Eckhard Worch

Adsorption
Technology in Water
Treatment
Fundamentals, Processes, and Modeling

DE GRUYTER

Contents

xi

Preface

Introduction

1.1

1.1.1

Basic concepts and definitions

Adsorption as a surface process

1.1.2

Some

general thermodynamic considerations

Adsorption versus absorption
Description of adsorption processes: The structure
adsorption theory

1.1.3
1.1.4

1.2

Engineered adsorption

1.2.1

Overview

1.2.2

Drinking

1.2.3

Wastewater treatment

1
3
of the
3
5

processes in water treatment

5
6

water treatment

6
7

1.2.4

processes in water treatment

Hybrid

1.3

Natural

Adsorbents and adsorbent characterization

11

2.1

Introduction and adsorbent classification

11

processes in water treatment

sorption

2.2

Engineered

2.2.1

Activated carbon

2.2.2

Polymeric

2.2.3

Oxidic adsorbents

12

adsorbents

12
15

adsorbents

16
17

2.2.4

zeolites

Synthetic

2.3

Natural and low-cost adsorbents

18

2.4

Geosorbents in environmental

19

2.5

Adsorbent characterization

20

2.5.1

Densities

20

2.5.2

Porosities

22

2.5.3

External surface

23

2.5.4

Internal surface

2.5.5

Pore-size distribution

28

2.5.6

Surface

34

Adsorption equilibrium

3.1

Introduction

3.2

Experimental determination

3.2.1

Basics

compartments

area

25

area

chemistry
I:

General aspects and single-solute adsorption

...

41
41

of

equihbrium

data

42
42

VI

Contents

3.2.2

Practical aspects of isotherm determination

45

3.3

Isotherm

for

single-solute adsorption
single-solute isotherm equations
Irreversible isotherm and one-parameter isotherm
Two-parameter isotherms

47

3.3.1

Classification of

55

3.3.5

Three-parameter isotherms
Isotherm equations with more

3.4

Prediction of isotherms

3.5

Temperature dependence

3.6

Slurry

3.6.1

General aspects

67

3.6.2

3.6.3

Single-stage adsorption
Two-stage adsorption

72

3.7

Application

3.3.2
3.3.3
3.3.4

curve

equations

adsorber

than three parameters

47
48
49
58
59

of

64

adsorption

67

design

69

of isotherm data in kinetic

or

breakthrough
74

models

II: Multisolute

Adsorption equilibrium

4.1

Introduction

4.2

Experimental

4.3

Overview of existing multisolute adsorption models

80

4.4

Multisolute isotherm

81

4.5
4.5.1

The ideal adsorbed solution theory (LAST)

Basics of the IAST

4.5.2

Solution to the IAST for

4.5.3

Solution to the IAST for

4.6

The

4.7
4.7.1

4.7.2

adsorption

77

77
determination of

equilibrium data

equations

84
84
concentrations

given equilibrium
given initial concentrations

pH dependence of adsorption:
competitive adsorption

special

98
98

100

Competitive adsorption

4.8

Slurry

4.8.1

Basics

4.8.2

NOM

of

micropollutants and NOM

for multisolute

adsorption

104
Ill
Ill

4.8.4

adsorption
Competitive adsorption of micropollutants and
Nonequilibrium adsorption in slurry reactors

4.9

Special applications

4.8.3

90

94

(adsorption analysis)
4.7.3

design

88

case of

Adsorption of natural organic matter (NOM)

The significance of NOM in activated carbon adsorption
Modeling of NOM adsorption: The Active component approach

adsorber

78

of the Active component

112
NOM

approach

113
118
120

Contents

VII

Adsorption kinetics

123

5.1

Introduction

123

5.2

Mass transfer mechanisms

123

5.3

Experimental

5.4

Mass transfer models

127

5.4.1

General considerations

127

5.4.2

Film diffusion

129

5.4.3

Surface diffusion

136

5.4.4

Pore diffusion

143

5.4.5

Combined surface and pore diffusion

149

5.4.6

Simplified intraparticle diffusion model (LDF model)

153

5.4.7

Reaction kinetic models

162

5.4.8

Adsorption

5.5

Practical aspects: Slurry adsorber design

Adsorption dynamics

6.1

Introduction

6.2

Experimental

6.3

Fixed-bed process parameters

176

6.4

Material balances

179

6.4.1

determination of kinetic

kinetics in

124

curves

multicomponent systems

164
166

in fixed-bed adsorbers

169
169

determination of

breakthrough

curves

175

of material balances

179

material balance

179

6.4.2

Types
Integral

6.4.3

Differential material balance

185

6.5

Practical aspects
Introduction

189

6.5.1
6.5.2

Topical operating

6.5.3

Fixed-bed versus batch adsorber

189
conditions

190
191

6.5.4

Multiple

adsorber systems

193

Fixed-bed adsorber design

197

7.1

Introduction and model classification

197

7.2

Scale-up

7.2.1

Mass transfer

7.2.2

Length

7.2.3

Rapid

7.3

Equilibrium

7.4

Complete breakthrough

7.4.1

Introduction

7.4.2

Homogeneous surface diffusion model

7.4.3

Constant pattern

methods

198

zone

(MTZ)

of unused bed

model

(LUB)

small-scale column test

column model

198

model

202

(RSSCT)

203

(ECM)

curve

207

models

211
211

approach

(HSDM)

to the HSDM

(CPHSDM)

213
217

Vlll

7.4.4

Contents

220

7.4.6

driving force (LDF) model

Comparison of HSDM and LDF model
Simplified breakthrough curve models with analytical solutions

7.5

Determination of model parameters

232

7.5.1

General considerations

232

7.5.2

Single-solute adsorption

233

7.5.3
7.5.4

Competitive adsorption in defined multisolute systems

Competitive adsorption in complex systems of unknown composition

7.6

Special applications

7.6.1
7.6.2

Micropollutant adsorption in presence of natural

Biologically active carbon filters

Desorption and reactivation

253

8.1

Introduction

253

8.2

254

8.2.2

Physicochemical regeneration processes

Desorption into the gas phase
Desorption into the liquid phase

8.3

Reactivation

261

Geosorption

9.1

Introduction

9.2

Experimental determination

9.3

The

7.4.5

8.2.1

Linear

of

breakthrough

curve

matter

238
....

238

240
248

254
256

processes in water treatment

265
265

of

geosorption

advection-dispersion equation (ADE)

concept

data

Simplified method for determination

experimental breakthrough curves

of

Rd

267

and the

retardation
9.4

226

240

models

organic

224

268
from
271

9.5

Breakthrough

9.5.1

Introduction and model classification

273

9.5.2

Local

275

9.5.3

Linear

9.5.4

Extension of the local equilibrium model

279

9.6

Combined

280

9.6.1

General model

9.6.2

Special
and

equilibrium

driving

model

force

(LEM)
(LDF) model

and

sorption

case:

273

modeling

curve

277

biodegradation

approach

Natural

organic

280
matter

(NOM) sorption
285

biodegradation

9.7

The influence of pH and NOM

9.7.1

pH-dependent sorption

287

9.7.2

Influence of NOM

289

9.8

Practical aspects: Prediction of subsurface solute transport

General considerations

9.8.1

on

on

geosorption

processes

micropollutant sorption

287

291
291

Contents

IX

9.8.2

Prediction of sorption coefficients

293

9.8.3

Prediction of the

295

10

Appendix

297

10.1

Conversion of Freundlich coefficients

297

10.2

Evaluation of surface diffusion coefficients from

10.3

Constant pattern solution to the

model

dispersivity

homogeneous

experimental

data

298

surface diffusion
302

(CPHSDM)

Nomenclature

307

References

319

Index

'.

327