

can be used to efficiently remove almost all metal ions (heavy metals, lanthanides,

radioactive materials, etc.) with reasonably high efficiency and throughput.

It also details the MEUF process for removal of inorganic (cations, anions, and

their mixture) and organic pollutants. The authors explain how the economy of

the overall process makes recovery and reuse of surfactants essential, and

they address various influencing factors on the increase in throughput and the

resulting operating problems. Elaborating on technologies involving precipitation

and other methods, they also illustrate additional potential applications for

MEUF technology.

ISBN: 978-1-4398-9568-9

9 781439 895689

9 0 0 0 0

K14243

Micellar

Enhanced

Ultrafiltration

SIRSHENDU DE

SOURAV MONDAL

Fundamentals & Applications

I I T K H A R A G P U R R E S E A R C H M O N O G R A P H S E R I E S

Micellar Enhanced Ultrafiltration DE • MONDAL

K14243_Cover_mech.indd 1 5/14/12 11:09 AM

Micellar

Enhanced

Ultrafiltration

Fundamentals & Applications

IIT Kharagpur Research

Monograph Series

Published Titles:

Modeling of Responsive Supply Chain, M.K. Tiwari, B. Mahanty, S. P. Sarmah,

and M. Jenamani

Micellar Enhanced Ultrafiltration: Fundamentals & Applications,

Sirshendu De and Sourav Mondal

CRC Press is an imprint of the

Taylor & Francis Group, an informa business

Boca Raton London New York

Micellar

Enhanced

Ultrafiltration

SirShEndU dE

SoUrav Mondal

Fundamentals & Applications

CRC Press

Taylor & Francis Group

6000 Broken Sound Parkway NW, Suite 300

Boca Raton, FL 33487-2742

© 2012 by Taylor & Francis Group, LLC

CRC Press is an imprint of Taylor & Francis Group, an Informa business

No claim to original U.S. Government works

Version Date: 20120516

International Standard Book Number-13: 978-1-4398-9803-1 (eBook - PDF)

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v

Contents

Preface.......................................................................................................................ix

Series Preface...........................................................................................................xi

Acknowledgments............................................................................................... xiii

About the Authors............................................................................................... xiv

1 Pollution and Importance of Micellar-Enhanced Ultrafiltration..........1

1.1 Sources of Water Pollution....................................................................1

1.1.1 Agricultural Wastewater.........................................................3

1.1.2 Industrial Effluent.....................................................................3

1.1.3 Household Waste......................................................................4

1.1.4 Natural Calamity......................................................................6

1.2 Types of Pollutants and Sources..........................................................6

1.3 Conventional Treatment Processes......................................................7

1.3.1 Chemical (Inorganic) Methods of Treatment........................7

1.3.2 Biological (Organic) Methods of Treatment..........................8

1.3.3 Common Effluent Treatment Plants (ETPs)..........................9

1.3.4 Primary, Secondary, and Tertiary Treatment..................... 10

1.3.4.1 Primary Treatment.................................................. 10

1.3.4.2 Secondary Treatment.............................................. 11

1.3.4.3 Tertiary Water Treatment.......................................12

1.4 Membrane-Based Separation Process............................................... 14

1.5 Micellar-Enhanced Ultrafiltration..................................................... 17

References........................................................................................................ 18

2 Fundamentals of Membrane Separation and Ultrafiltration................23

2.1 Fundamentals.......................................................................................23

2.1.1 Nature of Separation Process................................................23

2.1.2 Advantages of Membrane-Based Process...........................23

2.1.3 Material of Construction........................................................ 24

2.1.4 Membrane Casting................................................................. 24

2.1.5 Categorization of Processes................................................... 24

2.1.5.1 Reverse Osmosis (RO)............................................. 24

2.1.5.2 Nanofiltration (NF).................................................25

2.1.5.3 Ultrafiltration (UF)..................................................25

2.1.5.4 Microfiltration (MF)................................................25

2.1.6 Transport Mechanism............................................................25

2.1.6.1 Permeation................................................................25

2.1.6.2 Knudsen Diffusion (d/λ < 0.2)...............................25

2.1.6.3 Convection (d/λ > 20)..............................................26

vi Contents

2.1.7 Characterization of Membranes...........................................26

2.1.7.1 Observed Retention (Selectivity

of Membrane).......................................................26

2.1.7.2 Real Retention..........................................................26

2.1.7.3 Molecular Weight Cutoff (MWCO).......................26

2.1.7.4 Membrane Permeability (Lp)..................................28

2.1.8 Estimation of Retention and Permeability..........................28

2.1.8.1 Retention...................................................................28

2.1.8.2 Permeability.............................................................28

2.2 Membrane Modules.............................................................................29

2.2.1 Plate and Frame Modules......................................................29

2.2.2 Tubular Modules..................................................................... 31

2.2.3 Hollow Fiber Module............................................................. 32

2.2.4 Spiral Wound Module............................................................ 32

2.3 Operational Problems..........................................................................33

2.3.1 Concentration Polarization....................................................33

2.3.2 Membrane Fouling.................................................................33

2.3.2.1 Reversible Fouling...................................................34

2.3.2.2 Irreversible Fouling.................................................34

2.4 Modeling of Concentration Polarization..........................................34

2.4.1 First-Generation Models........................................................35

2.4.1.1 Shortcoming of the Above Method...................... 37

2.4.2 Second-Generation Models................................................... 37

2.4.3 Third-Generation Models......................................................39

2.5 Applications of Ultrafiltration............................................................ 41

2.5.1 Electropaint Recovery............................................................ 41

2.5.2 Textile Industry....................................................................... 41

2.5.3 Metal Finishing Industry....................................................... 41

2.5.4 Dairy Industries......................................................................42

2.5.5 Juice Processing.......................................................................42

2.5.6 Pulp and Paper Industry.......................................................42

2.5.7 Tannery Industry....................................................................43

2.5.8 Extraction of Costly Herbal Components from

Natural Products.....................................................................43

2.5.9 Pharmaceutical Industries.....................................................43

2.5.10 Pure Water Production...........................................................43

2.5.11 Upcoming Applications.........................................................44

References........................................................................................................44

3 Surfactants......................................................................................................49

3.1 Types of Surfactants.............................................................................49

3.1.1 Anionic Surfactant..................................................................49

3.1.1.1 Carboxylates.............................................................50

3.1.1.2 Sulfates...................................................................... 51

Contents vii

3.1.1.3 Sulfonates................................................................. 52

3.1.1.4 Phosphates................................................................ 52

3.1.2 Cationic Surfactant.................................................................53

3.1.3 Zwitterionic Surfactant..........................................................54

3.1.4 Nonionic Surfactant................................................................54

3.2 Structure................................................................................................55

3.3 Properties..............................................................................................56

3.4 Formation of Micelle............................................................................57

3.4.1 Factors That Influence the CMC of the Solution................59

3.5 Thermodynamics of Micelle Stability...............................................60

3.6 Micelle Characteristics........................................................................63

3.7 Counterion Binding to Micelles.........................................................66

3.8 Effects on Micelle Formation..............................................................69

References........................................................................................................72

4 Selection of Surfactant................................................................................. 81

4.1 Ionic Surfactant....................................................................................83

4.1.1 MEUF Using Cationic Surfactant.........................................83

4.1.2 Anionic Surfactant..................................................................84

4.2 Nonionic Surfactant.............................................................................85

References........................................................................................................90

5 Removal of Inorganic Pollutants................................................................93

5.1 Single Component System..................................................................93

5.2 Multicomponent System................................................................... 107

5.2.1 Cationic-Cationic Mixture................................................... 107

5.2.2 Anionic-Anionic Mixture.................................................... 109

5.2.3 Cationic-Anionic Mixture.................................................... 111

References...................................................................................................... 114

6 Removal of Organic Pollutants................................................................. 119

6.1 Removal of Single Component System........................................... 119

6.1.1 Removal of Dyes................................................................... 119

6.1.2 Removal of Phenol................................................................125

6.1.3 Removal of Alachlor............................................................. 128

6.1.4 Removal of Naphthenic Acid.............................................. 129

6.2 Removal of Multicomponent System (Exclusively Organic)........ 130

6.3 Organic-Inorganic Mixture.............................................................. 133

References...................................................................................................... 136

7 Permeate Flux: Influencing Factors.......................................................... 141

7.1 Application of External Electric Field............................................. 141

7.2 Surface Modification.......................................................................... 145

7.2.1 Chemical Treatment and Physical Coating....................... 145

7.2.2 Plasma Treatment................................................................. 145

viii Contents

7.2.3 Ion Beam Irradiation............................................................ 147

7.2.4 Grafting Polymers................................................................. 147

7.3 Hydrodynamic Modifications.......................................................... 148

7.3.1 Turbulent Flow...................................................................... 148

7.3.2 Unsteady Flows and Induction of Instabilities................. 148

7.3.2.1 Turbulence Promoter............................................ 148

7.3.2.2 Gas Sparging.......................................................... 148

7.3.2.3 Secondary Flow..................................................... 149

7.3.2.4 Pulsatile Flow........................................................ 149

References...................................................................................................... 149

8 Recovery of Surfactants............................................................................. 155

8.1 Recovery of Anionic Surfactant....................................................... 155

8.2 Recovery of Cationic Surfactant....................................................... 159

References...................................................................................................... 161

9 Other Applications of Micellar-Enhanced Ultrafiltration.................. 163

9.1 Recovery of Precious Metal Ions...................................................... 163

9.2 Recovery of Bioactive Compounds.................................................. 166

9.3 Enantioselective Micelles for Separation

of Racemic Mixture.....................................................................168

9.4 Preconcentration Applications......................................................... 169

References...................................................................................................... 173

Appendix: CMC Values of Some Surfactants............................................... 175

ix

Preface

Pollution of the environment from the waste emerging from various indus￾tries is a burning social issue. In view of this, the norms for regulation of

the level of toxicity in the industrial discharge are becoming more stringent

nowadays. Continuous removal of organic and inorganic pollutants from

aqueous streams with high efficiency and economy is therefore a big chal￾lenge to the scientific community. Traditional treatment processes are labor￾and cost-intensive and require bigger space.

Membrane-based separation technology can offer an attractive alternative

in this regard. Several membrane-based techniques, such as microfiltration,

ultrafiltration, nanofiltration, and reverse osmosis, are currently used in a

wide range of applications encompassing the textile, pulp and paper, sugar,

chemical, pharmaceutical, biomedical, biotechnological, and food industries.

Polluted water contains a large number of metal ions (Cu2+, Cr3+, Zn2+, Sr2+,

Ca2+, Pb2+, Ni2+, Mn2+, Co2+, As3+, Fe2+, etc.), anions (oxyanions, phosphates,

ferrocyanide, etc.), and organic compounds like phenol, aniline, dyes, etc.

A rate-governed separation process like reverse osmosis is very effective

and efficient in removal of these contaminants. Since the operating pres￾sure in reverse osmosis is quite high, this process is highly energy-intensive

and requires large investment, rendering its limited practical application.

Therefore, micellar-enhanced ultrafiltration, based on the principle of col￾loid and interfacial chemistry, is a better substitute. Micellar-enhanced

ultrafiltration is a technology that employs surfactant micelles to solubilize

inorganic and organic pollutants from the effluent stream and subsequently

filters them to restrict the micelle-pollutant complex formed in the permeate

stream. More than 90% removal efficiency along with high throughput can

be attained by using a pollutant-specific surfactant (or a mixed surfactant

system) and high-permeability membrane, depending on the charge and

other physical properties of the contaminants. Since more open-sized mem￾branes are used, this process involves less energy consumption. The amount

of surfactant required is a minimal amount (only to obtain a critical micelle

concentration), and the process is also economical. After the separation of

the waste from the effluent/process stream, recovery of the surfactant is also

possible. In fact, micellar-enhanced ultrafiltration is a viable technique that

can remove almost all metal ions (heavy metals, lanthanides, radioactive,

etc.) with a reasonably high efficiency and throughput by proper selection of

surfactant and membrane.

Therefore, use of MEUF technology ensures lower operating pressure, less

energy consumption, and removal of smaller-sized pollutants with higher

throughput. This book presents state-of-the-art research on this topic with

a detailed description of various aspects of this technology. Chapter 1 deals

x Preface

with the effects of pollution in water and its consequences. Comparison of

various treatment processes and membrane technologies has been addressed.

Fundamentals of ultrafiltration have been explained in Chapter 2. Different

types of membrane modules and modeling approaches have been outlined in

this chapter. Micellar-enhanced ultrafiltration involves principles of colloid

chemistry. Theories of micelle formation, stability and dynamics of micelles,

phenomena of counterion binding, and solubilization of organic pollutants

are important aspects. These are covered in detail in Chapter 3. Selection

of surfactants is of extreme importance in micellar-enhanced ultrafiltration,

which is elucidated in Chapter 4.

Removal of inorganic (cations, anions, and their mixture) and organic pol￾lutants by micellar-enhanced ultrafiltration has been described in depth in

Chapters 5 and 6, respectively. Removal of metal ions encompassing group II

to lanthanides has also been covered.

Various influencing factors regarding an increase in throughput and

the operating problems associated herewith are discussed in Chapter 7.

Considering the economy of the overall process,recovery and reuse of surfac￾tants are essential. Technologies involving precipitation and other methods

are elaborated in Chapter 8. Finally, a glimpse of other potential applications

of this technology is illustrated in Chapter 9.

Since a complete book on such a topic does not exist today, the importance

of it from an academic as well as industrial point of view is remarkably

high. This book can be used as one of the texts for the course involving

membrane technology and environmental science taught at the postgrad￾uate level. Of course, this book can be an extremely useful reference for

students and professionals in chemical engineering, environmental engi￾neering, civil engineering, bioengineering, agricultural engineering, and

industrial engineering.

We believe that this book would initiate some research interests and

industrial development on the lines of green and clean technology. We hope

that the readers will benefit from the applicability and significance of this

technology through this book. Although we have put in our best efforts to

organize all possible information regarding micellar-enhanced ultrafiltra￾tion, readers’ comments and suggestions for improvement will be gratefully

acknowledged.

Sirshendu De

Sourav Mondal

xi

Series Preface

IIT Kharagpur had been a forerunner in research publications and this

monograph series is a natural culmination. Empowered with vast experi￾ence of more than 60 years, the faculty now gets together with their glori￾ous alumni to present bibles of information under the IIT Kharagpur Research

Monograph Series.

Initiated during the Diamond Jubilee Year of the Institute, the Series aims

at collating research and developments in various branches of science and

engineering in a coherent manner. The Series, which will be an ongoing

endeavour, is expected to be a source reference to fundamental research as

well as to provide directions to young researchers. The presentations are in a

format that these can serve as stand alone texts or reference books.

The specific objective of this research monograph series is to encourage

the eminent faculty and coveted alumni to spread and share knowl￾edge and information to the global community for the betterment of

mankind

The Institute

Indian Institute of Technology Kharagpur is one of the pioneering techno￾logical institutes in India and it is the first of its kind to be established imme￾diately after the independence of India. It was founded in 18 August, 1951,

at Hijli, Kharagpur, West Bengal, India. The IIT Kharagpur has the largest

campus of all IITs, with an area of 2,100 acres. At present, it has 34 depart￾ments, centers, and schools and about 10,000 undergraduate, postgraduate,

and research students with faculty strength of nearly 600; the number of

faculty is expected to double within approximately five years. The faculty

and the alumni of IIT Kharagpur are having wide global exposures with the

advances of science and engineering. The experience and the contributions

of the faculty, students and the alumni are expected to get exposed through

this monograph series.

More on IIT Kharagpur is available at www.iitkgp.ac.in

xiii

Acknowledgments

It is a pleasure to thank all those who made this book possible and turned it

into reality. It is a small endeavor to acknowledge the good wishes, blessings,

and whole-hearted support of our near and dear ones, to those we are really

indebted to.