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DESALINATION,
TRENDS AND
TECHNOLOGIES
Edited by Michael Schorr
Desalination, Trends and Technologies
Edited by Michael Schorr

Published by InTech
Janeza Trdine 9, 51000 Rijeka, Croatia

Copyright © 2011 InTech

All chapters are Open Access articles distributed under the Creative Commons
Non Commercial Share Alike Attribution 3.0 license, which permits to copy,
distribute, transmit, and adapt the work in any medium, so long as the original
work is properly cited. After this work has been published by InTech, authors
have the right to republish it, in whole or part, in any publication of which they
are the author, and to make other personal use of the work. Any republication,
referencing or personal use of the work must explicitly identify the original source.

Statements and opinions expressed in the chapters are these of the individual contributors
and not necessarily those of the editors or publisher. No responsibility is accepted
for the accuracy of information contained in the published articles. The publisher
assumes no responsibility for any damage or injury to persons or property arising out
of the use of any materials, instructions, methods or ideas contained in the book.

Publishing Process Manager Iva Lipovic

Technical Editor Teodora Smiljanic
Cover Designer Martina Sirotic
Image Copyright Tyler Olson, 2010. Used under license from Shutterstock.com

First published February, 2011

Printed in India

A free online edition of this book is available at www.intechopen.com

Additional hard copies can be obtained from [email protected]

Desalination, Trends and Technologies, Edited by Michael Schorr

p. cm.
ISBN 978-953-307-311-8
free online editions of InTech
Books and Journals can be found at
www.intechopen.com
Contents

Preface IX

Part 1 Desalination Processes and Plants 1

Chapter 1 Electrodialysis Technology - Theory and Applications 3

Fernando Valero, Angel Barceló and Ramón Arbós

Chapter 2 Water Desalination by Membrane Distillation 21

Marek Gryta

Chapter 3 Desalination of Coastal Karst Springs by Hydro-geologic,

Hydro-technical and Adaptable Methods 41
Marko Breznik and Franci Steinman

Chapter 4 Corrosion Control in the Desalination Industry 71

Michael Schorr, Benjamín Valdez, Juan Ocampo and Amir Eliezer

Part 2 Novel Trends and Technologies 87

Chapter 5 Application of Renewable Energies

for Water Desalination 89
Mattheus Goosen, Hacene Mahmoudi,
Noreddine Ghaffour and Shyam S. Sablani

Chapter 6 Seawater Desalination: Trends and Technologies 119

Val S. Frenkel

Chapter 7 Advanced Mechanical

Vapor-Compression Desalination System 129
Jorge R. Lara, Omorinsola Osunsan and Mark T. Holtzapple

Chapter 8 Renewable Energy Opportunities in Water Desalination 149

Ali A. Al-Karaghouli and L.L. Kazmerski

Chapter 9 New Trend in the Development

of ME-TVC Desalination System 185
Anwar Bin Amer
VI Contents

Part 3 Environmental and Economical Aspects 215

Chapter 10 Solar Desalination 217

Bechir Chaouachi

Chapter 11 Reject Brine Management 237

Muftah H. El-Naas

Chapter 12 DOE Method for Optimizing Desalination Systems 253

Amin Behzadmehr

Chapter 13 Impacts of Brine Discharge on the Marine Environment.

Modelling as a Predictive Tool 279
Pilar Palomar and Iñigo. J. Losada

Chapter 14 Optimization of Hybrid Desalination Processes Including

Multi Stage Flash and Reverse Osmosis Systems 311
Marian G. Marcovecchio, Sergio F. Mussati,
Nicolás J. Scenna and Pío A. Aguirre
Preface

The sustainability and prosperity of the ancient civilizations of China, Egypt, Baby-
lonia, Phoenicia, Persia and Roma were based on the extensive use of water for hu-
man consumption, crop irrigation, canal navigation and energy generation. Today, the
worldwide scarcity of water and clean energy constitutes a central and critical prob-
lem for the whole humankind. This situation is aggravated as industrial, agricultural
and municipal effluents reach the water bodies, or the coastal seawater that is used as
feed for desalination plants. All these problems are linked to the actual, natural and
anthropogenic changes of climate, global warming and greenhouse-gas emissions, all
interrelated phenomena that affect our planet.

In order to avoid damage to its facilities and equipment, the desalination industry in-
vests considerable efforts to deal with these changes, in particular with extreme events
such as torrential rains, devastating floods, dry seasons with devouring fires, as well
as with extended spells of cold weather with freezing temperatures.

The book chapters are arranged in an hierarchical sequence, starting with conventional
and novel desalination processes and following with energy, environmental, economic
and ecological issues, all affecting the desalination industry image and profitability.

Leading experts from academia and industry, as well as environment researchers, dis-
tinguished teachers and experienced engineers have written special chapters for this
impressive collection. The contributing authors offer a large amount of practical infor-
mation, presenting it in a highly condensed yet coherent body of useful knowledge
and practical expertise. Moreover, the multi-authored characteristic of this volume
offers a wide spectrum of knowledge and experience, as the authors are specialists in
different fields and express diverse approaches and orientations. The intended multi-
facet content of this publication certainly contributes to enrich it.

This compendium provides valuable, encyclopedic knowledge on research, develop-

ment, processes, plants and technologies of this industry, from the fundamental con-
cepts up to many practical cases collected from around the world. Hence, it provides
a useful insight into the world of water, energy and desalination, easy to follow and
to apply.

This volume is an essential companion to chemists, as well as to civil and chemical

engineers who design, build and operate desalination plants. It is also highly relevant
to maintenance personnel, corrosion specialists, material- and mechanical engineers.
X Preface

Also, university lecturers and researchers will find it useful for their students while
preparing their thesis on subjects related to desalination processes and plants. Not less
so, desalination industry executives should make sure that their field managers and
engineers in charge of running their plants will have access to it, and apply the built-in
know-how in their daily work routine.

Another strong part of this book is the wealth of references listed for each chapter,
amounting to hundreds of sources of detailed information from the modern scientific
and technical literature. Anyone interested in desalination will be thrilled by their di-
verse content.

All in all, this volume enables the reader to gain a deeper understanding of the state
of the art of the desalination industry and to become acquainted with the most recent
developments and technologies in this area.

Finally, it is my pleasant duty to acknowledge with thanks each of the learned authors
for contributing their chapters to this volume.

December 2010

Prof. Michael Schorr

Institute of Engineering
University of Baja California
Mexicali, Mexico
 Part 1

Desalination Processes and Plants

 1

Electrodialysis Technology -
Theory and Applications
Fernando Valero, Angel Barceló and Ramón Arbós
Aigues Ter Llobregat (ATLL).
Spain

1. Introduction
First commercial equipment based on Electrodialysis (ED) technology was developed in the
1950s to demineralize brackish water (Juda & McRae, 1950; Winger et al. 1953). Since then
ED has advanced rapidly because of improved ion exchange membrane properties, better
materials of construction and advances in technology. In the 1960s, Electrodialysis Reversal
(EDR) was introduced, to avoid organic fouling problems (Mihara & Kato, 1969). Over the
past twenty years EDR has earned a reputation as a membrane desalination process that
works economically and reliably on surface water supplies, reuse water and some specific
industrial applications when designed and operated properly.
Some applications of ED/EDR were its use to reduce inorganics like radium (Hays, 2000),
perchlorate (Roquebert et al., 2000), bromide (Valero & Arbós, 2010), fluoride (GE W&P,
2010), iron and manganese (Heshka, 1992) and nitrate (Menkouchi Sahlia et al., 2008) in
drinking water. In addition the technology can be used to recycle municipal and industrial
wastewater (Broens et al,. 2004; Chao & Liang, 2008), recovering reverse osmosis reject
(Reahl, 1990; Korngold, 2009), desalting wells (Harries et al., 1991), surface waters (Lozier et
al. 1992), final effluent treatment for reuse in cooling towers (De barros, 2008), whey and soy
purification (MEGA a.s.,2010), table salt production (Kawahara, 1994) and many other
industrial uses (Schoeman & Stein, 2000; Dalla Costa et al., 2002; Pilat, 2003). For this kind of
applications, this technology had shown best hydraulic recovery and cost effective in front
of other membrane technologies, specially compared with Reversal Osmosis (RO). In these
sense, the lower residues produced during ED/EDR process, is another important
advantatge of this technique (AWWA, 2004). Moreover, electrodialysis is not always a cost
effective option for seawater desalination and does not have a barrier effect against
microbiological contamination.
This chapter reviews some aspects related with the theory of the technology, design, operation
and maintenance (O&M), manufacturers, applications, operational costs and finally shows two
cases studies involving the two world’s biggest EDR systems, both located near to Barcelona
(Spain). The first of them is located in Abrera (Valero et al., 2007) with a capacity of treatment
of 220.000 m3/d (576 stacks in two stages, provided by GE Water & Process) and it is related
with desalting brackish water to improve the quality of the produced drinking water. The
second one is located in Sant Boi del Llobregat (Segarra et al., 2009) with a capacity of
treatment of 57,000 m3/d (96 stacks in two stages, provided by MEGA a.s.) and represents a
tertiary treatment of a wastewater treatment plant (WWTP) for agricultural reuse.
4 Desalination, Trends and Technologies

2. Theory
ED is an electrochemical separation process in which ions are transferred through ion
exchange membranes by means of a direct current (DC) voltage. The process uses a driving
force to transfer ionic species from the source water through cathode (positively charged
ions) and anode (negatively charged ions) to a concentrate wastewater stream, creating a
more dilute stream (Figure 1).
inlet
water product
(-) cathode

CM
+
-
AM
-
+
CM
+
-
AM
+
-
CM
+
-
AM
+
-
CM
+
-
AM
+
-
CM
+
-
AM
+
-
CM

(+) anode

concentrate
Fig. 1. Principles of ED
ED selectively removes dissolved solids, based on their electrical charge, by transferring the
brackish water ions through a semi permeable ion exchange membrane charged with an
electrical potential. It points out that the feed water becomes separated into the following
three types of water (AWWA, 1995):
• product water, which has an acceptably low conductivity and TDS level;
• brine, or concentrate, which is the water that receives the brackish water ions; and
• electrode feed water, which is the water that passes directly over the electrodes that
create the electrical potential.
EDR is a variation on the ED process, which uses electrode polarity reversal to automatically
clean membrane surfaces. EDR works the same way as ED, except that the polarity of the
DC power is reversed two to four times per hour. When the polarity is reversed, the source
water dilute and concentrate compartments are also reversed and so are the chemical
reactions at the electrodes. This polarity reversal helps prevent the formation of scale on the
membranes. The setup is very similar to an ED system except for the presence of reversal
valves (Ionics Inc., 1984).

2.1 Membrane stacks

All ED and EDR systems are designed specifically for a particular application. The amount
of ions to be removed is determined by the configuration of the membrane stack. A
membrane stack may be oriented in either a horizontal or vertical position.
Electrodialysis Technology - Theory and Applications 5

Cell pairs form the basic building blocks of an EDR membrane stack (Figure 1). Each stack
assembled has the two electrodes and groups of cell pairs. The number of cell pairs
necessary to achieve a given product water quality is primarily determined by source water
quality, and can design stacks with more than 600 cell pairs for industrial applications
(Strathmann, 2004).
A cell pair consists of the following:
• Anion permeable membrane
• Concentrate spacer
• Cation permeable membrane
• Dilute stream spacer
In each stack, we can observe different flows (Figure 2):
1. Source water (feed) flows parallel only through demineralizing compartments, whereas
the concentrate stream flows parallel only through concentrating compartments.
2. As feed water flows along the membranes, ions are electrically transferred through
membranes from the demineralized stream to the concentrate stream.
3. Flows from the two electrode compartments do not mix with other streams. A
degasifier vents reaction gases from the electrode waste stream.
4. Top and bottom plates are steel blocks that compress the membranes and spacers to
prevent leakage inside the stack.
Effluent from these compartments may contain oxygen, hydrogen, and chlorine gas.
Concentrate from the electrode stream is sent to a degasifier to remove and safely dispose of
any reaction gases.
The first type of commercial ED system was the batch system. In this type of ED system,
source water is recirculated from a holding tank through the demineralizing spacers of a
single membrane stack and back to the holding tank until the final purity is obtained. The
production rate is dependent on the dissolved minerals concentration in the source water

Feed In
Concentrate In
Electrode Feed Top End Plate Electrode
waste
(-) cathode
Cation transfer
membrane
Demineralized
Flow spacer
Anion transfer
membrane
Concentrate
Flow spacer

(+) anode

Electrode Feed Bottom End Plate Electrode waste

Product
Concentrate Out

Fig. 2. Stack description (Ionics Inc., 1984)

6 Desalination, Trends and Technologies

and on the degree of demineralization required. The concentrate stream is also recirculated
to reduce wastewater volume, and continuous addition of acid is required to prevent
membrane stack scaling.
The second type of commercially available system was the unidirectional continuous-type
ED. In this type of system, the membrane stack contains two stages in series; each stage
helps demineralize the water. The demineralized stream makes a single pass through the
stack and exits as product water. The concentrate stream is partially recycled to reduce
wastewater volume and is injected with acid to prevent scaling. EDR was patented in 1969
(Mihara & Kato, 1969) and is a variation of this system which uses electrode polarity
reversal to automatically clean membrane surfaces.

2.2 Membranes
The membranes are produced in the form of foils composed of fine polymer particles with
ion exchange groups anchored by polymer matrix. Impermeable to water under pressure,
membranes are reinforced with synthetic fiber which improves the mechanical properties of
the membrane (AWWA, 1995).
The two types of ion exchange membranes used in electrodialysis are:
• Cation transfer membranes which are electrically conductive membranes that allow
only positively charged ions to pass through. Commercial cation membranes generally
consists of crosslinked polystyrene that has been sulfonated to produce –SO3H groups
attached to the polymer, in water this group ionizes producing a mobile counter ion
(H+) and a fixed charge (-SO3-).
• Anion transfer membranes, which are electrically conductive membranes that allow only
negatively, charged ions to pass through. Usually, the membrane matrix has fixed positive
charges from quaternary ammonium groups (-NR3+OH-) which repel positive ions.
Both types of membranes shows common properties: low electrical resistance, insoluble in
aqueous solutions, semi-rigid for ease of handling during stack assembly, resistant to
change in pH from 1 to 10, operate temperatures in excess of 46ºC, resistant to osmotic
swelling, long life expectancies, resistant to fouling and hand washable.
The membranes are permselective (or ion selective) that refers to their ability to discriminate
between different ions to allow passage or permeation through the membrane. In these
sense membranes can be tailored to inhibit the passage of divalent anions or cations, such as
sulfates, calcium, and magnesium. For example, some membranes show good permeation or
high transport numbers for monovalent anions, such as Cl– or NO3–, but have low transport
numbers and show very low permeation rates for divalent or trivalent ions, such as SO4–2,
PO4–3, or similar anions. This is achieved by specially treating the anion membrane, and the
effect can be exploited to separate various ions. The relative specificities vary, with the
monovalent anion membrane showing the greatest specificity, for example, the ratio of
chloride to sulfate ion transport numbers. (Xu, 2005).
It depends on the manufacturer by usually each membrane is 0.1 to 0.6 mm thick and is
either homogeneous or heterogeneous, according to the connection way of charge groups to
the matrix or their chemical structure (Xu, 2005). In the case of homogeneous membranes,
charged groups are chemically bonded and for heterogeneous they are physically mixed
with the membrane matrix. Different manufacturers of ion exchange membranes are
available in the market (Table 1). Each one offers membranes for specific applications, and
they have different properties involving, size, thickness, area resistance and composition.
Electrodialysis Technology - Theory and Applications 7

Commercial
Manufacturer/Reference Country
brand
Asahi Chemical Industry Co. Japan Aciplex
Asahi Glass Col. Ltd Japan Selemion
DuPont Co. USA Nafion
FuMA-Tech GmbH Germany Fumasep
GE Water & Process USA AR, CR,..
LanXess Sybron Chemicals Germany Ionac
MEGA a.s. Czech Republic Ralex
PCA GmbH Germany PC
Tianwei Membrane Co.Ltd. China TWAED
Tokuyama Co-Astom Japan Neosepta
Table 1. Main manufacturers of ion exchange membranes.

2.3 Spacers
The spaces between the membranes represent the flow paths of the demineralized and
concentrated streams formed by plastic separators which are called demineralized and
concentrate water flow spacers respectively. These spacers are made of polypropylene or
low density polyethylene and are alternately positioned between membranes in the stack to
create independent flow paths, so that all the demineralized streams are manifolded
together and all the concentrate streams are manifolded together too.
Demineralizing and concentrating spacers are created by rotating an identical spacer 180°.
Demineralizing spacers allow water to flow across membrane surfaces where ions are
removed, whereas concentrating spacers prevent the concentrate stream from
contaminating the demineralized stream.
There is a spacer design with a “tortuous path” in which the spacer is folded back upon it
self and the liquid flow path is much longer than the linear dimensions or the unit. Another
kind of spacers is a “sheet flow” that consists of an open frame with a plastic screen
separating the membranes. These spacers are operated at lower flow velocities, to achieve a
degree of desalting in each pass through the stack, comparable to the tortuous path or sheet
flow spacers. In general the increase of turbulence promotes mixing of the water, use of the
membrane area, and the transfer of ions. Turbulence resulting from spacers also breaks up
particles or slime on the membrane surface and attracts ions to the membrane surface. Flow
velocity ranges from (18 to 35 cm/s, creating a pressure drop between the inlet and outlet. A
velocity less than 18 cm/s promotes polarization, or the point of limiting density of water
(AWWA, 1995).
Maximum pressure for ED and EDR systems is generally limited to 50 psi (345 kPa), and
pressure is lost at each stage of the system. Since pressure must be maintained throughout
the system, the impact of spacers on pressure is an important design consideration.
Different models and sizes of spacers satisfy specific design applications. The main
difference in spacer models is the number of flow paths, which determines water velocity
across the membrane stack and contact time of the source water with the membrane. Since
water velocity is responsible for the degree of mixing and the amount of desalting that
occurs across membranes, velocity is an important design parameter for spacer choice.
Because the same spacers are used for both demineralized and concentrated water in EDR
8 Desalination, Trends and Technologies

systems, the flow rates of both these streams should be equalized to prevent high
differential pressures across the membranes.

2.4 Electrodes
A metal electrode at each end of the membrane stack conducts DC into the stack. Electrode
compartments consist of an electrode, an electrode water-flow spacer, and a heavy cation
membrane. The electrode spacer is thicker than a normal spacer, which increases water
velocity to prevent scaling. This spacer also prevents the electrode waste from entering the
main flow paths of the stack (Ionics, 1984).
Because of the corrosive nature of the anode compartments, electrodes are usually made of
titanium and plated with platinum. Its life span is dependent on the ionic composition of the
source water and the amperage applied to the electrode. Large amounts of chlorides in the
source water and high amperages reduce electrode life. Polarity reversal (as in EDR) also
results in significantly shorter electrode lifetimes than for nonreversing systems (AWWA,
1995).

2.5 Operation
When DC potential is applied across the electrodes, the following take place (AWWA, 1995):
At the cathode, or negative electrode (-):
• Cations (Na+) attraction
• Pairs of water molecules break down (dissociate) at the cathode to produce two
hydroxyl (OH–) ions plus hydrogen gas (H2). Hydroxide raises the pH of the water,
causing calcium carbonate (CaCO3) precipitation.
And at the anode, or positive electrode (+):
• Anions (Cl–) attraction
• Pairs of water molecules dissociate at the anode to produce four hydrogen ions (H+),
one molecule of oxygen (O2), and four electrons (e–). The acid tends to dissolve any
calcium carbonate present to inhibit scaling.
• Chlorine gas (Cl2) may be formed.
Colloidal particles or slimes that are slightly electronegative may accumulate on the anion
membrane and cause membrane fouling. This problem is common to all classes of ED
systems. These fouling agents are removed by flushing with cleaning systems. In EDR
systems, the polarity of the electrodes is reversed two to four times each hour. When
polarity is reversed, chemical reactions at the electrodes are reversed. Valves in the electrode
streams automatically switch flows in the two types of compartments. Streams that were in
demineralizing compartments become concentrate streams, and concentrate streams become
demineralizing streams. The alternating exposure of membrane surfaces to the product
dilute and brine concentrate streams provides a self-cleaning capability that enables
purification and recovery higher than 90% of source water, reducing the burden on water
sources, and minimizing the volume of waste that requires disposal (AWWA, 2004).

2.6 Design
In commercial practice, the basic apparatus for ED/EDR is a stack of rectangular
membranes terminated on each end by an electrode. Flow of the process streams is
contained and directed by spacers that alternate with the membranes. The membranes are
arranged alternately cation and anion. The assembly of membrane spacers and electrodes is
Electrodialysis Technology - Theory and Applications 9

held in compression by a pair of end plates. The apparatus thus resembles a plate-and-frame
filter press. Stack is completed with pumps, piping and an electrical subsystem trhat
includes: adjustable DC power supply, rectifiers to convert alternating current (AC) power
to DC power, internal control system with controls, reversal timing (only for EDR), and
alarms.
The design of an ED/EDR plant is based on the product water requeriments of the
application and the characteristic of the inlet water to be treated (Tsiakis & Papageorgiou,
2005). The parameters, which characterize the working optimum of an EDR, are the values
of the applied voltage used in the electrical stages and the feed water pressure
corresponding to the maximum separation percentage and minimum energy consumption.
These values were obtained from the surfaces corresponding to separation percentage and
consumed power versus applied voltage and pressure. It could be important to carry out a
pilot study before the industrial design of the system (Valerdi-Pérez et al., 2001). Along the
pilot study, operators had to been check the quality of the product in different conditions,
focused in the behaviour of several limiting parameters characterizing an ED/EDR system
(Ionics, 1984):
• Limiting Current Density (Polarization)
• Current Leakage
• Back Diffusion
• Langelier Saturation Index
• Calcium Sulfate Saturation
• Pressure Drop
• Differential Pressure
• Water Transfer
• Temperature Limits
With these data, ED and EDR plants can be designed to remove from 50 to 99 percent of
source water contaminants or dissolved solids. Source water salinities of less than 100 mg/L
up to 12,000 mg/L TDS can be successfully treated to produce finished water of less than 10
mg/L TDS.
To calculate the efficiency of the process during the design step, we have to take into
account the Faraday’s Law. In these sense, the passage of 96,500 amperes of electric current
for one second will transfer one gram equivalent of salt. One Faraday is equal to 96,500
ampere-second and that is equal to 26,8 amperes, of current passing for one hour. Thus,
when 26.8 ampere-hours, one gram equivalent of salt will be transferred in each cell pair, we
have a process 100 percent efficient. To determine the voltage requirements for a given
system, the current is determined from Faraday’s Law and the resistance is determined by
the components of the membrane stack and the solution under treatment, according to the
Ohm’s Law (Lee et al, 2006; Valerdi-Pérez & Ibañez-Mengual, 2001).
Typically, maximum salt removal for any hydraulic stage is 55-60 percent with normal
design values at 40-50 percent. To increase the amount of salt removal in a EDR system,
additional hydraulic stages must be incorporated. Then in systems where high capacities are
required, additional hydraulic stages are made by simply adding more stacks in series to
achieve the desired water purity (Larchet et al, 2008).
In addition, to increase water recovery some functions can be incorporated into the EDR
system to take advantage of a substantial increase in recovery and production rates at
minimal costs. In this sense, three main flows can be recycled: concentrate stream, off-
10 Desalination, Trends and Technologies

specification product and electrode stream. With those products, water can be recycled back
to the system feed, eliminating the need to send it to waste. To achieve this water recovery,
it could be necessary to dose some chemical into the system. In this sense, an antiscalant (1-
5mg/L) can be added into the concentrate stream to control calcium scaling, and acid (HCl)
is continuously feed into the electrode flow and into the concentrate stream to maintain the
Langelier Saturation Index (LSI) at +1.8 for calcium carbonate control.

3. Maintenance
Scheduled maintenance depends on the use and application of the system and varies with
each manufacturer. Nowadays, ED and EDR systems are designed with fully automated
control systems. Thus O&M procedures are scheduled to check control settings and
operating parameters, supported with detection systems that recognize operation levels or
critical conditions.
Several setpoints are implemented to operate the system. In these sense, operators check the
values and alarms related with temperature, conductivitiy, pH, current voltage, intensity,
flows and pressures. Data are collected or logged for the different streams and, in the case of
EDR, during positive or negative polarity.
It could be necessary to clean the membranes periodically. Cleaning is a means of removing
mineral scale, organic matter, biological growth (slime), colloidal particles, or insoluble
constituents which build up on the surface of the membrane. To prevent scaling and fouling,
ED and EDR units are equipped with a clean-in-place (CIP) system to allow periodic
flushing of the membrane stack and piping with an acid solution. A chemical feed pump
and storage tank form the main components of the CIP system.
In ED systems, acid is continuously fed into the electrode stream of the cathode to prevent
scaling. In EDR systems, on the other hand, electrode clean-in-place (ECIP) is a routine
preventive-maintenance procedure to remove scale or fouling from the electrode system. In
addition during the preventive maintenance a CIP process is a required procedure that
flushes scale or reversible fouling from the membrane stack and hydraulic piping. The
chemical solution circulated through the stack depends on the type of contamination. The
following chemical solutions used in the CIP process are the only chemicals that should be
used for stack cleaning (AWWA, 1995):
• Hydrochloric acid solution. Periodic cleaning with a 2 to 5 percent hydrochloric acid
(HCl) solution is the most frequently used method to remove scale and biofouling.
• Sodium chloride solution. A 3 to 5 percent NaCl solution removes organic foulants,
which are present in many surface waters, from the membranes. The solution should be
at least 3 percent NaCl (0.55N chloride) and have a pH between 8.0 and 10.0, adjusted
with NaOH. A pH greater than 11 can damage the anion membrane. This solution
should then be circulated through the system. After the NaCl application, the operator
should flush the membranes with HCl to remove excess salt.
• Chlorine solution. A 10- to 50-mg/L chlorine solution disinfects the membranes and
hydraulic piping.
The use of chlorine is one of the advantatges of ED/EDR membranes in front of other
membranes technologies. They can operate on waters with up to 0.5 mg/L chlorine to
control the biological nature of feed water, and can be shock-chlorinated up to 30 mg/L for
maximum cleaning efficiency if required. Additionally, ED/EDR presents some other
advantages, for example it is possible to repair and disassembly the stack and if it is
Electrodialysis Technology - Theory and Applications 11

necessary, it easy to manually clean the membranes or replaced them. In these cases, stacks
should not be allowed to remain dry for long periods of time because membranes may
become damaged. Generally, disassembly requires that each piece be removed separately,
with the exception of the top electrode, which can be replaced without the removal of any of
the membranes. It is important to maintain correct component orientation and to store
membranes in water. The stack should be rebuilt in the order it was disassembled; incorrect
assembly can reduce performance or cause scaling.
Besides the cleaning procedure, the most frequent manual operation is to check the
intermembrane voltage to prevent “hot spots” or current leakage. The intermembrane
voltage has to be similar along the entire stack, and operators had to check it frequently.
Excess current can melt or “burn” the membranes and spacers. Normal design practices
limit this voltage to 80% of the current that would cause burning. The limits is determined
by water temperature, conductivity of the source water, membrane stack size, and the
internal manifold that splits flow into concentrate and dilute streams. When operators find
increases of current in a located point, they had to check the voltage along some days to
prevent a “hot spot”.

4. EDR vs RO
Most of desalting processes are related with membrane pressure technologies in general and
especially with RO. In this way, RO represents a worldwide solution for many desalination
problems, but EDR could be a cost effective solution for many industrial applications of
different size (Strathmann, 2010). The RO process requires extensive pretreatment, higher
pumping power and more chemicals. RO also has a lower water recovery rate if the water
has positive scaling tendencies.
Only EDR could be innapropiate in two cases: desalting sea water directly as drinking water
(because is not cost effective) and if the problem to solve is a microbiological contamination
(because EDR not provides a barrier effect). In the case of the emerging contaminants, it will
depend of the chemical status of each compound, and it needs to check it.
Then it is possible to point out some advantatges in favour of EDR in comparison with RO.
Most of these advantages are included in O&M tasks, and are listed below (Strathmann,
2004, GE W&P, 2010):
1. The EDR system does not require high feedwater quality and is less sensitive to pre-
treatment problem in comparison with an RO system. EDR system is able to operate
with Silt Density Index (SDI) average of 12 compared to 3 for the RO system. High SiO2
content water can be treated without forming precipitation on ion exchange membranes
2. The EDR system is capable of operating with a continuous free chlorine residual of up
to 1 ppm. The RO system will require a dechlorination process to protect RO membrane
from degradation by free chlorine oxidation. The EDR ability to operate with chlorine
residual minimises biological fouling of the membrane in a more reliable system.
3. The EDR system has a nominal initial brackish water recovery in the range of 80%-90%.
The RO system normally has a water recovery in a much lower range, 65%-75%. The
high EDR water recovery reduces this project's feedwater usage and wastewater
discharge cost.
4. The EDR membrane is not attacked by bacteria or affected by high temperatures.
Therefore no special storage solutions are necessary for long term storage. The RO
system requires special storage solutions and controlled storage temperatures. The EDR
12 Desalination, Trends and Technologies

membrane can be cleaned with acid and brine/caustic flush while the RO membrane
requires special and expensive cleaning chemicals. It is important to determine if these
chemicals can be discharged to the environment without further treatment.
5. The EDR rugged thick membrane technology has ensured membrane life of 7 to 10
years. The RO membrane is designed for 5-7 years due to the membrane sensitivity to
various operating factors.
6. The reversal feature of the EDR system controls membrane scaling with no chemical
addition. The RO system requires the addition of acid and a sequestering agent. The
resulting waste from the RO system is highly acidic requiring caustic neutralisation and
may not be discharged to the environment.
7. The EDR membrane can be manually cleaned without damaging the membrane
properties. This is due to the "plate and frame" configuration. The RO membrane has a
spiralwound configuration, it can not be cleaned manually, and therefore it must be
replaced.

5. Applications
Over the last ten to fifteen years, numerous advances in membrane and system technology
have made EDR an especially attractive technology, both in terms of performance and cost-
effectiveness.
Many applications of EDR technology can be founded worldwide. From small installations
that have only one stack to the biggest one equipped with 576 stacks. Diferent suppliers and
applications are involved. Desalting process is applied mainly to brackish water process,
tertiary wastewater production and specific industrial applications, ranging from mining to
pharmaceutical and food & beverages industries.
Table 2, shows a list of some of the worldwide industrial installations. Diferent suppliers
and membrane manufacturers are available. The biggest supplier is General Electric Water

3
LOCATION COUNTRY APPLICATION Production m /d YEAR

EURODIA
Montefano Italy Groundwater Nitrate removal 1.000 1991
Munchenbuschsee Switzerland Groundwater Nitrate removal 1.200 1996
Kleylehof Austria Groundwater Nitrate removal 3.500 1997
GENERAL ELECTRIC WATER & PROCESS (fomerly ionics Inc)
Abrera, BCN SPAIN Surface water bromide reduction 200.000 2008
Magna, Utah USA Groundwater As, Perchlorate reduction 22.728 2008
Sherman, Texas USA Surface water salinty reduction 27.700 1993-96-98
Suffolk, Virginia USA Groundwater Fluoride reduction 56.000 1990
Sarasota, Or USA Groundwater Hardness & salts reduction 45.420 1995
Maspalomas SPAIN Groundwater salinty reduction 37.000 1986
Barranco Seco, Canary Is. SPAIN Waste Water Reuse 26.000 2002
Bermuda WaterWorks Bermudas Groundwater Hardness & Nitrate reduction 2.300 1989
Falconera, Valencia SPAIN Groundwater Nitrate reduction 16.000 2007
MEGA a.s.
Sant Boi, BCN SPAIN Waste Water salinty reduction 55.296 2010
Dolni Rozinka Czech Rep. Uranium mining Desalination of sludge 1.752 2007
ZIAR nad HRONOM Slovakia Waste water Desalination of sludge 350 2003
Arak Iran Waste water cooling tower 4.800 2008 -10
Alberta Canada Well water Gas well water desalination 40 2008

Table 2. Some worldwide EDR systems

Electrodialysis Technology - Theory and Applications 13

& Process (USA), that adquired Ionics Inc. in 2004. Ionics Inc. developed the first ED
commercial system in the 1950s (Juda and Mc Rae, 1950). Now is it possible to use differents
suppliers of this technology, involving the whole system, or associated with membrane
manufacturers as internal suppliers. In this sense, could cite: MEGA (Czech Republic),
Eurodia (France), Hydrodex (Brasil) and Tecnoimpanti (Italy).

6. Case studies
We show two technical cases involved the biggest EDR plants for drinking water and reuse
water for agricultural applications, respectively. Both are located near Barcelona (Spain).
The first one is the Abrera Drinking Water Treatment Plant (DWTP) and the second the
Depurbaix Waste Water Treatment Plant (WWTP).

6.1 Case study 1: The Abrera DWTP.

The Llobregat and the Ter rivers, typical Mediterranean catchments in Northeast Spain,
supply water to more than 4.5 millions inhabitants residing in the metropolitan area of
Barcelona. Aigües Ter Llobregat (ATLL) a public company of the Autonomous Government
of Catalonia has been appointed to manage the system that includes two DWTP and one sea
water reverse osmosis (SWRO) plant, with a whole capacity of continuous treatment of
14 m3/s.
The Abrera DWTP takes raw water directly from the Llobregat River. It presents a low and
irregular flow and some quality problems such as high salinity with a significant presence of
sulphates, Ba2+, Sr2+, Na+, Ca2+, K+, Cl- and specially Br- (Fernández-Turiel et al., 2000).
Furthermore, many problems are associated with the increase in micropollutant and
microbiological levels due to both urban and industrial sewage. These problems produce
many interruptions of the process, some of them lasting many hours. Consequently, the
high levels of bromide (ranging between 0.5-1.2 mg/L), NOM and T, produce high
concentrations of trihalomethanes (THMs) after chlorination (Chang et al., 2001; Rook, 1977),
showing a high brominated profile.
The total THMs represent the sum of the concentrations of four THMs; chloroform (CHCl3),
bromoform (CHBr3), bromodichloromethane (CHBrCl2), and dibromochloromethane
(CHBr2Cl). They have been regulated since 1998 in the European Union (Council Directive
98/83/CE), and in Spain since 2003, with a parametric value of 100 µg/L established in 2009
(Real Decreto 140/2003).
To minimize the THMs problem, ATLL searched for a new technology based on a membrane
process. In this sense, the concern about THMs at the Llobregat DWTP has to do with
changes in the treatment process, starting with enhanced coagulation in 1994, followed by
the inclusion of a new step of GAC filtration in 1995, after sand filters. Subsequently, several
changes have been carried out to improve the process. In 1999 ATLL carried out some trials
using a pilot plant of Reverse Osmosis (RO) during a period of 6 months. The study showed
that RO technology had a low recovery and certain instability due to the frequent
shutdowns of the process because of the poor quality of raw water (floods, high turbidity,
high fouling potential, chemical pollution…). Additional problems were the sensibility to
high concentrations of sulphates, barium, calcium, alumina, and the disinfectant chlorine,
that can be used at different points of the process. Later, to assess the reduction of the salts
concentration (Kimbrough & Suffet, 2005) and consequently the THMs-Formation Potential
(THMs-FP, 25ºC, 48h), a pilot study was carried out during 28 months using a pilot plant of
14 Desalination, Trends and Technologies

EDR technology. Results showed that the EDR step improved the chemical and aesthetic
quality of drinking water (Devesa et al., 2009, García et al., 2010) and allows a THMs-FP
after 48h that is lower than the regulated level of 100 µg/L (Valero et al., 2007).
The final decision was the enlargement of the plant production from 3 m3/s to 4m3/s and
the inclusion of a new EDR step after Granular Activated Carbon (GAC) filtration, with a
production capacity of 2.3 m3/s. EDR takes feedwater from GAC step by means of a
derivation of filtered water pipeline.
In addition, EDR permeates are aggressive showing a pH ranged between 6.5 and 7.3 and a
LSI that varies between –1 and -2. Thus, a remineralization step is necessary, to supply EDR
product water without blending with GAC filtered water. In this sense remineralization of
EDR produced water was applied using lime contactors and CO2 dosing. Only if the quality
of raw water makes it possible, conventional treatment will be blended to produce up to 4
m3/s.
This plant is the world's largest desalination plant using this technology, and a new example
of a large scale application of a desalting technology to improve the quality of drinking
water. The work was carried out by the Spanish temporary consortium SACYR-SADYT
using EDR technology provided by General Electric Water&Process.
The main characteristics of the DWTP are:
• Conventional process: pre-oxidation with potassium permanganate, coagulation,
flocculation, oxidation with chlorine dioxide, sand filtration, GAC filtration and final
chlorination using chlorine gas.
• Average current flow supplied by the DWTP: 2.3 m3/s. Maximum extended flow of the
DWTP: 4 m3/s
Design of EDR's Stage:
• Maximum flow treatment : 2.3 m3/s (58 MGD)
• Range conductivity inlet water: 900-3000 µS/cm.
• Temperature range inlet water: 5-29 ºC
• Pump station : 9+3 pumps of 1030m3/h to 60 mca
• Cartridge filters: 18 filters with 170 cartridges each of 50 inches and 5 µm.
• 9 modules with 576 stacks wit 600 cell pairs each one, in double stage.
• Homogeneous membranes: AR204 (anionic) and CR67 (cationic)
• Wet technology.
• Voltage range: 340-450 V 1st stage, 320-390 V 2nd stage.
• Bromides reduction: 60-80 %
• Conductivity reduction: 60-80 %
• Maximum volume of brines: 154 Tm/d, sent via a pipeline to the sea at the mouth of the
Llobregat River.
• Water recovery>90% (including off-spec and concentrate recycle).
• Remineralization (when necessary) with Ca(OH)2 up to 7 Tm/d and CO2.
Every module is provided with reversing systems of flow for the changes of polarity,
automatic valves and pumps equipped with electronic frequency variators that allow a full
automated system. EDR process is operated according with the levels of THMs expected in
the final drinking water. Then 1 to 9 modules were worked when necessary to blend with
conventional treatment product to get the THMs levels at the lower cost.
The plant started operating on a trial basis in June 2008, and came into the normal operation
from April 2009. Along the period April, 2009 to August, 2010, more than 20 hm3 had been
Electrodialysis Technology - Theory and Applications 15

Fig. 3. Details of the EDR step at the Abrera DWTP.

produced through the EDR line. THMs's average values in the water product of the DWTP
ranged between 40 and 60 µg/L. The energetic average consumption for the EDR process
(stacks and pumps) has been lower than 0.6 kWh/m3. During the indicated period the
hydraulic performance has been higher than 90%, with a reduction of salts (measures like
conductivity) higher than 80% in summer. Specifics consumptions of HCl were of 0.08 Kg
HCl/m3 and for antiscalant in the rejection of brine 0,002 Kg/m3 (Valero et al., 2010)
Due to the large size of the industrial plant, additional R&D studies will be focused on O&M
procedures. Maintenance related to cleaning membranes and spacers, the measure of the
inter-membranes voltages and “hot spots” detection, would be simplified using specific
tools designed by the technical staff.
The cost of the new enlargement project was 61,218,478€. Given the considerable interest of
these works, their repercussion on the quality of the supply and the technology used, a
subsidy of 85% of the budget of the works was obtained from European Union funds.

6.2 Case study 2: The Depurbaix WWTP.

The project is located in Sant Boi de Llobregat, near Barcelona. It is a brackish water
desalination facility for some of the effluent treated in the Depurbaix WWTP, which
produces more than 57,000 m3/d using EDR technology (Segarra et al., 2009).
The facility is one of the largest in the world that treats wastewater for agricultural use. The
work was carried out by the Spanish temporary consortium BEFESA-ACSA using EDR
technology provided by MEGA a.s.
The main characteristics of the EDR system are:
• Inlet water: tertiary treatment of the WWTP + anthracite/sand filters. Average
conductivity 3.040 µS/cm
• Expected EDR product water: 55,296 m3/d.
• Expected plant product water after blending: 57,024 m3/d.
• Pump station : 2+1 pumps
16 Desalination, Trends and Technologies

• Cartridge filters: 4 filters with 300 cartridges each one (20 µm).
• 4 modules with 96 stacks with 600 cell pairs each one, in double stage.
• Heterogeneous ion-exchange membranes: RALEX AM(H) (anionic) and CM(H)
(cationic)
• Dry technologie
• Conductivity reduction: 60-80 %
• Water recovery>85%.
The plant started operating on a trial basis in January 2010 and came into the normal
operation from September 2010. The full automatic modular system allows the operation
according to the expected use of the product water.

Fig. 4. EDR stacks at the Depurbaix WWTP.

7. Discussion
In recent years membrane technology has become an important useful tool for the
desalination of seawater, the use of brackish water and polluted water resources which were
not suitable for producing drinking water, and for the physicochemical and microbiological
improvement of the water obtained by conventional treatment.
Based in the important advantatges of ion-exchange membranes (rugged, resistant to
organic fouling, chlorine stable, broad range for pH and Temperature,..) compared with
other membranes technologies, the improvement of EDR allows to use it for many
applications that are cost effective than other technologies with a better commercial
marketing like UF or RO. Maybe the use of EDR still has a label of a technology to solve
local problems involving small communities or specific industrial applications. However,
during last years big systems are in operation showing good performances and cost effective
results. In this sense the T. Maybry Carlton WTP located at Sarasota (FL, USA) was pioneer
in operate a big system since 1995. In that case, EDR was selected due to its ability to
Electrodialysis Technology - Theory and Applications 17

maximize recovery of freshwater and minimize wastewater volume. The plant produces
45.420 m3/d and is equipped with 320 stacks. Later, improvement of EDR allows installing
more systems worldwide, some of them in Spain related with drinking water and water
reuse. EDR was introduced in the Canary Islands during the 80’s, but during lasts years
some big facilities were building in the Spanish Mediterranean area: two plants (16,000
m3/d each) in Valencia to reduce nitrate levels and two more in Barcelona: the first to
reduce bromide levels and then the THMs formation (200.000 m3/d, 576 stacks) and the last
to reduce salinity for reuse water for irrigation (55.296 m3/d, 96 stacks).
In addition, desalination of brackish water using membranes technologies like ED and
specially EDR it is a cost effective method to supply good quality drinking water water and
could be a good solution for some industrial water utilities. Besides, EDR systems now are
simpler and more reliable, which means that the demineralization of difficult-to-treat water
is easier for municipalities to handle. In addition, the costs are becoming easier to swallow.
Some aspects could be improved in a near future: spacer configuration, membranes
chemistry, materials and configuration of electrodes, specific antiscalants for EDR,
elimination of degasifiers and the increase of the production of the stacks.
Finally, there are some interesting works related with the use of hybrid systems to get
synergies between technologies (Turek, 2002; Kahraman, 2004), and some innovations are
under study to improving the EDR technology (Balster et al., 2009; Charcosset, 2009; Ortiz et
al., 2008; Turek et al., 2008; Veerman et al., 2009).

8. Conclusions
• EDR should be effectively applied for water and salt recovery from an industrial
effluent for pollution prevention and for resource recovery.
• The growing popularity among municipalities of the EDR systems is related with its
capacity to reduce TDS and some inorganics elements like nitrates, sulphates, radon,
bromides and others, with high water recovery and easily operation and control by
adjusting amount of electricity applied to membrane stack.
• The correct operation of big EDR systems, compared with classical membrane pressure
systems like RO, allows extending EDR to new cost effective applications.
• Future steps of EDR systems could improve the design of membranes and spacers as
well as a more compact design, lowering the capital and O&M costs.
• EDR could be in a near future the technology of choice for many applications because
its efficiency to desalt water needed in differents fields like drinking water, reuse water
and many industrial applications, like food, beverages and mining among others.
• Hybrid systems between different membranes technologies including EDR, could be
useful solutions for specific applications, and could improve recovery and reduce
waste.

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Veerman J., Saakes M., Metz, S.J. & Harmsen, G.J. (2009).Reverse elecrodialysis: Performance
of a stack with 50 cells on the mixing of sea river water. J. Memb. Sci. 327: 136-144.
Winger, A.G., Bodamer, G.W. & Kunin, R. (1953) Some electrochemical properties of new
synthetic ion exchange memebranes. J. Electrochem. Soc. 100: 178.
Xu, T. (2005). Ion exchange membranes: state of their development and perspective. J.
Memb. Sci. 263:1-29.
 2

Water Desalination by Membrane Distillation

Marek Gryta
West Pomeranian University of Technology, Szczecin
Poland

1. Introduction
Water is the most common substance in the world, however, 97% is seawater and only 3% is
fresh water. The availability of water for human consumption is decreasing due to
increasing the environmental pollution. According to the World Health Organisation
(WHO), about 2.4 billion people do not have access to basic sanitation facilities, and more
than one billion people do not have access to safe drinking water (Singh, 2006). Moreover,
the world’s population is expected to rise to nine billion from the current six billion in the
next 50 years. Chronic water pollution and growing economies are driving municipalities
and companies to consider the desalination as a solution to their water supply problems.
Generally, desalination processes can be categorized into two major types: 1) phase-
change/thermal and 2) membrane process separation. Some of the phase-change processes
include multi-stage flash, multiple effect boiling, vapour compression, freezing and solar
stills. The pressure driven membrane processes, such as reverse osmosis (RO), nanofiltration
(NF), ultrafiltration (UF) and microfiltration (MF), have found a wide application in water
treatment (Charcosset, 2009).
The energy required to run desalination plants remains a drawback. The energy limitations
of traditional separation processes provided the impetus for the development and the
commercialisation of membrane processes. Membrane technologies (simple, homogenous in
their basic concepts, flexible in application), might contribute to the solution of most of the
existing separation problems. Nowadays, membranes are used for the desalination of
seawater and brackish water, potable water production, and for treating industrial effluents.
RO membrane separation has been traditionally used for sweater desalination (Charcosset,
2009; Schäfer et al., 2005; Singh, 2006).
One of the limitations of membrane processes is severe loss of productivity due to
concentration polarisation and fouling or scaling (Baker & Dudley, 1998; Schäfer et al., 2005).
Membrane pretreatment processes are designed to minimise the potential problems of
scaling resulting from the precipitation of the slightly soluble ions. Membrane (MF or UF)
pretreatment of RO desalinations plants is now a viable options for removing suspended
solids, fine particles, colloids, and organic compounds (Banat & Jwaied, 2008; Singh, 2006).
NF pretreatment of sweater is also being used to soften RO feed water instead of traditional
softening (Schäfer et al., 2005).
The industrial development of new membrane processes, such as membrane distillation
(MD), is now being observed (Banat & Jwaied, 2008; Gryta, 2007). In MD process feed water
is heated to increase its vapour pressure, which generates the difference between the partial
22 Desalination, Trends and Technologies

pressure at both sides of the membrane (El-Bourawi et al., 2006). Hot water evaporates
through non-wetted pores of hydrophobic membranes, which cannot be wetted by liquid
water (Gryta & Barancewicz, 2010). The passing vapour is then condensed on a cooler
surface to produce fresh water (Alklaibi & Lior, 2005; Charcosset, 2009). In the case of
solutions of non-volatile substances only water vapour is transported through the
membrane. Thus, MD process has a potential application for the water desalination and the
treatment of wastewater (Banat et al., 2007; El-Bourawi et al., 2006; Wang, et al., 2008). The
MD has a significantly lower requirements concerning pretreatment of feed water, therefore,
it enables the production of pure water from water sources, the quality of which impedes a
direct application of the RO for this purpose. However, the feed usually contains various
impurities, which in turn lead to the formation of deposit (Gryta, 2008). Deposits both
pollute surfaces of membranes and make it easier for water to penetrate membrane pores
(Gryta, 2007b; He et al., 2008). Consequently, membranes lose their separation properties
and the MD process stops. This is why it is essential to prevent formation of deposits on the
membrane surfaces.

2. Principles of membrane distillation

An expanded definition of MD process was created in 1986 at the “Workshop on Membrane
Distillation” in Rome (Smolder & Franken, 1989). The term “Membrane Distillation” should
be applied for membrane operations having the following characteristics:
- the membrane should be porous and not be wetted by the process liquids;
- no capillary condensation should take place inside the pores of the membrane;
- only vapour should be transported through the pores;
- the membrane must not alter the vapour-liquid equilibrium of the different components
in the process liquids;
- at least one side of the membrane should be in direct contact with the process liquid;
- the driving force for each component is a partial pressure gradient in the vapour phase.
In membrane distillation heat is required to evaporate the feed components, therefore, in
such context (similarly as in the classical distillation) it can be concluded that MD is a
thermal-diffusion driven process. However, it operates at low temperatures (323-363 K),
therefore, the feed water can be heated be using renewable energy (Banat & Jwaied, 2008).
The MD is carried out in various modes differing in a way of permeate collection, the mass
transfer mechanism through the membrane, and the reason for driving force formation
(Gryta, 2005; Smolder & Franken, 1989). These differences were taken into consideration in
the nomenclature by the addition to the term “Membrane Distillation” the words, which
emphasised a feature of a given variant. Various types of MD are known for several years
(Fig.1): direct contact MD (DCMD), air gap MD (AGMD), sweeping gas MD (SGMD) and
vacuum MD (VMD). DCMD variant is the most frequently studied and described mode of
MD process (Alklaibi & Lior, 2005; El-Bourawi et al., 2006; Gryta, 2010; Wang, et al., 2008).
Several theoretical mass transfer models have been presented to describe membrane
distillation. The models of DCMD were based on the assumption that vapour permeates
through the porous membrane, as a result of molecular diffusion, Knudsen flow and/or the
transition between them (Alklaibi & Lior, 2005; El-Bourawi et al., 2006; Gryta, 2008). Using
the Stefan-Maxwell model diffusion of vapour through the air layer, the permeate flux can
be described as proportional to the membrane permeability and water partial pressure
difference (Alklaibi & Lior, 2007; Gryta et al., 1998):
Water Desalination by Membrane Distillation 23

ε D WA M W P
JV = (pF − pD ) (1)
χ s m R Tm p in

where pF and pD are the partial pressures of the saturated water vapour at interfacial
temperatures T1 and T2; ε , χ, sm, MW, R, Tm, P, DWA and pin are membrane porosity, pore
tortousity, membrane thickness, molecular weight, gas constant, membrane temperature,
total pressure, vapour diffusion coefficient and air concentration inside the pores,
respectively.

A) B)

Cooling
seawater
seawater

water
distillate

vapour
Cold

Hot
Hot

membrane membrane

C) D)
Sweeping
gas
vacuum
seawater

seawater
Hot

Hot

Vapour

Vapour

Fig. 1. Types of membrane distillation: A) DCMD, B) AGMD, C) VMD, D) SGMD

In MD process the mass transfer (JV) occur simultaneously with heat conduction (Q) across
the membrane material, and as a results, the temperature of the boundary layer on the feed
side is lower, whereas on the distillate side it is higher than that of the bulk (Fig.2). This
phenomenon is termed as the temperature polarization (Martínez-Díez & Vázquez-
González, 1999). It causes the decrease of vapour pressure difference across the membrane
which leads to the reduction of the magnitude of the mass flux (permeate) flowing through
the membrane. The interfacial temperatures T1 and T2 cannot be measured directly. Several
equations used to calculate these temperatures have been presented in the MD literature
(Gryta et al., 1998; Khayet et al., 2004; Srisurichan et al., 2006). Their values depend in
essential way on the conditions of a heat exchange in the MD module. Thus the correct
description of the heat transport across the membrane will determine the accuracy of the
mathematical calculation of MD process run (El-Bourawi et al., 2006; Gryta et al., 1998;
Gryta, 2008).
24 Desalination, Trends and Technologies

pF Δp
pD
JV
TF
T1 ΔΤ
T2
TD

Distillate
Feed
Q

membrane

Fig. 2. Principles of DCMD: T1, T2, TF, TD — temperatures at both sides of the membrane,
and temperatures of feed and distillate, respectively; pF, pD — water vapor partial pressure
at the feed and distillate sides, respectively

2.1 Membranes and modules

The porous and hydrophobic MD membranes are not selective and their pores are filled
only by the gas phase. This creates a vapour gap between the feed and the produced
distillate, what is necessary for MD process operation. However, during the MD a part of
the membrane pores may be wetted, that decreases a thickness of vapour gap inside the
membrane wall (Gryta & Barancewicz, 2010). Therefore, the properties of membrane
material and membrane porous structure are important for MD process performance
(Bonyadi & Chung, 2009; Khayet et al., 2006).
Membrane for MD process should be highly porous, hydrophobic, exhibit a desirable
thermal stability and chemical resistance to feed solution (El-Bourawi et al., Gryta et al.,
2009). These requirements are mostly fulfilled by the membranes prepared from polymers
with a low value of the surface energy such as polytetrafluoroethylene (PTFE),
polypropylene (PP) or poly(vinylidene fluoride) (PVDF) (El Fray & Gryta, 2008; Gryta, 2008;
Li & Sirkar, 2004; Teoh et al., 2008; Tomaszewska, 1996). Apart from the hydrophobic
character of the membrane material, also the liquid surface tension, pores diameter and the
hydraulic pressure decide about the possibility of the liquid penetration into the pores. This
relation is described by the Laplace – Young (Kelvin law) equation (Schneider et al., 1988):

−4 B σ cos Θ
ΔP = PF − PD = (2)
dp

where: ΔP is liquid entry pressure (LEP), B is the pore geometry coefficient (B = 1 for
cylindrical pores), σ is the surface tension of the liquid, Θ is the liquid contact angle, dP is the
diameter of the pores, PF and PD are the hydraulic pressure on the feed and distillate side,
respectively. Water and the solutions of inorganic compounds have high surface tension (σ
> 72x10–3 N/m), however, when the organics are present, its value diminishes rapidly. Thus,
taking into consideration the possibility of membrane wetting, it is recommended that for
MD the maximum diameter of membrane pores does not exceed the 0.5 μm (Gryta, 2007b;
Gryta & Barancewicz, 2010; Schneider et al., 1988).
Water Desalination by Membrane Distillation 25

Hydrophobic polymers are usually low reactive and stable, but the formation of the
hydrophilic groups on their surface is sometimes observed (Gryta et al., 2009). The surface
reactions usually create a more hydrophilic polymer matrix, which may facilitate the
membrane wettability (El Fray & Gryta, 2008; Khayet & Matsuura, 2003). The amount of
hydrophilic groups can be also increased during MD process and their presence leads to an
increase the membrane wettability (Gryta et al., 2009; Gryta & Barancewicz, 2010).
The application of membranes with improved hydrophobic properties allows to reduce the
rate of membrane wettability. Blending of PTFE particles into a spinning solution modified
the PVDF membrane, and enhances the hydrophobicity of prepared membranes (Teoh &
Chung, 2009). Moreover, the resistance to wetting can be improved by the preparation of
MD membranes with the uniform sponge-like membrane structure (Gryta & Barancewicz,
2010).
Apart from membrane properties, the MD performance also depends on the module design.
The capillary modules can offer several significant advantages in comparison with the plate
modules (flat sheet membranes), such as a simple construction and suppression of the
temperature polarization (El-Bourawi et al., 2006; Gryta, 2007; He et al., 2008; Li & Sirkar,
2004; Teoh et al., 2008). The efficiency of the MD capillary module is significantly affected by
the mode of the membranes arrangement within the housing (Fig. 3).

M3
500

M2
Permeate flux, JV [dm3/m2d]

400

300

200
M1

100

0
330 340 350 360 370
Feed temperature, TF [K]

Fig. 3. The influence of feed temperature and the mode of membrane arrangement in a
capillary module on the permeate flux. M1 - bundle of parallel membranes; M2 - braided
capillaries; and M3 – capillaries mounted inside mesh of sieve baffles
The driving force for the mass transfer increases with increasing the feed temperature,
therefore, the permeate flux is also increased at higher feed temperatures. A traditional
construction (module M1) based upon the fixation of a bundle of parallel membranes solely
at their ends results in that the membranes arrange themselves in a random way. This
creates the unfavourable conditions of cooling of the membrane surface by the distillate,
which resulted in a decrease of the module efficiency. In module M3 the membranes were
26 Desalination, Trends and Technologies

positioned in every second mesh of six sieve baffles, arranged across the housing with in
0.1–0.15 m. The most advantageous operating conditions of MD module were obtained with
the membranes arranged in a form of braided capillaries (module M2). This membrane
arrangement improves the hydrodynamic conditions (shape of braided membranes acted as
a static mixer), and as a consequence, the module yield was enhanced.

2.2 MD process efficiency

Although the potentialities of MD process are well recognised, its application on industrial
scale is limited by the energy requirements associated. Therefore, high fluxes must be
obtained with moderate energy consumption. DCMD has been widely recognised as cost-
efficient for desalination operating at higher temperatures, when waste heat is employed to
power the process (Alklaibi & Lior, 2005). The performance of membrane distillation mainly
depends on the membrane properties, the module design and it operating conditions (Bui et
al., 2010; Li & Sirkar, 2004).
Concerning the operating conditions (Figs. 3 and 4), the feed temperature has the most
significant influence on the permeate flux, followed by the feed flow rate and the partial
pressure established at the permeate side. This last depending on the distillate temperature
for DCMD and on the vacuum applied for VMD (Criscuoli et al, 2008; El-Bourawi et al.,
2006).
The results presented in Fig. 4 confirmed that the distillate velocities had a minor role in
improving the mass transfer, but a distillate velocity below 0.3 m/s would cause a rapid
decrease in mass flux (Bui et al., 2010). Moreover, Bui et al. were indicated, that the distillate
temperature has had a significant greater influence on DCMD energy efficiency. It is known
that decreasing the water temperature from 283 to 273 K results in a very small an increase
of mass driving force. Therefore, it is recommended that the DCMD process be operated at a
distillate temperature higher than 283 K.

800

700
Permeate flux JV [dm3/m2d]

600

vD [m/s]:
500 - 0.26
- 0.38
400 - 0.72

300
0.2 0.4 0.6 0.8 1
Feed flow rate, vF [m/s]

Fig. 4. The effect of the flow rate of streams in a module with braided membranes (module
M1) on the permeate flux. TF = 353 K, TD = 293 K
Water Desalination by Membrane Distillation 27

The viability of MD process depends on an efficient use of available energy. The heat
transfer inside the membrane (Q – total heat) takes place by two possible mechanisms, as
conduction across the membrane material (QC) and as latent heat associated with vapour
flowing through the membrane (QV). The heat efficiency (ηT) in the MD process can be
defined by Eq. 3.

QV QV
ηT = = (3)
Q QV + QC

The heat transfer which occurs in MD module leads to a cooling of the hot feed and to a
heating of the distillate. Therefore, in the DCMD process it is necessary to supply heat to the
hot stream and to remove heat from the distillate stream. The heating and the cooling steps
represent the energy requirements of the DCMD process.
The amount of heat exchanged in the MD module increases along with an increase of the
feed temperature (Fig. 5). However, under these conditions the permeate flux also increases,
which causes the limitation of heat losses (heat conducted through the membrane material).
As a results, an increase in the module yield influences on the enhancement of heat
efficiency of the MD process (Fig. 6). For the highest permeate flux the ηT coefficient equal to
0.75 was obtained. It was concluded that energy efficiency of DCMD process could be
maximised if the process were operated at the highest allowable feed temperature and
velocity (Bui et al., 2010). A nonuniform arrangement of the capillary membranes in the
module housing (module M1) caused a decrease in the energy consumption efficiency.
The unitary energy consumption in the MD process decreases along with temperature of
feeding solution. This consumption was reduced from 5000 to 3000 kJ per 1 kg of obtained
distillate when the feed temperature increased from 333 to 363 K (Gryta, 2006).
A decrease of the membrane wall thickness significantly increases the obtained permeate
flux. However, during the MD process the liquid systematically wetted the consecutives
pores, which reduced the thickness of the air-layer inside the membrane wall. In this

500 20
TD= 293 K
- module M1
Permeate flux, JV [dm3/m2d]

18
400 - module M2
Total heat, Q [kW/m2]

16
300 14

200 12

10
100
8

0 6
330 340 350 360 370
Feed temperature, TF [K]
Fig. 5. Effect of feed inlet temperature and mode of membrane arrangement (M1 - parallel,
irregular, M2 – braided membranes) on permeate flux and heat transfer in DCMD
28 Desalination, Trends and Technologies

6 T = 293 K 0.8
D
– module M1

Heat conducted, QC [kW/m2]

– module M2
5 0.7

Heat efficiency, ηT
4 0.6

3 0.5

2 0.4
330 340 350 360 370
Feed temperature, TF [K]

Fig. 6. Effect of feed temperature and mode of membrane arrangement (M1 - parallel,
irregular, M2 – braided membranes) on heat conducted and heat efficiency in DCMD
situation, the membranes having a thin wall will be wetted in a relatively short time.
Therefore, the hydrophobic membranes with thicker walls are recommended for
commercial DCMD applications (Gryta & Barancewicz, 2010).

3. Membranes fouling
Fouling is identified as a decrease of the membrane permeability (permeate flux) due to
deposition of suspended or dissolved substances on the membrane surface and/or within
its pores (Schäfer et al., 2005). Several types of fouling can occur in the membrane systems,
e.g. inorganic fouling or scaling, particulate and colloidal fouling, organic fouling and
biological fouling (Baker & Dudley, 1998; Singh, 2006; Srisurichan et al., 2005). Scaling
occurs in a membrane process when the ionic product of sparingly soluble salt in the
concentrate feed exceeds its equilibrium solubility product. The term scaling is commonly
used when the hard scales are formed (e.g. CaCO3, CaSO4) (He et al., 2008; Lee & Lee, 2000).
Fouling is also one of the major obstacles in MD process because the deposit layer formed
on the membrane surface may cause membrane wetting. This phenomenon will certainly be
accelerated if the salt crystals were formed inside the pores (Alklaibi & Lior, 2005; Gryta,
2002; Gryta, 2007; Tun et al., 2005).
The possible origins of fouling in MD process as follows: chemical reaction of solutes at the
membrane boundary layer (e.g. formation of ferric hydroxides from soluble forms of iron),
precipitation of compounds which solubility product was exceeded (scaling), adsorption of
organic compounds by membrane-forming polymer, irreversible gel formation of
macromolecular substances and colonization by bacteria and fungi (Gryta, 2002; Gryta,
2005b; Gryta, 2007; Gryta, 2008). The operating conditions of membrane distillation
restricted the microbial growth in the MD installation; therefore, one should not expect the
problems associated with biofouling in the degree encountered in other membrane
processes such as UF, NF or RO (Gryta, 2002b).
A large influence on the fouling intensity has a level of feed temperature. During concentration
of bovine serum albumin aqueous solution by DCMD was found that fouling was practically
Water Desalination by Membrane Distillation 29

absent in the process operated at low temperature (i.e. 293–311 K) (Ortiz de Zárate et al., 1998).
On the contrary, a severe fouling by proteins was observed at higher feed temperatures (Gryta
et al., 2001; Gryta et al., 2006c). The CaCO3 scaling is also increased with an increase of the feed
temperature. As a result of feed heating the HCO3– ions, present in the water, undergo the
decomposition and a significant amount of CaCO3 precipitates on the membrane surface
(Drioli et al., 2004; Karakulski & Gryta, 2005; Gryta, 2005b; Schneider, et al., 1988). Although
the acidification of feed water to pH 4 limited CaCO3 scaling in the MD process, a slight
fouling caused by other compounds (such as silicates), was still observed (Karakulski & Gryta,
2005). The foulants concentration may be reduced in the pretreatment stage, e.g. by using the
NF or RO processes (Karakulski et al, 2002; Gryta, 2005b).
The deposit layers can be divided into two basic categories: porous and homogenous (non-
porous) - Fig. 7. The deposit covered a part of the membrane surfaces, which reduced the
membrane permeability and changed the temperature polarisation (Gryta, 2007). The values
of heat transfer coefficients in both liquid phases and the membrane have a dominant
influence on the values of T1 and T2 temperature of surfaces adjacent to the membrane
(Fig. 2). The deposit layer creates an additional thermal resistance, thus decreasing the heat
transfer coefficient from the feed bulk to the evaporation and condensation surfaces, and the
temperature polarisation increased. As a result, the driving force for mass transfer is
reduced and a significant decline of the permeate flux was observed (Gryta, 2008). The
formation of non-porous layer causes a significant increase in the mass transfer resistance
and the value of the permeate flux approach zero in an exponential way (Gryta, 2008).

Fig. 7. SEM image of deposit on the MD membranes (Accurel PP S6/2). A) porous (CaCO3);
B) non-porous (proteins)
The supersaturation state enables the nucleation and crystal growth, what in MD is mainly
caused by water evaporation and temperature changes (Alklaibi & Lior, 2005; Gryta, 2002;
He et al., 2008; Yun et al., 2006). In the case when the solute solubility decreases along with a
temperature drop, deposit can be formed as a result of the temperature polarization (He et
al., 2008; Gryta, 2002).
The formation of deposit on the MD membrane surface begins in the largest pores (Fig. 8),
because they undergo wettability the most rapidly (Alklaibi & Lior, 2005; Schneider et al.,
1988). The wetted pores are filled by the feed, what facilitates the oversaturation and
formation of deposits. The salt crystallization inside the pores was limited through a
reduction of the surface porosity (Gryta, 2007b; He et al., 2008).
30 Desalination, Trends and Technologies

Fig. 8. SEM images of deposits formed inside the large pores (3-5 μm of diameter)
The adherence of the deposit to the membrane surface is a critical factor for MD
performance, as well as for other membrane processes (Gryta, 2008; Gryta, 2009). It was
found, that the deposit of CaCO3 on the membrane surface can easily be removed by rinsing
the module with a 2–5 wt.% solution of HCl, what allowed to restore the initial permeate
flux (Fig. 9). However, the repetitions of module cleaning procedure by this method resulted
in a gradual decline of the maximum permeate flux (Gryta, 2008).

800
Permeate flux, JV [dm3/m2 d]

Module rinsing – 3 wt.% HCl

700

600

500

400

300

200
0 200 400 600 800 1000
Time of MD process, t [h]

Fig. 9. Changes of the permeate flux during MD process of tap water

The SEM investigation of the membrane cross-sections revealed that the deposit covered not
only the membrane surfaces but also penetrated into the pore interior (Fig. 10). The SEM-
EDS line analysis of a change of the calcium content located into the membrane wall
demonstrated that the deposit occurred up to the depth of 20–30 μm. Although, a rinsing
acid solution dissolves the crystals, the wettability of the pores filled by deposit was
accompanied to this operation. Therefore, the elimination of the scaling phenomenon is very
important for MD process. The application of chemical water softening and the net filters
(surface crystallization) allows to limit the amounts of precipitates deposited on the
membrane surface during water desalination by MD process (Gryta, 2008c).
Water Desalination by Membrane Distillation 31

a) A b)

Ca
0 10 20 30 40
Distance, L [μm]

Fig. 10. CaCO3 deposit on the membrane surface. a) membrane cross section, b) SEM-EDS
line analysis (direction A)

4. Water pretreatment and membrane cleaning

The main techniques currently used to control fouling are feed pretreatment and membrane
cleaning (Baker & Dudley, 1998; Schäfer et al., 2005, Gryta, 2008). The degree of
pretreatment depends on the nature of the feeding water, the kind of membrane, the water
recovery level and frequency of membrane cleaning (Karakulski et al., 2006; Schäfer et al.,
2005). It was found that a significant amount of foulants from effluents obtained during ion-
exchangers regeneration was successfully removed by the addition of the Ca(OH)2 to treated
wastewater (Gryta et al., 2005c). The fouling intensity can be also limited by combining the
MD with other membrane processes (Drioli et al., 2004; Jiao, 2004; Karakulski et al., 2006).
The UF/MD integrated processes enables the concentration of solutions polluted by
significant amounts of petroleum derivatives (Karakulski et al., 2002; Gryta et al., 2001b). On
the other hand, an excessively advanced pretreatment system significantly increases the
installation costs (Karakulski et al., 2006), which may render the application of MD process
as unprofitable. Moreover, an effective water pretreatment by NF and RO processes did not
allow to completely eliminate fouling (Karakulski et al., 2002; Karakulski & Gryta, 2005),
therefore, its negative consequences should also be limited through the development of
appropriate procedure of installation operation.
The majority of problems encountered during the water desalination by MD process are
associated with water hardness. As the water is heated, CO2 content decreases and the
precipitation of CaCO3 takes place due to the decomposition of bicarbonate ions (Figs. 7–11).
For this reason, the feed water has to be pretreated before feeding the MD installation
(Singh, 2006; Karakulski et al., 2006; Gryta, 2006b). Several operations such as coagulation,
softening and filtration are used during the production of technological water. The
possibility of such pretreated water utilization as a feed for the MD process is an attractive
option (Gryta, 2008b). Contact clarifiers (accelators) are usually applied to the chemical
pretreatment of feed water in power stations (Powell, 1954, Singh, 2006). The chemicals (e.g.
lime, aluminum or ferric sulphate) are added directly to the accelator containing a relatively
high concentration of precipitated sludge near the bottom of the tank, and raw water is
treated with this mixture. Inside the accelator, water flowing downward from the mixing
and reaction zone passes the outer section of a much larger diameter, which is free of
turbulence. Subsequently, the water flows upward, and the removal of flocks by settling
takes place. A larger portion of this water passes through the return zone to the primary
mixing and to the reaction zone. This recirculation improves the quality of the treated water.
32 Desalination, Trends and Technologies

Fig. 11. SEM images of CaCO3 deposit on membrane surface after: A) 10 h, and B) 50 h
desalination of surface water by MD process

Ca(OH)2 Fe2(SO4)3
clean
water

raw
water

sludge

Fig. 12. Water treatment using the contact clarifiers (accelator)

The chemical pretreatment of ground water caused a significant decrease of the
concentration of compounds responsible for the formation of a deposit on the membrane
surface during the MD process (Gryta, 2008). However, the treatment of water carried out in
an accelator, employed in the power station for production of demineralized water by the
ion exchange process, was found to be insufficient for the MD process (Fig. 13). The
formation of crystallites on the membrane surface was confirmed by SEM observations.
Thus, a further purification of water produced by accelator is required in order to use it as a
feed for the MD process.
A very efficient method for preventing CaCO3 precipitation is dosing an acid (Karakulski &
Gryta, 2005). In this case HCO3– ions are converted into CO2 according to the following
reaction:

HCO3– + H+ → CO2 + H2O (4)

A major disadvantage of this method is an increase of concentration of chloride (HCl) or
sulphates (H2SO4) in the retentate. The later anions (SO4–2) are particularly hazardous for the
membrane (Fig. 14).
Water Desalination by Membrane Distillation 33

700

Permeate flux, JV [dm3/m2d]

600

500

400
raw water
pretreated water (accelator)
300
0 50 100 150 200 250 300
Time of MD process, t [h]

Fig. 13. Effect of the feed pretreatment (accelator) on the MD permeate flux

Fig. 14. SEM image of CaSO4 deposit on the MD membrane surface

Sulphates comprise the second type of fouling components, the scaling of which can be
encountered during water desalination by MD. The CaSO4 solubility often determines the
maximum recovery rate of demineralised water from feeding water (Gryta, 2009b).
The feed water before flowing into MD modules is heated in heat exchangers. In this case, a
thermal softening of water can also be performed (Gryta, 2006b). As the water is heated, CO2
content decreases and the precipitation of CaCO3 takes place due to the decomposition of
bicarbonate ions. A precipitated deposit may also cause substantial fouling of membranes;
therefore, this deposit should be removed by using an additional filtration (Karakulski &
Gryta, 2005). Other option is the application of heat exchanger, the design of which allows to
remove the deposit of carbonates formed during water heating (Gryta, 2004).
Thermal pretreatment allows to remove most bicarbonates from water, which in turn
reduces the amount of precipitate forming during MD process. However, the degree of
water purification sometimes is too low and precipitate is still forming on the membrane
surface. The SEM-EDS analysis revealed that apart a large amount of Ca, this deposit also
contained Mg, Si, S, Fe, Ni, Al and Na. When the majority of HCO3– ions was removed from
water, the carbonates formed an amorphous deposit with increased content of silicon
(Gryta, 2010b). Such a nonporous form of deposit increases the rate of decline of the MD
Discovering Diverse Content Through
Random Scribd Documents
 “Where are we going?” asked Larry.

“Back to the hotel,” replied Mr. Newton. “We’ll be safe there. I

want to get a line off to the paper.”

“You’ll have to hurry,” said the boy. “The telegraph operator said if
the dam broke he’d have to leave.”

“Wait, and I’ll scribble a line now,” said the reporter. He hastily
wrote something on a piece of paper, addressed it to the Leader,
and gave it to Larry.

“Take it on a jump now, Larry, my boy!” he cried, and Larry rushed

off on his wheel. “I’ll meet you at the hotel,” called Mr. Newton after
him.

Larry reached the telegraph office just as the operator was leaving
it.

“Wait a minute!” called the boy. “I have some copy for you.”

“Can’t wait!” exclaimed the telegraph man. “The water’s rising and
I’m going to get out while there’s time.”

“This will only take you a second,” said Larry. “It’s got to get to the
Leader. It tells about the dam breaking. They’re going to get out an
extra!”

“Well, I wouldn’t do it for anyone else,” said the operator, “but

you’re a plucky boy to come here with the copy when everyone else
is thinking of getting away, so I’ll send the dispatch for you. After
this you may find me in a temporary office in a tent up on the hill.”

“I’m much obliged to you,” said Larry, handing over the copy. He
waited until he saw the operator send it off, and then the man,
taking some of his instruments with him, left the office.
 As he did so a small stream of water began to run down the
middle of the street.

“Flood’s coming!” exclaimed the telegrapher. “You were just in

time!”

Then he began to run, and Larry, abandoning his wheel, did

likewise, for he knew because of the formation of the ground that
there might be deep water there soon.

The rain had stopped once more, and this time it seemed as if it
might let up for some time, as the clouds grew lighter. But that was
too late to prevent the damage by the rising waters, which
continued to increase in depth. Fortunately most of the people in
that section of the town had been given plenty of warning and had
left their homes, taking all their most valued possessions with them.

However, there were some who lingered too late, and they were
now fleeing with only a few necessaries. They made for the other
side of the place, where the high ground around the hotel offered a
chance for safety.

Larry and the operator hurried along, the former aiming to reach
the hotel, and the telegrapher to make arrangements to set up a
temporary office. At the hotel Larry found Mr. Newton, surrounded
by a number of newspaper men, waiting for him.

“Did you make it?” asked Mr. Newton.

“Just in time. It was the last message,” said the boy.

“What’s that, Newton?” asked some of his acquaintances.

“I just sent a wire about the dam bursting,” was the answer.

“You don’t mean you’ve got another beat on us?”

 “Well, I guess Larry did the biggest part of it,” replied Mr. Newton.

“Well, you two are a great team,” said some of the other
reporters, disgusted at being beaten again.
 CHAPTER XXXIV

UNDER WATER

The town was now a scene of wild confusion. The people were
nearly out of their senses with fear, for they were alarmed lest the
waters reach even the high places. Cooler heads did their best to
quiet the excited ones, but it was hard work.

Boats were plying everywhere, taking people from the second

stories of their houses in some cases, and saving some from possible
death by drowning. The waters, which were now turned into a
raging torrent, were filled with débris brought down from up country.

Sometimes whole houses or barns would be borne along, and

when they struck a building in Stoneville there was a crash that
could be heard for some distance and the stationary residence would
be knocked from its foundation and carried away.

The houses of those whom the flood had not reached were
thrown open to the unfortunates. The hotel took in all it could hold,
but the proprietor was obliged to put everyone on short rations, for
food was getting scarce, and the railroad was under water, so no
more could be brought in that way.

There was plenty of material for newspaper copy now. The

reporters, Mr. Newton included, went out on a tour of investigation,
making notes of what they saw. The men who worked on morning
papers were in a quandary how to get their news off until someone
said there was a telegraph office in the next town, about five miles
away over the hills.
 Several of them clubbed together, hired a horse and carriage, and
drove over with their copy.

“I wonder if I’ll have to do that in the morning,” Mr. Newton said

to Larry.

“I think I have a better plan,” said the boy.

“What is it?”

Then Larry told of how the Stoneville operator was going to open
a temporary office on the hill in a tent.

“If he does that, in time for us, it will be just the thing,” said Mr.
Newton. “Keep quiet concerning it. Don’t say anything about it to the
other fellows.”

“Why not?”

“Because we don’t want them to know it. If they find it out they’ll
go there and file stuff, and ours may be delayed. You must learn, in
the newspaper business, to know everything and tell nothing,
especially to the fellow on the other paper.”

“I’ll go over the first thing in the morning and find out if he’s
opened his place,” said Larry.

That night was one of terror. Fortunately there was enough

warning about the bursting of the dam so that most of the people
were out of the way in time, and none was killed. But the property
loss was tremendous. About midnight the waters ceased to rise, but
they still inundated most of the town, and would for some time,
since the country for quite a distance above was covered with the
flood.

Early the next morning Larry got up, dressed, and went
downstairs. He was surprised to find the corridor of the hotel partly
filled with water.

“What’s the matter?” he asked the clerk.

“Oh, they tried to drown us out last night,” was the reply.

“Has the flood reached here?” asked the boy.

“Take a look out front and you’ll think so,” the man went on.

Larry looked from the windows. He saw that the street was
inundated, the water being about four feet deep.

“How am I going to get out?” he asked in dismay.

“Swim,” said the clerk with a laugh, in spite of the gravity of the
situation. “It’s not very cold. Or you might wait for the flood to go
down.”

“I haven’t time for that,” said Larry, “and I don’t believe I could
swim as far as I intend to go.”

“There are some fellows outside with boats, and they may take
you where you want to go,” the clerk said.

“That’s a good idea,” said the boy. “I’ll try it.”

He went out on the front steps, through the corridor, which

contained about an inch of water. As he reached the front door a
rowboat, propelled by a big man, shot up.

“Boat?” asked the man, in the manner of one inquiring whether

one would have a cab. “Take you anywhere for half a dollar.”

Larry mentioned where he wanted to be landed, and got in the

boat. The oarsman said he would take him as near the place on the
hill as he could go.
 “You’ll have to walk the rest of the way,” the improvised ferryman
said.

“I’m willing,” replied the boy.

He found that the operator had set up a small tent, and was busy
over his instruments, which he had attached to the telegraph line
that passed over the brow of the hill.

“How soon can you take messages?” asked Larry.

“Oh, it’s you, eh?” asked the operator. “You were my last customer
in the old place, and you’re the first one in the new.”

“Will you soon be ready?” asked Larry.

“In about an hour,” was the reply.

The man busied himself over his instruments, connecting them to

batteries he had procured and then adjusting them. Next he climbed
a telegraph pole and “cut in” as it is called on the main line,
fastening the wire from his machines to the regular line. Larry
watched him with interest.

“I’ll soon be ready for you,” said the man.

“Then I’ll go back and get some copy,” said Larry.

He went down to the boat which was waiting for him, and in a
little while found himself back at the hotel. By this time nearly all the
guests were up and the women, especially, were much frightened
when they saw that the place was in the middle of a miniature lake,
and that there was water in the corridor.

“Don’t be alarmed,” the clerk was saying. “The water is not rising,
and, though it will probably stay here for some time, there is no
danger. We’ll make you as comfortable as we can, but you can’t
expect many comforts.”

“Have the fires gone out?” asked one man. “My room is cold.”

“The water has put the fire out in the furnace down in the cellar,”
was the reply, “but we’ve sent for oil stoves, and we’ll be able to
give you a little heat.”

The clerk’s assurances did much to quiet the excited throng, and
then breakfast was announced, though it was not a very liberal
meal. However, there was plenty of good hot coffee and bread and
butter.

“Where have you been?” asked Mr. Newton of Larry.

“Looking for a telegraph office,” replied the boy in a low tone, for
there were other newspaper men near by.

“Did you find one?”

“I did,” and then Larry whispered that the man would take
messages soon. “Get some stuff ready,” he went on, “and I’ll take it
to him before the other fellows locate him.”

“Good idea,” said Mr. Newton. “I’ll have a bunch of copy ready in
about an hour.”

He hurried through the meal and went over to a table, where he

began writing at a rapid rate.

“How you going to get your stuff off?” asked some of the other
reporters.

“That’s a secret,” replied Mr. Newton good-naturedly as he went

on describing in vigorous language the scenes in the flooded district,
for much more of the town was under water than had been
expected would be covered.

All about were men plying here and there in boats, saving
household goods, carrying people hither and yon, and taking
provisions from the centers where food had been collected to the
different places where the people were congregated. There were
one or two naphtha launches, and any number of rowboats.

Altogether it made a lively and unusual story. Fortunately there

was no loss of life, though there were many narrow escapes. Many
head of stock, and hundreds of horses and pigs in the country
section had been drowned.

The breaking of the dam Mr. Newton described more fully than in
his first hasty dispatch, and putting in many exciting incidents he
had a story that he felt sure would be read with interest when it was
printed in the Leader.

“Now to get it on the wire ahead of the other fellows,” he

remarked to himself, as he folded up the copy and gave it to Larry.

“Now don’t let any of the others find out where you are going,”
cautioned Mr. Newton to the boy. “Try and fool them. Have the man
row you in a different direction, and then circle about and get to the
telegraph tent. Do you think you can do it?”

“I guess so,” replied Larry. “I don’t believe the other reporters

know where the tent is. You can’t see it from the hotel, and they
haven’t gone out very far.”

“All right,” replied Mr. Newton. “Come back as soon as you can.
Here is some money to pay the boatman with.”

Larry had donned his rubber boots, but, as it was not raining, he
had no need to hoist his umbrella. It seemed at last that the storm
had ceased, though the waters had not yet begun to recede.
 Larry walked through the damp corridor, trying not to seem in a
hurry or as if he was going anywhere. He thought he had
succeeded, but, just as he was about to get into the same boat he
had hired before, he saw Peter Manton come hurrying out. Peter had
a bundle of copy in his hand, and was, evidently, going to look for a
telegraph office. He glared at Larry.

“Here’s where we beat you,” sneered Peter.

Larry wondered whether Peter had discovered where the

telegraph office was. If he knew, Larry thought there would be no
use in trying to fool him by taking a round-about course. If he did
not, then there was a chance of Larry reaching it first and getting Mr.
Newton’s copy on the wire.

“Row me to the telegraph office,” was the order Larry heard Peter
give to a boatman he had engaged.

“I don’t know where there is one,” the man said.

“Well, row about until you find one,” said Peter, with as much airs
as though he was a reporter instead of a copy boy. “When you find it
I’ll send this stuff.”

The man started off, rowing at random. Larry waited a while, and
then, telling his boatman to send the craft in the opposite direction
from that in which the telegraph tent was, he too started away.

“We mustn’t let them find out where we’re going,” said Larry. “I
must get to the office first.”
 CHAPTER XXXV

THE RACE

In a little while the boat containing Peter was out of sight around
the corner of the street. Larry thought it would be a good time to
start in the right direction toward the telegraph office. Accordingly
he told the man at the oars to head the craft the other way.

“I’ll bet they’re up to some trick,” the man said. “The fellow rowing
that boat is a foxy chap. I think he suspects something.”

“Well, we’ll give him a race if we have to,” replied Larry.

If Larry had not been so intent on his errand he would have been
interested in the strange sights all about him. The flooded city was
alive with boats rowed or being propelled in all directions.

The people seemed to have gotten over their first fear, and,
though there was much discomfort, they were making the best of
circumstances. A large number of houses were under water to the
second stories, and the families were living on the upper floors. A
corps of men brought them food and supplies.

Fortunately the weather was mild for November, and there was
little real suffering. There was not much food, but, now that the
waters had ceased rising, trains were being sent over the railroad
bearing goods of various sorts for the relief of the homeless ones.

On and on Larry’s boatman rowed him. It was quite a distance to

the foot of the hill on which the telegraph tent was located, and
progress was slow while they were threading their way in and out
among the inundated streets. Care had to be taken, also, not to be
struck with the floating débris that was swirling along on the current.

“Look behind you,” said the boatman suddenly to Larry, who was
in the stern, facing the oarsman. The boy turned.

There, coming after them, as fast as the man could bend to the
sweeps, was the boat containing Peter. The craft was forging
through the water at a rapid pace and would be up to them in a
short time.

“They’re following us!” exclaimed Larry’s rower.

“I guess they’ve found out where the telegraph office is,” said
Larry, “and they’re going to try and get there first.”

“Then it’s to be a race,” replied Tony, Larry’s man. “Well, Jim

Dexter will find I’m as good a hand at the oars as he is!” With this
Tony braced himself and began taking long strokes that sent the
boat through the water at a good clip.

“Mind where you steer now,” cautioned Tony to Larry. “Don’t run
us on a log or a floating house and I’ll get you to the telegraph place
first.”

“I hope you do,” replied Larry, as he took a firm grasp of the

rudder. “If the Scorcher beats the Leader I’m liable to lose my job,
and so is Mr. Newton.”

The other boat was almost up to them now. Larry could hear Peter
urging Jim to greater exertion as the boy sat in the sternsheets and
steered, as Larry was doing.

“Ten dollars if you beat ’em!” Peter exclaimed as his boat crept up
inch by inch, until it was almost even with Larry’s craft.
 “I don’t need any ten dollars to beat him,” said Tony, with a nod at
Jim. “He and I aren’t any too friendly and I’d like to wallop him, just
for the looks of the thing, to say nothing of helping you out.”

“Thanks,” spoke Larry. “I haven’t ten dollars to offer you, but I’ve
no doubt Mr. Newton will pay you well if you get me to the telegraph
office first.”

The race was now on in earnest. The boats were side by side, and
not far apart. Both were headed for the hill, on the summit of which
could be seen the white tent where the telegraph office was located.
Peter had played a trick on Larry, by pretending to be hunting for the
place. As a matter of fact he merely had Jim row about until they
saw in which direction Larry’s boat went. Then he followed.

They were now pretty well clear of the town, and were going over
flooded fields. The water was filled with logs and stumps of trees,
planks, bits of barnyard wreckage, and occasionally the dead body of
a horse or cow. It required careful steerage to avoid hitting these
objects, and in consequence the speed was not as great as it might
otherwise have been.

The two men, who were old-time rivals, bent to the oars until the
stout ash handles almost broke. The blades swirled through the
water and the bows made ripples and foam as both craft forged
ahead.

For a while the two boats were almost on even terms. They raced
along not ten feet apart, and so nearly alike did Jim and Tony row
that it looked as if the two were but one craft. But, little by little
Tony began to pull ahead. He put a little more force into his strokes
and took longer ones, while Jim was rowing in a rather ragged
fashion.

Once Jim caught a “crab,” and nearly went overboard. This gave
Tony a big advantage, and he got almost a length ahead. However,
he lost this lead in a little while, for Larry, by some mischance, hit a
log a glancing blow and Tony had to stop rowing in order not to
upset.

“Be careful,” cautioned Tony. “Another one like that and we’ll lose
the race.”

“I’ll be careful,” replied Larry, ashamed of his error.

Once again the two boats were about in line. The rowers were
tiring, however, and could not go so fast. Tony, who was an old hand
at the oars, stuck to his task with grim determination, and soon he
was half a length ahead of his rival.

By this time a crowd of people on the shore, which they were fast
approaching, were aware that something unusual was under way.
They came down close to the water’s edge to see the outcome of
the race. The boats were now a little over a quarter of a mile away
from the land.

“They’re beating us!” exclaimed Peter, as he saw Larry’s boat

pulling steadily ahead. “Can’t you row faster, Jim?”

“I’m doing the best I can,” was the reply, but Jim gritted his teeth
and tried to get a little more power out of his strokes. It was
seemingly useless, however, for Tony with the regularity of clockwork
was sending his boat through the water at a good clip.

“I can’t let him beat me!” exclaimed Peter, while an ugly look stole
over his face. “If I don’t get my copy there first I’ll be discharged.
I’ve got to beat him, by fair means or foul.”

The distance between the boats was fast widening. Larry’s was
three-quarters of a length ahead now.

“I’ve got to do it!” exclaimed Peter in a low tone.

 Then, with a sudden yank on the tiller ropes, he shifted the rudder
so that the bow of his boat was pointed straight at Larry’s craft.

“Look out!” cried Tony, who saw the movement. “You’ll upset us!”

Larry, hearing the shout, turned to see Peter’s boat racing toward
him. He tried to steer out of the way, but there was no chance. An
instant later the two boats came together with a crash. The gunwale
of Larry’s boat was cracked, and the force of the impact was so
heavy that his craft careened until the water came over the other
rail.

“We’re upsetting!” cried Tony, throwing himself to one side in an

endeavor to prevent what seemed certain to happen.

Nor could he avoid it, for a second later the boat turned turtle,
throwing the two occupants into the water.

“You did that on purpose!” cried Tony, as he began to strike out

vigorously toward Peter’s boat.

“It was an accident!” cried Peter, somewhat alarmed at the

outcome of his mean trick.

“Can you swim?” asked Tony of Larry, who had sunk once, but
who soon bobbed up again.

“Yes—I—can!” gasped the boy. “I had—to—kick—my—rubber—

boots—off—though!”

They both struck out for Peter’s boat, expecting that the
occupants would stop and assist them. But this was not Peter’s idea.
Jim would have stopped rowing and gone to the rescue of those in
the water, but Peter steered the boat to one side and the momentum
carried it a considerable distance away.

“Aren’t you going to help them?” asked Jim.

 “No!” snapped Peter. “You keep on rowing. We must get to the
telegraph office first! I’ve got to beat them!”

“But they may drown!”

“No danger. They can both swim, and they can cling to their boat
until we come back. Someone will come out from shore for them.
See, some boats are starting already.”

This was so, several small craft putting out as soon as those on
shore saw the accident happen.

“Now you row on!” commanded Peter. “I hired you to take me to

the telegraph office and we haven’t time to stop and rescue people.”

“Well, of all the mean—” began Jim, and then he stopped. He

realized that Larry and Tony were in no particular danger, but he felt
that they should be taken into his boat. However, he wanted to earn
the ten dollars Peter had promised him.

“Are you going to leave us?” called Tony.

“It ain’t my doings,” called back Jim. “He won’t let me stop.”

“Then he’ll get his stuff to the telegraph office first,” said Larry.
“He’ll beat me!”

He and Tony were clinging to the keel of their overturned boat.

“Maybe we can get this right side up and catch them,” suggested
Tony.

“No, it’s too late,” said Larry sorrowfully. “They have too much of a
start.”

It seemed so, for Peter’s boat was now about a quarter of a mile
from shore, and Jim was rowing fast.
 “Shall we swim in or wait until someone comes out and picks us
up?” asked Tony.

“Might as well stay here,” replied Larry. “It’s hard swimming in

your clothes.”

His heart was full of bitterness, both at the mean trick Peter had
played, and at the thought of being beaten, for he knew that there
would not be time for the telegraph operator to send both Peter’s
copy and his also in time for the afternoon paper. The Leader would
be beaten.

“Hark! What’s that?” asked Tony, as they moved about to get

better positions in grasping the overturned boat.

“Sounded like a whistle,” said Larry.

“It was a whistle! A motor boat is coming toward us!” cried Tony.
 CHAPTER XXXVI

LARRY SCORES A BIG BEAT

Larry looked up. There, bearing down on them, was a swift

gasolene launch, one of several that had been doing rescue work
about the flooded town. The man at the wheel had her headed for
the upset rowboat.

“They’re going to pick us up!” cried Tony.

“But it will be too late,” said Larry.

“Maybe not, that’s a powerful craft, and maybe they’ll get you to
shore ahead of that little skunk!” spoke Tony.

“Stand by to be taken off!” cried the captain of the motor boat.

With a graceful curve the craft swung up to where Larry and Tony
clung to the keel of their boat. The man at the wheel pulled a lever
and the screw reversed, though the engines did not stop. The motor
boat slowed up, and, as it slowly passed by, the two in the water
grasped the gunwale, which was low, and pulled themselves aboard,
before the craft had come to a stop.

“Saw you upset,” said the motor boat’s captain, “and I headed
right for you.”

“We didn’t upset, we were run down,” said Tony, “and there goes
the mean chap that did it,” he added, pointing to Peter’s boat.

“Can you put us ashore in a hurry?” asked Larry. “I must get some
press dispatches to the telegraph office. I want to beat the boy in
that boat. We were beating him, but he ran his boat into ours and
upset us. Then he wouldn’t stop to pick us up.”

“So you want to get ashore first, eh?” asked the owner of the
motor craft. “What paper are you from?”

“I’m with Mr. Newton of the Leader,” said Larry.

“What, Harvey Newton?” asked the man.

“Yes,” said Larry.

“Well, I’d do a good bit for Harvey Newton,” the captain went on.
“He was at our motor boat races in New York bay last summer, and I
found him a good friend.”

“Do you think you can get me ashore first?” asked Larry.

“Well, he’s got a pretty good start,” said the captain, “but I never
saw anything that could beat the Porpoise if you gave her half a
show. We’ll see what we can do. Can you steer while I attend to the
engines?”

“I guess so,” replied Larry.

“Better let me,” put in Tony. “I know the lay of the land better
than you do.”

“Go ahead then,” said the captain. “I’ll speed her up for all she’s
worth.”

He went back to the stern. The steady chug-chug of the motor,

which had not ceased, was now increased threefold as the captain
shifted various levers, let more gasolene into the cylinders and
advanced the spark. Then, with Tony at the wheel, the Porpoise shot
ahead, in an attempt to beat Peter to the shore.
 How the swift craft cut through the water! A big wave arose on
either side of the bow. The motors were exploding like a battery of
gatling guns as the captain, in the role of engineer, opened the
exhaust to clean out the cylinders. Then, shutting it down, the
engine throbbed like a big turbine wheel under heavy pressure.

Nearer and nearer to the shore the craft forged. Peter, looking
back, saw that Larry and Tony had been rescued and, in the fast
boat, were bearing down on him.

“Row! Row!” he cried to Jim. “They’re going to run us down!”

“Don’t worry, they’re not as mean as you are,” said Jim.

“Then they’ll beat us ashore!” yelled Peter.

“I shouldn’t wonder if they did,” was Jim’s cool reply. “I’m doing
my best, but I can’t beat the Porpoise. She’s the fastest boat around
here.”

Peter’s craft was now about three hundred feet from the shore.
There was a big crowd waiting to see the outcome of the affair.
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