~UTS

University of Technology, Sydney

Assessment of Pre-treatment to Seawater

Reverse Osmosis

By

Khorshed Jahan Chino

A thesis submitted to fulfilment

of the req uirements for the degree of
Master of E ngineering

University of Technology, Sydney

Faculty of Engineering

January, 2009
 CERTIFICATE OF AUTHORSHIP

I certify that the work in this thesis has not previously been submitted for any degree
nor has it been submitted as part of requirements for a degree except as fully
acknowledge within the text.

l also certify that the thesis has been written by me. And help that I have received in my
research work and the preparation of the thesis itself has been acknowledged . In
addition, I certify that all information sources and literature used are indicated in the
thesis.

Signature of Candidatu re

\'-nars ~.;tJ J ~h cJvfJI\A.,\.

-- ------------ --- ------ ----------
(Khorshed Jahan Chinu)
Sydney, January 2009

II
 ACKNOWLEDGEMENT

I express my deep sense of gratitude towards my Supervisor Professor Vigneswaran for

his excellent motivation and guidance of my study. I would like to express my gratitude
to my principle supervisor, Professor S. Vigneswaran and my co-supervisor, Dr H.K.
Shon, for providing me with the opportunity to work in the research project of the
pretreatment to seawater, for their valuable guidance and support at all levels during my
study at UTS. I would also like to thank Dr Kandasamy for proofreading the thesis and
offering constructive comments.

I extend my gratitude to Professor Vigneswaran, who guided me continuously from start

to end of my study. I would like to thank him for his financial support during my study.
I would also like to thank my co-supervisor, Dr. Hokyong Shon, who offered generous
assistance on the start-up as well as the progress of the study. Also, I wish to
acknow ledge Dr. Hokyong Shon for his financial support during the study. I would like
to also thank Dr Hao for his support while working in the Environmental lab.
In addition, l would like to thank Professor Tally Palmer from the fnstitute Water for
Environment and Resource Management (IWERM) for her encouragement and
financial support of the study. My special thanks for Johir for his helping hands which
lead to successful completion of this difficult task. My appreciation also goes to LaszJo,
Javeed, Ben, Rupak, Wen Xing, Dang and Yoshuf for their generous help in the
experimental phase of this research, and staff in the Research Office for their friendship
and companionship. My appreciation also goes to all the people in SIMS (Sydney
marine institute, Chowder Bay, Sydney) for their support to do experiments on-site.

I greatly acknowledge the financial support for the final semester of my Masters degree
by Faculty of Engineering, University of Technology, Sydney (UTS) .

Finally, I wish to thank my Mother, sisters and brothers for their love and support.
Especially my sister lshrat, without her encouragement and support, it was not possible
to come and study in Australia. I am also grateful to my husband for his support.

Ill
 TABLE OF CONTENTS

Title page
Certificate ll

Acknowledgements Ill

Table of contents IV

Nomenclature X

List of the tables Xll

List of the figures XIV

Abstract xvi

Chapter 1

Background & Introduction 1-1

1.1 Water crisis 1-2

1.2 Desalination in Australia 1-3
1.3 Reverse Osmosis (RO) 1-4
1.4 Membrane fouling and Pretreatment 1-5
1.5 MF/UF as a pretreatment 1·-6
1.6 Characterisation of organics present in sea/brackish water 1-7
1. 7 Fouling indices 1-7
1.8 Pre-treatment by biofiltration 1-8
1.9 Aim ofthe study 1-8

IV
Chapter 2

Literature Review 2- 1

2.1 Introduction 2-2

2.1.1 Seawater 2-2
2.1 .1.1 Seawater organic matter (SWOM) 2-2
2.1.1.2 Dissolved organic matter in seawater 2-3
2.1 .1.3 Characterization of organics present in seawater 2-3
2.1.1.4 Inorganic matter 2-5
2.1.2 Seawater Reverse Osmosis in desalination 2-5
2.1.3 Membrane Fouling 2-6
2.1.4 Types of membrane fouling 2-6
2.1.4.1 Particulate/Colloidal fouling 2-8
2.1.4.2 Organic fouling 2-8
2.1.4.3 Inorganic fouling/Scaling 2-10
2.1.4.4 Biofouling 2-10
2.1.5 Pretreatment 2-11
2.1 .5 .1 Conventional pre-treatment 2-1 1
2.1.5.2 Non-Conventional pre-treatment ( MFIUF as a pre-treatment 2-13
2.1.5.3 Biofilter 2-14
2 .1.6 Comparison of Conventional and Non-conventional pretreatment 2-15
2.] .7 Case studies of existing plants 2-16
2.1.8 Fouling Indices 2-21
2.1 .8.1 SDI and MFI 2-21
2.1.8.2 MFI-UF 2-22
2.1.8.3 MFI-NF 2-23

v
Chapter 3
Experimental Investigation 3-1

3.1 Introduction 3-2

3.2 Experimental Materials 3-2
3.2.1 Seawater (Rose bay) 3-2
3.2.2 Seawater (Chowder bay) 3-2
3.2.3 Synthetic wastewater 3-3
3.2.4 Physical properties of GAC and Anthracite 3-4
3.3 Experimental Methods 3-5
3.3.1 Flocculation as pretreatment 3-5
3.3.2 Adsorption using powdered activated carbon (PAC) as pretreatment 3-5
3.3.3 Deep bed filtration as pretreatment 3-5
3.3.4 Flocculation followed by microfiltration 3-6
3.3.5 Long term biofiltration 3-6
3.3 .6 Membranes and Flux decline experiments 3-7
3.3.7 Reverse osmosis (RO) as a post treatment 3-8
3.4 Analytical methods 3-9
3.4.1 SDI and MFI 3-9
3.4.2 Pore blocking index 3-11
3.4.3 CF-MFI 3-12
3.5 Molecular weight distribution (MWD) of organic matter 3-14

Chapter 4
Results and Discussion 4-1

4.1 The effect of pre-treatment on the fo ul ing propensity of the feed 4-2
4.1.1 Fouling Indices 4-2
VI
 4.1.1.1 Silt Density Index (SDI) 4-2
4.1.1.2 Modified fouling index (MFI) 4-3
4.1.1.3 Cross-flow sampler MFI (CFS - MFI) 4-5
4.1.1.4 Pore Blocking Index (Spb) 4-5
4.1.2 Effect of pre-treatment on the fouling propensity 4-6
4.1.2.1 Effect of different pretreatments on MFI and CFS-MFI 4-7
4.1.2.2 Effect ofFeCl3 dose on MFI and CFS-MFI 4-8
4.1.2.3 The effect of PAC dose 4-9
4.1.2.4 MWD of the effluents after flocculation and adsorption 4-10
4.1.2.5 The effect ofMWD on Spb, MFI and CFS-MFI 4-1 1
4.1.3 Conclusions 4-14
4.2 Effect of pre-treatment in reducing the fouling: A Laboratory scale study with
seawater 4-15
4.2.1 Seawater 4-15
4.2 .2 Pretreatments 4-17
4.2.2.1 Comparison of different pretreatment in terms ofMFI 4-17
4.2.2.2 Comparison of pre-treatment in terms of SWOM removal
efficiency 4-1 8
4.2.2.3 MWD ofSWOM after different pre-treatments 4-19
4.2.3 GAC biofi!tration as pre-treatment 4-20
4.2.3.1 MFI 4-20
4.2 .3.2 DOC removal efficiency 4-20
4.2 .3.3 MWD ofthe permeate ofGAC filtration 4-21
4.2.4 Concluding remark 4-22

4.3 Assessment of pre-treatment to microfiltration for desalination in terms of fouling

index and molecular weight distribution 4-23
4.3 .1 Characteristics of seawater 4-23
4.3.2 Comparison of different pretreatment methods 4-23
4.3.2.1 Effect ofPretreatment on microfiltration (MF) flux decline 4-24
4.3.2.2 Effect of pre-treatment on Turbidity removal 4-18
4.3.2.3 Pre-treatment and change in molecular weight distribution of
organic matter (MWD) 4-25

Vll
 4.3.3 Pre-treatment and Modified Fouling Index (MFI) 4-26
4.3.4 Conclusion 4-27
4.4 Biofilter as Pretreatment to Membrane Based Desalination: Evaluation in terms of
Fouling Index 4-28
4.4.1 Characteristics of seawater 4-29
4.4.2 Pre-treatment 4-29
4.4 .2 .1 Variation of seawater Characteristics during experiments 4-29
4.4.2.2 Effect of filtration velocity to turbidity removal 4-30
4.4 .2.3 SDI 10 and MFI 4-31
4.4.2.4 Correlation between different fouling indices 4-33
4.4.2.5 Head build up 4-35
4.4.3 Reverse Osmosis as post-treatment after pretreatments 4-36
4.4.4 Concluding remarks 4-37

Chapter 5
Conclusions 5- 1

5.1 Comparison of pre-treatments to wastewater in terms of modified fouling index

(MFI) and cross-flow sampler modified fouling index- CFS-MFT 5-2
5.2 Comparison of different pretreatment for seawater (lab scale) 5-2
5.3 Assessment of pretreatment to micro filtrat ion for desalination in terms of fouling
index and molecular weight d istribution (on-site) 5-3

References R- 1

Appendix A A-I

Modified foulin g index calculation

Vlll
Appendix B A-3

Publications made from the study

IX
 Nomenclature

2
A the membrane surface area (m )

ASTM American Society for Testing and Materials

BOD Biological oxygen demand

BTSE Biologically treated sewage effluent

BOM biodegradable organic matter

the concentration of particles in a feed water (mg/1)

COD Chemical oxygen demand

CFS-IvlFI cross-flow sampler modified fouling index
Da Dalton

DOC dissolved organic carbon

DMF dual media filter

EfOM effluent organic matter

HPSEC High pressure size exclusion chromatography

MFI modified fouling index
NIWD molecular weight distribution
MF microfiltration
MFI-UF modified fouling index by using ultra filter membrane
MFl-NF modified fouling index by using nano filter membrane
MWCO molecular weight cut-off
NF nanofiltration
NOM Natural Organic Matter
PAC Powdered activated carbon
membrane resistance
RO reverse osmosis
SEC size exclusion chromatography
SWOM Seawater organic matter
Spb pore blocking slope by critical time- pore blocking index (1/L)
filtration time (s)
X
TDS total dissolved solid
v total permeate volume (l)
~p applied trans-membrane pressure (Pa)
2
11 water viscosity at 20°C (N s/m )

a the specific resistance of the cake deposited

XI
 LIST OF TABLES

Table 1.1 Water use by an average household in NS W

Table 1.2 Water supply capacity and desalination status for some Australian big
cities
Table 2.1 The characteristics of seawater at Chowder Bay during June- October
2008
Table 2.2 Organic matter and Molecular weight found in this study
Table 2.3 Inorganic matter present in seawater
Table 2.4 Organic matter fouling factors (adapted from Al-Amoudi and Lovitt,
2007)
Table 2.5 Characteristics of media filter used before seawater desalination
(According to the Water desalination technical manual, Department of
army, USA, 1986)
Table 2.6 Comparison of conventional and non-conventional pretreatment
Table 2.7 Jeddah SWRO Plant (capacity 56,800 m 3/d)
Table 2.8 Doha Research Plant, Kuwait
Table 2.9 French Institute of l\!larine Research
Table 2.10 Persian Gulf
Table 2. I 1 The International Power Mitsui Operation, Indonesia
Table 2.12 ONDEO Services, Gibraltar
Table 2.13 Singapore SWRO
Table 2.14 Ashdod, Mediterranean Sea
Table 2.15 Addur SWRO Desalination Plant, Bahrain
Table 3.1 Characteristics ofthe seawater (Rose bay, Sydney)
Table 3.2 Characteristics of seawater used in this study
Table 3.3 Composition of synthetic wastewater (Seo et al, 1996)
Table 3.4 Physical properties of Anthracite and GAC
Table 3.5 Characteristics ofRO membrane used
Table 4.1 MFI-CFS- MFI ofSWW (synthetic wastewater) for different pre-treatment
Table 4.2 Weight-averaged MW values of the effluent samples after flocculation
Table 4.3 Weight-averaged MW values of the effluent samples after adsorption

Xll
Table 4.4 t/V vs. V of standard MFI and tN vs. V ofCFS-MFI with different pre-
treatment
Table 4.5 MFI for different pre-treatment
Table 4.6 MFI and CF-MFI after GAC filtration
Table 4.7 Comparison of different pre-treatment methods
Table 4.8 Characteristics of the seawater (SIMS, Chowder Bay, Sydney)
Table 4.9 Comparison of different fouling indices for Anthracite biofilter (filtration
velocity= 10 m/h)
Table 4.10 Comparison of different fouling indices for GAC biofilter
(filtration velocity =10m/h)
Table 4.11 Comparison of different fouling indices for Anthracite biofilter
(fi ltration velocity = 5 m/h)
Table 4.12 Comparison of different fouling indices for GAC biofilter
(fi ltration velocity= 5 m/h)

X Ill
 LIST OF FIGURES

Figure 2.1 MWD of SWOM (seawater organic matter)

Figure 2.2 Complete picture of fouling (Adapted from Vrouwenvelder et al., 2003)
Figure 2.3 Types of membrane foulant in reverse osmosis membrane (adapted from
Khedr et al., 2000)
Figure 3.1 Schematic of the batch experiment using Jar test apparatus
Figure 3.2 Schematic diagram of biofiltration column
Figure 3.3 Schematic drawing of cross flow unit
Figure 3.4 Schematic drawing of cross-flow SWRO unit used in this study
Figure 3.5 MFI and SDI experimental setup
Figure 3.6 Cake filtration curve (Boerlage, Kennedy et al . 1997)
Figure 3.7 t (time)/v (permeate volume) vs. t for feed water
Figure 3.8 Schematic diagram of cross flow unit
Figure 4.1 Cake filtration curve (Boerlage, Kennedy et al. 1997)
F igure 4.2 t (time)/v (permeate volume) vs. v for feed water (0 .45 llm membrane,
Pressure = 200 KPa, Temperature= 20 oC)
Figure 4.3 t (time)/v (permeate volume) vs. t for feed water
Figure 4.4 a tN vs. V of standard MFI w ith different pretreatment
Figure 4.4 b t/V vs. V ofCFS-MFI with different pretreatment
Figure 4.5 The effect of FeC13 dosage on Mf [ and CFS-MFI
Figure 4.6 The effect of PAC dosage on MFI and CFS-MFI
Figure 4.7 (a) MWD of the effluent of flocculation
Figure 4.7 (b) MWD of the effluent of adsorption
Figure 4.8 M WD of SWOM (seawater organic matter)
Figure 4.9 SWOM removal by pre-treatment ofMF, FeCh Flocculation, PAC
adsorpti on and GAC Biofiltration (seawater DOC= 1.8 mg/L)
Figure 4. 10 M WD of SWOM after FeCh flocculation, PAC adsorption and GAC
Biofi ltration pretreatments (FeCb dose= 2 mg/L; PAC dose= 0.05 giL,
GAC co lumn depth of 30 em)
Figure 4. 11 DOC removal of the GAC biofilter (filtration rate =1 m/h , GAC medium
depth= 30 em , average influent DOC= 1.8 mg/L)
Figure 4.12 MWD of SWOM after different days from GAC pretreatment

XIV
Figure 4.13 Variation of CFMF flux for seawater with and without of pre-treatment
(membrane pore size= 0.45 !J.m, Cross flow velocity = 0.5 m/s, Pressure
= 60kPa)
Figure 4.14 MW distribution of SWOM (seawater organic matter) of seawater and
with pre-treated seawater
Figure 4.15 Seawater characteristics during the experimental period
Figure 4.16 Effect of filtration velocity on filtrate turbidity (GAC and anthracite
column depth: 80 em, velocity: 5 and 10 m/h
Figure 4.17 SDI and MFI profiles for Anthracite and GAC biofilters at 5 m/h and 10
m/h
Figure 4.18 Effect of filter media and filtration velocity on head loss development
(filter medium depth= 80 em)
Figure 4.19 Temporal variation of RO filtration flux for seawater with and without
pretreatment (SR membrane, crossflow velocity= 0.5 m/s, operating
pressure 6000 kPa, feeding volume: 5 Leach day)

XV
 ABSTRACT

Membrane based desalination is widely used process to produce fresh water either from
wastewater or seawater. However, membrane fouling on the reverse osmosis is a major
hurdle. It increases the energy consumption as well as operating cost of reverse osmosis.
A pre-treatment before reverse osmosis (RO) desalination can sign ificantly reduce the
membrane fouling.
The main objective of this study was to assess the relative merits of different pre-
treatment processes in terms of membrane fouling reduction, and removal of organic
matter in terms of molecular weight distribution and dissolved organic carbon (DOC).
Different fouling indices (such as silt density index (SDI), modified fouling index (MFI)
and cross-flow samp ler modified fouling index (CFS-MFI)) were used to study the pre-
treatment efficiency of different process such as flocculation, adsorption, microfiltration
and biofiltration.

The effectiveness of different pretreatment on the fouling propensity of the feed was
studied using synthetic waste water. The fouling potential of the feed was characterized by
standard modified fouling index (MFI) and cross-11ow sampler modified fouling index
(CFS-1\tfFT). In CFS-MFI, a cross-flow sampler was used to simulate the condition of a
cross-flow filtration. The results indicated that the pretreatment such as flocculation with
an optimum dose of 68 mg/1 FeCb and adsorption with powdered activated carbon (PAC)
of 1 g/I substantially reduced the fouling propensity of the feed. The standard MFI of
flocculated wastewater was reduced by around 99% compared to that of the untreated
wastewater. The effect of molecular weight distribution (MWD) of the foulants in the
wastewater on the fouling propensity of the feed was also investigated. The MWD of
pretreated effluent was correlated well with the MFT and CFS-MFI indices.

Different processes such as flocculation with ferric chloride (FeCb) and deep bed filtration
(sand filtration and dual media filtration) as a pre-treatment to microfiltration (MF) were
used for seawater desalination. The performance of these pre-treatments was determined in
terms of silt density index (SDI) and modified fouling index (MFI) and flux decline in MF.
Flux decline of MF with seawater was 45% without any pre-treatment, 42% after pre-
xvt
treatment of FeCb flocculation , 24% after pre-treatment of sand filtration with in-line
coagulation and 22o/o after pre-treatment of dual media filtration (sand and anthracite),
respectively. MFI and SDI also indicated that deep bed filtration with in-line flocculation
was better pre-treatment than flocculation alone. Detailed molecular weight distribution
(MWD) of seawater organic matter was examined after different pretreatments. MWD of
the initial seawater mainly ranged from 1510 Da to 130 Da. Deep bed filtration with in-line
flocculation removed relatively large molecular weight of organic matter (151 0 - 1180 Da),
while the sma ll mol ecular weights (less than 530 Da) were not removed.

The removal of particulate matter and dissolved organic matter from seawater by the use of
biofi ltration was investigated through long term on-site operation of biofilters. Granular
activated carbon (GAC) and anthracite were used as biofi lter med ia at two different
fi ltration velocities. Filtrate quality was measured in terms of silt density index (SDI),
modi fied fo uling index (MFI) and turbidity removal. Reverse osmosis (RO) was used as a
post treatment. Both biofilters demonstrated similar fouling reduction behavior in terms of
SDI and MFI. Fouling potential in terms of MFI values decreased to 10 s/L2 within the
first 10-15 days of operation and kept constant up to the remain ing experimental period of
55 days of operation for both GAC and anthracite biofilter. The filtrate turbidity was
steady after 10 days and remained low at a value of 0.2-0.3 NTU and 0.28-0.31 NTU for
anthracite and GAC biofilter respectively. Furthermore, the headloss development was low
and within 20 em for biofilter operated at a low velocity of 5 m/h. A post treatment of
reverse osmosis after a pretreatment of GAC and anthracite biofilters showed a reduction
in normalized flux decline (J/Jo) from 0.22 to 0.12 and 0.35 to 0.21 during the first 20
hours respectively. The RO flux for seawater declined at a faster rate and continued even
after 3 days when no pretreatment was provided.

Based on the experiments, it was found that both med ia fi ltration (dual media) and
biofi ltration are appropriate pre-treatment before RO. In patticular, Biofilter led to a
consistent removal of organic matter over a long period of time.

XVII
 ~UTS
University of Technology, Sydney

CHAPTER!

Background and Introductiotl

1- 1
1.1 Water crisis
Water is essential element for human being. Water covers about two-thirds of the earth
surface although most is too salty to use. Only 2.5% of the world's water is not salty,
and two-thirds of that is locked up in the ice cap and glaciers. Moreover, 20% of the
fresh water also is in remote place. So, only 0.08% earth water is available for us. With
the increase of population, water demand will be increased by about 40% over the next
decade. Limited source of water trigger the threat of fresh water for the human being.
Moreover, climate change enhances this problem. United Nations Environment Program
(UNEP) in 1999 identified water shortage as one of the two most worrying problems
51
during the 21 century.
However, water is not only a proble1n for developing countries but also for many
developed countries. Australia is one of them. Most of Australia's large urban
populations are currently facing the water shortage proble1n. Australia's four largest
urban areas have water storage volume less than 50% of their capacities. Climate
change and population growth is giving pressure on limited water resources. Moreover,
Australia is the world's driest continent. For example, Sydney has been as one of the
worst on record in tenns of water shortages (NSW Govenunent, 2006). As a result,
there is a renewed focus on increasing water supplies in the urban areas. At the same
ti1ne, traditional options for expanding urban water supplies are being questioned
because of increased awareness of the significant enviromnental impacts. Furthennore,
physical and economic limits are being reached in terms of greater river flow and
groundwater extraction. For example, both the NSW and Victorian Govemn1ents have
ruled out constructing new water supply storage infrastructure for Sydney and
Melbourne (NSW Government, 2006).
Water recycle is one of the solutions for the community water management. At present,
potable-quality water is supplied for all household purposes. But more than 50% of this
water is used for gardens, toilets and laundry, where water of lesser quality would be
adequate. Table 1.1 indicates the total amount of wastewater and grey water produced
by an average household.

1-2
 Tablel.l Water use by an average household in NSW (Adapted from enviro-friendly,
http ://www.enviro-friendly.com/greywater-systems-australia.shtml, online accessed ih
September 2008)

Wastewater Total Total grey

source wastewater water

1°/o Total I Litres/day 0/o Total Litres/day

!Toilet I 32 I 186 - -
[Hand basin I 5 28 8 28
!Bath/shower I 33 193 54 I 193 I
!Kitchen II 7 II 44 I
- -
!Laundry I 23 I 135 38 135
!Total II 100 I 586 100 356

Australia over the last 20 years has been very effective in reducing water use, but
fmiher savings through water management is hard to achieve. The continued growth of
cities calls for the development of alternative sources. Desalinated seawater is an
alten1ative solution as a source of fresh water.

1.2 Desalination in Australia

Desalination is now being in1plemented in a nmnber of urban centres as a supplement to
existing water sources. Previously in Australia, large desalination plants were used only
in the 1nining and power generating industry. Desalination for urban water usage was
restricted to small isolated urban communities with access to no other water supply,
such as Kangaroo and Rottnest Islands (AFFA, 2002) . The ability to produce potable
water independent of rainfall is seen as the major advantage of desalination(NSW
Government, 2006, Victorian Government, 2006).
Furthermore, the cost of seawater reverse osmosis plants has fallen by 300% over the
last 15 years (Leslie, 2004) . Desalination is already considered alternative source of
drinking water in Australia (Table 1.2). In recent years, desalination has increasingly
been used throughout the world to produce potable water from brackish groundwater
and seawater, to improve the quality of fresh water for drinking and industrial use, and
to treat industrial wastewater prior to discharge or reuse. Technologies that were
originally developed to desalinate water are now widely applied in this country to
remove contaminants other than salt from freshwater supplies.

1-3
 Table 1.2 Water supply capacity and desalination status for some Australian big cities
(adapted from
http://www .ceem. unsw .edu.au/content/userDocs/OzW aterpaperiMRP_ 000. pdf)

Urban Centre Population Desalination

Sydney & Wollongong 4.41 n1illion Construction of a desalination plant of 250 ML/d
capacity currently underway
Melbourne & Geelong 3.6 million 150GL/annum desalination plant approved, to
supply Melbourne, Gee long, Westernport and
Wonthaggi.
Brisbane and Gold Coast 2. 77 million Approval granted for a 120 ML/d plant at Tugun to
be connected to the SEQ grid
Perth 1.46 million A 130 ML/d desalination plant at Kwinana, is
operational since November 2006.
Second 130 ML/d desalination plant proposed as
alternative supply option for future growth.

Adelaide 1.12 million Desalination proposed at Port Augusta, in

conjunction with BHP.
- - - - - - - - - - - - - · -- - - - -- !-·- - - - - - - - -- - - - - - - - - ---
Central Coast 0.3 million Approval being sought for the use of temporary
desalination plants with capacity of up to 10 ML/d

Therefore, it is important to find a sustainable technology for the desalination where

desalinated water can fulfi l the demand for drinking water demand together with
agricultural and industrial use of water.

1.3 Reverse osmosis (RO)

The growth in membrane applications for desalination has been exponential over the
last decade. Frost & Sullivan (2004) estimated the desalination plant market to be worth
about $1.32 billion in 2003. Growth is expected to continue as per capita water
requirements increase and populations multiply. The world's largest (reverse osmosis)
desalination plant is in Ashkelon, Israel that began operating in 2005 to produce 320
ML of water per day. Recent advances in membrane technology and performance have
led to broad application, and RO systems now represent the fastest growing segment of
the desalination market with more than 50% of the world's desalination capacity.
Nevertheless, under challenging water quality conditions, the operation of membrane-
based desalination plants still remains complex mainly due to membrane fouling.

1-4
1.4 Membrane fouling and pre-treatment
Apart from salt precipitation (scaling), which is generally resolved by using complexing
agents, membrane fouling can be widely classified as particulate/colloidal and organic
fouling. Particulate/colloidal fouling has been extensively studied and can be controlled
efficiently by flocculation and filtration. On the other hand, the quantification of organic
fouling requires sophisticated methods and analytical tools to characterize soluble
organic matter. Organic fouling occurs by the adsorption of various dissolved organic
materials on and in the membrane. A fraction of this organic matter (generally small
molecules) is easily biodegradable, and when it is accumulated on the membrane
surface in the presence of microorganisms it will result in the formation of biofilm
which is considered as the n1ain cause of fouling in reverse osmosis. Periodic chemical
cleaning (chlorination) is needed to control biofouling. However RO membranes are not
very tolerant to chlorine which decreases their life expectancy thus increasing the
running costs. This is why a prior removal of microorganisms by employing
microfiltration and ultrafiltration (1\tfF/UF) as pre-treatment is essential. Further, hollow
fiber MF/UF membranes used for pre-treatn1ent are tolerant to chlorine and can be more
efficiently cleaned than spiral wound RO n1embranes.
If RO is used as a sole process in desalination, both col1oidal and dissolved organic
matter will be retained by RO membrane which will lead to severe fouling. A study by
researchers from Yale University (Li and Elimelech, 2005) showed a synergistic effect
when both colloidal and dissolved organ1cs were present. This caused significant
fouling .
Feed pre-treatn1ent is a key factor determining the success or failure of a desalination
installation and influencing the overall performanc e of the plant. The recent case of
Tampa Bay, Florida desalination plant is a perfect illustration of the technical and
econom1c disaster resulting from a poor design of pre-treatment. Traditional pre-
treatment is based on the removal of suspended material (by processes such as
flocculation, and filtration), supported by an extensive chemical treatment, including
biofoulin g control (chlorination, dechlorination), and scaling prevention (dosing of
acids or antiscalant additives). Membrane cleaning involves alkaline solutions (pH 11-
12) for removal of silt deposits and biofilms, and acidic solutions (pH 1-2) to dissolve
n1etal oxides or scales, as well as a wide range of extra chen1icals such as detergents,
oxidants, complexing agents and biocides. As a result, the pre-treatment and cleaning

1-5
accounts for a significant part of the total cost (Bruggen and Vandecasteele, 2002). On
the other hand, if one uses MF /UF as pretreatment, particulate matter can be removed in
a cost-effective manner. Further, adsorption and flocculation (alone or together with
MFIUF in hybrid configuration) can remove most of the dissolved organic foulants.

1. 5 MF/UF as pre-treatment
Pressure driven membrane processes, such as microfiltration (MF) and ultrafiltration
(UF), are excellent techniques for the removal of suspended solids and for lowering
fouling. Energy consumption in MF is relatively low, less than one half of matching
conventional pre-treatment (Bruggen and Vandecasteele, 2002). MF generally provides
good quality feedwater for RO, with slightly lower COD/BOD, and silt density index
(SDI) in comparison to the untreated seawater. Further improvements can be obtained
by using UF, where microorganisms, macromolecules and colloids can also be
removed. Because of higher applied pressure, UF cost is higher than that for MF, but
still competitive with conventional pre-treatment. On the other hand, the UF permeate
used as RO feed is significantly i1nproved . Despite the above advantages of MF and UF,
organic fouling remains a problem both for the pre-treatn1ent (MFIUF) and also the
downstream process (RO) due to the existence of small organic molecules which pass
even through UF membranes. Studies with biologically treated sewage eftluent (BTSE)
proved that hybrid membrane processes (coupling flocculation and/or adsorption and/or
ion exchange resins with membranes) are efficient in simultaneously reducing
membrane fouling and improving water quality (Shon et al. , 2004; Guo et al. , 2004).
However, such results are not available for sea and brackish waters and are of
paramount importance for the rational design of pre-treatment.

1.6 Characterization of organics present in sea and brackish

'\tvaters
The characteri stics and organic matter concentration are different in sea/brackish waters
con1pared to fresh surface waters or BTSE. Detailed pre-treatment studies conducted
with different fractions of freshwater and BTSE showed varying degree of removal
(Shon et a1. , 2004 ; Jarusutthirak and Amy, 2002). Thus, it is necessary to optimize
sea/brackish water pre-treatment through a detailed characterization of organic n1atter.

1-6
Further, the techniques developed for freshwater must be modified to analyse organics
present in seaweater, as organic concentrations in seawater are typically low. Again, the
organic constituents of brackish waters will differ from that of seawater. One of the
aims of this study is to characterise the organics present in sea/brackish water by size
exclusion chromatography (SEC).

1.7 Fouling indices

To assess membrane fouling, a rapid and reliable measurement is needed. The Silt
Density Index (SDI) is the only standard method presently used. It has many
shortcomings and limitations (Schippers and Verdouw , 1980; Boerlage et al., 2003)
the most important being the use of a MF membrane, the characteristics of which are
not precisely specified in the standard. Some of these shortcomings were taken into
account in the development of the Modified Fouling Index (MFI) and the Mini-
Plugging Factor Index (Vrouwenvelder et al., 2003). However, all these indices neglect
the role of colloidal and dissolved matter in water. Boerlage et al (Boerlage et al., 2002)
recommended the use of UF tnembranes in establishing a new MFI -UF index, which
considers the effect of colloids. This index is suitable for the fouling of UF membranes
used in the pretreatment process but not for the fouling of RO membranes. Based on
recent studies (Boerlage et al., 2003; Boer]age et al., 2002; Boerlage et al., 2004), it
seems that fouling of RO membranes is better represented by the value of the specific
resistance of the cake fmmed by the fouling components on a NF membrane during a
standard filtration test. Khirani and Ben Aim (Khirani, 2006) developed a new method
using nanofiltration (NF) n1embranes (NF-MFI) which is applicable to most waters,
including the ones which have a high fraction of small MW (dissolved) matter. Their
method is practical, as it requires only about one hour to complete the measurement.
However the choice of a standard NF membrane with high organic rejection and low
salt rejection remains unresolved.

1.8 Pre-treatment by biofiltration

Feed pre-treatment is a key factor determining the success or failure of a desalination
installation and influencing the overall performance of the plant. Traditional pre-
tTeatment do not remove dissolved organic matter which is mainly responsible tor RO

1-7
fouling. Thus it is necessary to go for new generation of pre-treatment methods to
reduce operational and energy costs of RO. The use of granular activated carbon (GAC)
as biofilter n1edia has several advantages. GAC possesses an extremely large and
irregular surface of the order of several hundred m 2/g of carbon that provides a large
number of available sites for the adsorption of substrates and microorganisms (McKay,
1996). The GAC structure can protect microbes from shear loss during biofilter
operation.
The development of pre-treatment by using GAC biofiltration and low dose coagulation
presented in this study will help to improve the fouling problem while reducing the cost
for RO operation. The flo cculation and adsorption used as pre-treatment will help in
removing large and small molecular weight organic compounds. Thus these processes
are also studied and compared with that of GAC biofiltration.

1.9 Aim of the study

The research work involved extensive experin1ents both in laboratory and in field. The
main objectives and scope of this study are as follows:
• Assess the relative merits of different pre-treatment processes In terms of
tnembrane fouling reduction.
• Evaluation of different fouling indices. Assessment of different pretreatments
such as MF, UF, flocculation and adsorption in terms of fouling indices.
• Evaluate GAC biofiltration as a cost-effective pre-treatment.
• Establishing an optimum design for the biofiltration pre-treatment with low
flocculant dose to reduce the fouling of the RO desalination.
• Observation of the behaviour of the fouling tendency of Reverse Osmosis (RO)
after different pre-treatment

1- 8
~UTS
University of Technology, Sydney

CHAPTER2

Literature Review

2- 1
 2.1 Introduction

Seawater desalination is one possible solution to produce drinking water using reverse
osmosis technology (RO). Seawater contains impurities such as various cations, anions,
particulate matters, organic matter and living organisms. These impurities cause severe
fouling of RO membrane. Pre-treatment can ensure lower fouling of RO membrane.
Choice of pre-treatment varies as the characteristics of seawater depend on the climate
and location.
Membrane fouling, different pre-treatment methods and fouling indices are reviewed in
this chapter.

2.1.1 Seawater
The characteristics of seawater at Chowder Bay, Sydney is given in table 2.1 .
Table 2.1 The characteristics of seawater at Chowder Bay during June- October 2008

Analysis category Concentration Analysis category Concentration

_Qt! 8.2 N02-N (mg/L) <0.01
r---'=';al ini!Y_(g/L) 37-40 Se ( ~ giL) <25
Cond uctivity 51. 8-55 .5 C r (~ g/L) <25
(ms/cm) I
r - · - · - · - --- - - - -
r---_I'S S_L11]_g[l2_ ___ 2-l3 Fe (mg/L) <0.05
Turbidity (NTU) 0.5-0.7 J\1n (Jlg/L) 2-3
Alkalinity (mg/L as 66-80 (mostly Ni (~ giL) <1 0
1
CaC0 3) bicarbonate) I
UV2s4 0.026 C~[!J___ <10
<]
~-

DOC (mg/L) Pb (Jlg/L) <2

r--__ BOD J!!l_&L) ___ <1
--- - - - - - - - -
_ _ As___(gg/L) <25
Coliforms/1 OOm L <2 -- ---- - Cd (~g/L) <0.1
TotaJ phosphorus <0 .01-0.06 Hg (Jlg/L) <1
(mg/L) ------------·
N03-N (mg/L) 0.01 Zn (~g /L) <25
NH4-N (mg/L) 0.02

2.1.1.1 Seawater organic matter (SWOM)

Although organics are negligible in concentration (2-4 mg/L) as compared to inorganic
constituents, they create severe fouling problems to reverse osmosis used in the
desalination process. SWOM varies with the season and location. SWOM is mainly
dominated by humic substances which mainly consists of acid rich aliphatic polymers

2-2
with molecular weight of 500-1000 (Da) that bear little resemblance to any known
biochemical or humic substances in soil (Hedges 1987).

2.1.1.2 Dissolved organic matter in seawater

It is not possible to characterise total organic matter present in seawater. It is possible to

measure only dissolved organic carbon (DOC) present in the seawater (which is
equivalent to half of the organic matter present in the seawater) by complete combustion
of C0 2 • Although the amount of DOC present in seawater is very small it undergoes
various marine processes. The surface-active DOC that concentrates on the surface level
undergoes photochemical reaction as well as affects the transfer of light, gases and wind
energy (Hedges 1987). The tendency to concentrate on interfaces also causes DOC to
adsorb onto particles suspended in seawater, thereby changing their charge and surface
properties. Finally some DOC components chemically combine with some dissolved
metals to form complexes that affect the chemical properties of seawater and
phytoplankton production. Fouling of RO membrane results in serious problem
including:
i) A gradual decline in membrane flux, as a result of decrease of permeate
flow
ii) With the increase of membrane fouling, the transmembrane pressure
(L:~P) also increases. So, high pumping rate is required.
iii) Degradation of membrane
The above mentioned factors affect the cost of water production from seawater. To
overcome these problems research is continuing in an attempt to reduce the dissolved
organic matter and inorganic constituents from the feed to RO by various pre-treatment
methods.

2.1.1.3 Characterization of organics present in seawater

The characteristics and organic matter concentration are different in sea/brackish waters
compared to fresh surface waters or biologically treated sewage effluent (BTSE).
Detailed pre-treatment studies conducted with different fractions of BTSE showed
varying degree of removal (Shon et al., 2004; Jarusutthirak and Amy, 2002). Organic
concentrations in seawater are typically low. In this study characterisation of the
orgamcs present in sea/brackish water was done by size exclusion chromatography

2-3
(SEC) . The MW ofthe untreated seawater ranged from about 1070 Da to 100 Da (figure
2.1 and table 2.2) .

2.0
346 Da

~
SWOM

Biopnlymes Low lVl\V

II
neutrals and
>E
1.5 Fulvic acids,
hu rnit.• II I a m p hiphilics
<!.~
~uhstanccs
>
-
::::>
Cl)
1.0
f/)
c: 1066 D
0
c.
f/)
Cl) 93 Da
0::
0.5

0.0+---~--~-------L~-----L--~------~~--~

600 800 1000 1200 1400

Time (sec)
Figure 2.1 l\.1WD of SWOM (seawater organic matter)

Table 2.2 Organic matter and Molecular weight found in this study
-·
Classification
Organic (1-3 mg/L) Molecular weight (Da)
--
Biopolymer
Fulvic acid 1000-1100

Low molecular Acids 300-400

Low molecular neutra ls
Amphiphilic compounds <100

The MW fraction found in this study represents biopolymers (polysaccharides and

proteins), fulvic acid, low MW acids (hydrolysates of humic substances), and
amphiphilics, respectively (Huber, 1998; Shon et al., 2008).

2.1.1.4 Inorganic matter

Inorganic constituents present in seawater that are most likely to cause foul ing are Ca+2,
Mg+2, C03-2. S04-~, sil ica and iron (table 2.3). The concentration of these inorganic

2-4
constituents mcreases in the brine steam with the increase of water recovery. If the
solubility limits are exceeded, precipitation of calcium carbonate (CaC03), calcium
sulphate and magnesium carbonate and silica may deposit on the membrane surface.
These formations of scale on the membrane surface lead to the inorganic fouling as a
result decrease of permeate flow.
Table 2.3 Inorganic matter present in seawater
Inorganic (40-50,000 mg/L)
Chloride: 55%

Sodium: 30.6%

Sulfate: 7.7o/o

Magnesium: 3.7%

Calcium: 1.2o/o

Minor compounds: 0.7%

2.1.2 Seawater Reverse Osmosis in desalination

Worldwide, everyday 23 million cubic meters of water is produced using desalination
technology. Most of the world's desalination plants are situated in Middle East and
North Africa. The growth in membrane applications for desalination has been
exponential over the last decade. Frost & Sullivan (2004) estimated the desalination
plant market to be worth about $1.32 billion in 2003. Growth is expected to continue as
per capita water requirements increase and populations multiply. The world's largest
(reverse osmosis) desalination plant is in Ashkelon, Israel that began operating in 2005
to produce 320 ML of water per day. Recent advances in membrane technology have
led to broad application, and RO systems now represent the fastest growing segment of
the desalination market with more than 50% of the world's desalination capacity.
Nevertheless, under challenging water quality conditions, the operation of membrane-
based desalination plants still remains complex mainly due to membrane fouling.

2.1.3 Membrane Fouling

Apart from salt precipitation (scaling), which is generally resolved by using complexing
agents, membrane fouling can be widely classified as particulate/colloidal and organic
fouling. Particulate/colloidal fouling has been extensively studied and can be controlled

2-5
efficiently by using flocculants. On the other hand, the quantification of organic fouling
requires sophisticated methods and analytical tools to characterize soluble organic
matter. Organic fouling is usually discussed in terms of adsorption of various dissolved
organic materials on and in the membrane. A fraction of this organic matter (generally
small molecules) is easily biodegradable, and when it is accumulated on the membrane
surface in the presence of microorganisms it will result in the formation of biofilm
which is considered as the main cause of fouling in reverse osmosis (RO). Periodic
chemical cleaning (chlorination) is needed to control biofouling. However RO
membranes are not very tolerant to chlorine which decreases their life expectancy thus
increasing the running costs. As a result, pre-treatment and cleaning account for a
significant part of the total cost. Coagulation-flocculation processes have limitations in
removing small MW organic matter, especially those having trans- and hydrophilic
character. In contrast, the same biodegradable organic matter (BOM), the primary cause
of membrane biofouling, is the food for microorganisms. For this reason, Biological
filtration (biofiltration) can be applied for removing organic matter from water. By
utilizing activities of microorganisms fixed on filter media, biofilter can effectively
eliminate organic substances through the biodegradation process. If RO is used as a sole
process in desalination, both colloidal and dissolved organic matter will be retained by
RO membrane which will lead to severe fouling. A study by researchers from Yale
University showed a synergistic effect when both colloidal and dissolved organics were
present to cause significant fouling(Li and Elimelech, 2006).

2.1.4 Types ofnlembranefouling

Membrane fouling is an extremely complex phenomenon which occurs by the formation
of undesirable deposition of particulate/colloidal or organic matter to the membrane
surfaces. (Amoudi and Lovitt, 2007)
The types of RO Fouling can be classified on the basis of fouling material

1. inorganic fouling due to deposition on membrane surface of

inorganic scales (mainly BaS04, CaS04 CaC0 3) ;
2. organic fouling due to organic material (OM) found
in the process stream (humic acids, protein and carbohydrate),
and ;
3 . biofouling due to microbial attachment to membrane surface
followed thereafter by their growth and multiplication

2-6
 in presence of adequate supply of nutrients in the pretreated
feed or nutrients that deposited on membrane surfaces.

Figure 2.2 Complete picture of fouling (Adapted from Vrouwenvelder et al., 2003)

Inorganic colloids: 1
Coagulants: 5%

Silicites/silicates: 13%
Organic compounds: 15%

Figure 2.3 Types of membrane foulant in reverse osmosis membrane (adapted from
Khedr et al., 2000)

2-7
 2.1.4.1 Particulate/Colloidal fouling
Colloids or particulate matters dominate the membrane fouling (Potts, 1981). Particulate
matters in the size range of nanometres to micrometer are defined as colloids. Inorganic
(clays, si I ica salt, metal oxides), organic (aggregated natural and synthetic organic) and
biological (bacteria, microorganism) are the examples of common colloidal foulants.
Champlin (2000) reported that removal of the particles size of down to 1 jlm may not be
sufficient to avoid fouling in many cases. MF/UF pre-treatment sometimes fail to
remove colloids below the size of few hundred nm in diameter and conventional
processes used to pre-treat NF/RO feed water fail to remove sub-micron colloids
(Schafer 2005). The high concentration of the rejected ions in the membrane surface
could promote the aggregation of dissolved matter in to colloidal sized particles .
Moreover, the influence of salt retention and concentration polarization in the
membrane surface area electrostatic particle-membrane and particle-particle interaction
allow collo ids to foul the membrane.

2.1.4.2 Organic fouling

Following are the parameters those influence membrane fouling:
i. membrane characteristics (Van der Bruggen et al.) 2002; Manttari et al., 2000;
Van der Bruggen et al., 1999; Schafer et al., 1998; Elime lech et aL , 1997;
Bouchard et al., 1997),
i- surface structure as well as surface chemical properties, chemistry of feed
so lut ion including ioni c strength (Elimelech et al. , 1997; Ghosh and Schnitzer,
1980) ,
.i- pH (Manttari et al. , 2000; Schafer et al. , 1988; E limelech et al. , 1997; Schafer et
al. , 2004; Childress and Deshmukh, 1998; Childress and Elimelech, 1996;
Elim elech 1994; Suess 1973);
~ the concentration of monovalent tons and divalent ions (Schaferl998;
Elimelech et al. , 1997; Schafer et al., 2004; Yuan and Zydney, 1999; Agui et
al., 1992)
~ the properties of OM, including molecular weight and polarity (Van der

Bruggen 2002; Van der Bruggen et al., 1999; Bouchard et al. , 1997; Bellona et
a l. , 2004 ; Vander Bruggen et al. , 2001);

2-8
 ~ the hydrodynamics and the operating conditions at the membrane surface
including permeate flux (Van der Bruggen et al., 2002; Wiesner and Chellam,
1999; Song and Elimelech, 1995; A WWA membrane technology 1992),
pressure (Roudman and DiGiano, 2000; Schafer and Fane, 1998; Roux et al. ,
2005),
~ concentration polarization (Schafer et al., 1998), and
.4- the mass transfer properties of the fluid boundary layer.
These factors either increase or decrease the fouling rate as have been summarized in
Tab le 2.4. More information can be found elsewhere (Al-Amoudi and Lovitt, 2007). As
it can be seen the Table 2.4, that the chemical (Ionic strength, NOM fraction , etc.) and
physical parameters, such as pressure, velocity, and permeate flux, play a major role in
OM fouling at the RO membrane surface.

Tab le 2.4 Organic matter fouling factors (adapted from Al-Amoudi and Lovitt, 2007)
Value Organic matter Cause
fouling rate
Ionic strength Increase Increase E Iectrostati c

r
concentration repulsion
I
High pH Increase Hydrophobic force
pH Low pH Increase Electrostatic
repulsion
r - - - - - - - - - - - - - - - --
Electrostatic
repulsion and
Divalent cations Presence Increase bridging between
organic matter and
membrane surface
Hydrophobic Increase Hydrophobicity
SWOM fraction Hydrophilic Decrease
- - r--- --
Molecule or High charge Increase Electrostatic
membrane charge repu lsion
Concentration High Increase
polarization
Surface Higher Increase Valley blocking

2-9
 morphology
Permeate flux (high higher Increase Hydrophobicity
recovery)
Pressure higher Increase Compaction

2.1.4.3 Inorganic fouling/Scaling

Inorganic fouling or scale formation 1s senous problem which is occur from the
increased concentration of inorganic matter present in the seawater beyond their
solubility limits and their ultimate precipitation onto the membranes (Wiesner et al. ,
1992). Scaling usually refers to the formation of deposits of inverse-solubility salts such
as CaC03, CaS04·xH20 , silica, and calcium phosphate. To prevent the inorganic
fouling or scaling, it is very important to operate RO systems at conditions lower than
the critical solubility limits. Scale formation also increases the possibility to physical
damage of the RO membrane. It also increase the chemical cost of the RO plant and it is
difficult to restore RO membrane performance due to the difficulties of scale removal
and irreversible membrane pore plugging (Schafer and Fane, 2005).

2.1.4.4 Biofouling
Lappin and Costerton ( 1989) reported biofouling is the fouling where biologically
active organism s are involved. Membrane biofouling is caused by bacteria, fungi and
other eukaryote microorganisms (Flemming et al., 1997). Biofouling is a dynamic
process of microbial colonization and growth, which results in the formation of
microbial biofilms. Biofilm formation consistently precedes biofouling, which becomes
an issue only when biofilms reach thickness and surface coverage that may cause
problems such as declined normalized flux and/or increase in normalized pressure drops
during RO operation (Vrouwenvelder et al., 1998; Ridgway and Flemming, 1996).
Biofouling can be controlled:
4- By removal of degradable components from the feed water, (Al-Rewiali et al.,
2000; Temperely, 1995),
L Ensuring the relative purity of the chemicals dosed and (Dabbagh, 1995)
performing effective cleaning procedures.
-4- Also, it has been reported that cleaning procedures applied when fouling is not a
problem might delay biofilm formation (Hila! et al., 2004). The surface of the

2-10
 membrane offers good site for microbial colonization as it concentrates nutrients
for growth.

2.1. 5 Pretreatment
Feed pre-treatment is a key factor determining the success or failure of a desalination
installation and influencing the overall performance of the plant. The recent case of
Tampa Bay, Florida desalination plant is a perfect illustration of the technical and
economic disaster resulting from a poor design of pre-treatment. Traditional pre-
treatment is based on the removal of suspended material (by processes such as
flocculation, and filtration), supported by an extensive chemical treatment, including
biofouling control (chlorination, dechlorination), and scaling prevention (dosing of
acids or antiscalant additives). Tvlembrane cleaning involves alkaline solutions (pH 11-
12) for removal of silt deposits and biofilms, and acidic solutions (pH 1-2) to dissolve
metal ox ides or scales, as well as a wide range of extra chemicals such as detergents,
oxidants, complexing agents and biocides. As a result, the pre-treatment and cleaning
accounts for a significant part of the total cost (Bruggen and Yandecasteele, 2002). On
the other hand, if one uses MF/UF as pretreatment, particulate matter can be removed in
a cost-effective manner. Further, adsorption and flocculation (alone or together with
MF/ UF in hybrid configuration) can remove most of the dissolved organic foulants .

2.1.5.1 Conventional pre-treatn1ent

In RO applications, the frequently used filter types are pressure or gravity filters in
single or two stage configurations. Pressure filters are cylindrical pressure vessels filled
with a layer(s) of filtration media. The characteristics of media used are shown in table
2.5 . The diameter of pressure filters is limited by the transportation constraints. Usually
the diameter is limited to 3m. The above constraint limits the use of pressure filters to
mainly smaller RO systems.
For RO applications, filtrate quality is determined through measurement of turbidity and
SDI. There is no defined and consistent correlation between turbidity and silt density
index (SDI). However, field experience indicates that to achieve an SDI below 3, the
filtrate turbidity has to be below 0.1 NTU, preferably below 0.05 NTU. Except for
relatively clean surface water sources, such low filtrate turbidity is difficult to achieve in
a single stage filtration. Additional treatment steps many include clarification or
diffused air flotation , prior to filtration .

2-11
Table 2.5 Characteristics of media filter used before seawater desalination (Accord ing
to the Water desalination technical manual, Department of army, USA, 1986)

Characteristics Sand fi lter Anthracite filter

Filtration rate, m/h 10-20 10-20

Depth of bed, em 80 80
Particle size, mm 0.35-0.5 0.7-0.8
Max head loss (gravity Filter), 5 5
m
Max head loss (pressure filter), 200-400 200-400
Kpa
Backwash rate, m/h 40-50 40-50

2.1.5.2 Non-Conventional pre-treatment ( MFIUF as a pre-treat1nent)

Pressure driven membrane processes, such as microfiltration (MF) and ultrafiltration
(UF), are exce llent techniques fo r the remova l of suspended sol ids and for loweri ng
fouling. Energy consumption in MF is relatively low, less than one half of matching
conventio nal pre-treatment (Bruggen and Vandecasteele, 2002 ; Ebrahim et al. , 200 1).
MF generally provides good q uality feedwater fo r RO, with slightly lower COD/BOD,
and silt density index (SDI) compared to untreated seawater. Fmiher improvements can
be obtained by using UF, where microorganisms, macromolecules and colloids can also
be removed. Because of higher applied pressure, UF cost is higher than that for MF, but
is still competitive w ith conventional pre-treatment. On the other hand, the UF permeate
used as RO feed is significantly improved. Despite the above advantages ofMF and UF,
organic fouling remains a problem both for the pre-treatment (MF/UF) and also the
downstream process (RO) due to the existence of small organic molecules which pass
even through UF membranes. Detailed studies have been carried out to characterize
Natural Organic I\1atter (NOM) which is present in surface waters, and effluent organic
matter (EfOM) in biologically treated secondary effluent (BTSE) (Shon et al., 2004).
Furthermore, recent studies proved that hybrid membrane processes (coupling
flocculation and/or adsorption and/or ion exchange resins with membranes) are efficient
in simultaneously reducing membrane fouling and improving water quality (Shon et al.,

2-12
2004; Guo et a!. , 2004; Rong et a!., 2008). However, such results are not available for
sea and brackish waters and are of paramount importance for the rational design of pre-
treatment.
Past studies focused on cross-flow MF/UF which is energy intensive processes. Low-
pressure immersed (submerged) MF/UF is energy efficient and is presently used
successfully from small-scale (0.1 ML/d) to large-scale (375 ML/d) in surface water and
wastewater treatment plants.
Deep bed filtration is widely used to RO desalination plant. Wolf et a!. (2005) compared
UF with conventional pre-treatment (in-line coagulation and 2 stage sand filters) for
seawater. They measured silt density index (SDI 15) and it was found to be lower than
2.5 for UF but greater than 4 for conventional pre-treatment. Treated water quality was
consistent for UF but fluctuating for conventional pre-treatment. UF is a positive barrier
to particles and pathogens but conventional pre-treatment is not a positive barrier for
colloidal and suspended solids (Wolf et al., 2005). Brehant et al. (2002) compared
UF/MF with conventional filtration for surface seawater (SDI 15 ~ 13-25). They found
out with conventional filtration (dual media filtration) that SDI does not reduce below
2.5. SDl was reduced to 1 with UF (UF+ 1 mg/1 FeCb dose) . UF as pre-treatment with
in line coagulation of 1 mg/1 FeCb reduces the RO foul ing and RO plant cost (B rehant et
al., 2002). Pearce (2007) from their study with waste and brackish water observed that
UF/MF pre-treatment ensures higher RO flux, less fo uli ng, chemical dose reductio n and
better on-stream time.

2.1.5.3 Biofilter
The above discussed pre-treatment do not remove dissolved organic matter which is
mainly responsible for RO fouling. Thus it is necessary to go for a new generation of
pre-treatment methods to reduce organic fouling and thus reduce the operational and
energy costs of RO . Even though GAC has a high adsorption capacity, it can only
maintain its adsorption for a short time of biofilter operation and then its adsorption
capacity become exhausted , thus leading to lower treatment efficiency. To recover its
capacity, GAC can be regenerated by different methods such as thermal, hydrothermal,
chemical, ultrasonic regeneration. However, regeneration usually reduces GAC
adsorption capacity and requires a large amount of energy. Another way to extend GAC
life time is using exhausted GAC as support filter media for biological filtration. GAC
provides a high surface area for microorganism growth and development in biofilter. In

2-13
this case, both adsorption and biological degradation take place in treatment processes.
Adsorption is more dominant in the first stage or acclimatized stage when GAC has
attained its full adsorption capacity and microbes start to attach to surface of filter media
and grow up . The latter stage or pseudo steady state is controlled by microbiological
activity (Dussert and Van Stone, 1994). In this stage, biological degradation plays a
major ro le in biofilter. Therefore maintaining sufficient biomass is very important.
Applying backwash is an effective method to avoid the accumulation of excess biomass
that can cause biofilter clogging.
It is found in many studies that biofilter can remove the greater part of organic matters
from water and wastewater (McKay 1996; Loan Hoang 2007). Visvanathan et al. (2003)
observed that, in continuous experiments, MBR gave better DOC removal efficiency
than control membrane reactor. Hu et al. (2005) studied the biofiltration (activated clay,
zeolite) and found out that biofilter can reduce biofouling for RO. The following are the
advantages of biofilter used in water and wastewater treatment:
• Widely applied for removing biodegradable organic matter (BOM) from water
• Biofilter can effectively eliminate organic substances through the biodegradation
process utilizing activities of microorganisms fixed on filter media
• GAC (granular activated carbon) provides a high surface area for micro-
organism growth
• Adsorption and biological degradation take place in treatment processes
The use of GAC and anthracite as biofilter media has several advantages. GAC
possesses an extremely large and irregular surface of the order of several hundred m 2/g
of carbon that provides a large number of available sites for the adsorption of organic
substrates and microorganisms (McKay, 1996). During the biofilter operation the GAC
structure can protect microbes from shear loss. On the other hand anthracite as medium
is cheaper and provides similar advantages like GAC.

2.1.6 Comparison of Conventional and Non-conventional pretreatment

Since membranes provide a barrier to particulates, they provide significant benefits to
the RO/NF, and to the overall system design. These benefits fall into two broad
categories, namely reduced cost of the overall system, and improved on-stream time and
security of supply.

2-14
Table 2.6 Comparison of conventional and non-conventional pretreatment

Parameter Conventional pre- Non-conventional pre-

treatment treatment
Capital cost Less compared to MF/UF Higher than conventional
treatment

Energy required Less energy required using Higher than conventional

gravity flow treatment

Foot print Needs a large foot print Significantly smaller foot print

Chern ical cost Relative high due to Low cost due to low chemical
coagulation required for dosages although this depends
optimization on the water quality.

RO capital cost Comparatively high as RO Higher RO flux reasonably

operate at low flux leads to lower capital cost

RO operation cost Higher than UF /MF Less compared with

conventional treatment

The capital cost of membrane pre-treatment normally exceeds that of conventional pre-
treatment by 20-50o/o depending on the flow rate, feed quality, and local factors.
However, the improved treated water quality can reduce the size of the RO by allowing
a higher RO flux to be used . This advantage tends to be marginal for high salinity
waters above 40,000 ppm TDS, since the RO flux at this salinity is limited by the
osmotic pressure. However, for any feed below 30,000 ppm TDS, the RO flux could
typically be increased by at least 25%, which would create a substantial saving for the
RO system.
In addition to the savings due to the system size, UF/MF pre·-treatment has the
advantage of requiring less space; typically, UF/MF requires 33o/o smaller plant area,
and this too can often translate into capital savings for the plant.

2.1. 7 Case studies of existing plants

The details of pre-treatment process used in the desalination plants are summarized
below.

2-15
 3
Table 2.7 Jeddah SWRO Plant (capacity 56,800 m /d)

Characteristics of Pre- Post Problems during

seawater reatment Coagulant reatment operation Solution
i- Red Sea *- dual Ferric 10 !J.m '*-
membrane ·~ cationic
surface water media filter chloride cartridge degradation due to poly-
with the mixture (DMF) before filters oxidation caused electrolyte at
of sodium (anthracite DMF by chlorine a rate of 0.1
hypochlorite and sand) reaction ppm with 0.3
ppm of ferric
.t- TDS: 43,300 "*- control the SDI chloride
mg/L limit during helps to
i- SDI1s of5.5-6 seasonal variation improve the
feed SDI.

Tabl e 2 .8 Doha Research Plant, Kuwait

Characteristics of Problems during

seawater Pre-treatment Coagulant operation
·~ clogging of dual
' surface seawater in
+- J-flocculation and 4 FeCIS04 media filters,
Doha media filtration (ferric chloride ·+. effect of pH,
(silica sand (0.7- !sulfate) 4. dosing rate of
~ TDS: 47,000 mg/L 1.2 mm, 1m) and FeCJS04
anthracite (1.4-2.5 i- dosing rate of
i'- SDl1 s > 6.5 in flllm, 0.7 m) polyelectrolyte,
average ~ energy input, and
.4-- Climatic conditions
(such as temperature, dust
storm and wind).

2-16
Table 2.9 French Institute of Marine Research

Characteristics of Pre-treatment Results

seawater
'*- Turbidity 4-5 NTU, "~ coagulation and
followed by sand
i- SDI1s: 6.1-6.4, filtration (1 0 ~m)
i- Conductivity level ·+- Pilot trial ofUF; PAC
50-57.3 mS/cm, polysulfone hollow
fiber membrane in "~ UF membrane pilot trial showed a
dead-end mode,
i- pH-8 MWCO 100 kDa and
pore size ofO.Ol ~m.
l- SS: 10-20 mg/L,
For conventional, Permeate SDI
'~* remained between 5. 8 and 5. 9
while the RO membrane had lost
28% of its permeability within 30
days.
constant TMP under the condition
that the flux was lower than 50
LMH with backwash water
containing chlorine.

·*- The SDI of the UF permeate was

i- Temperature constantly between 1 and 2,
variation 9-25 °C turbidity was lower than 0.1
NTU, and SS was lower than 0.01
~fL. ____________

Table 2.10 Persian Gulf

Problems during
I Characteristics of
Pre-treatment Coagulant operation
seawater
i- high turb id water, i- Dissolved air ·i- FeCh and 4- SDI in the range of
possibility of algae flotation (DAF) 1.8-2.9%/min
bloom and/or and
:L hydrocarbon L. DAF with i·•4,. flocculant -~ UV absorbance
pollution, double direct aid removal was in the
;~ SDI 1s (1 0-45%/min) filtration and range of20-30%
two coagulants
injection

Table 2.11 The International Power Mitsui Operation, Indonesia

Characteristics of
Pre-treatment Coagulant Problems during operation
seawater

* Conductivity
(37,900 52,200 )-lS/cm), * DAF unit
followed by a
i- FeCb and ·*- turbidity was less than
0.25 NTU and
~ TDS 25 ,153 - 50,491 polishing filter
ppm, using horizontal ·~ polymers ~ SDI less than 1.5
4- pH 8-8.5 , and filter.
·4-- Turbidity 5-20 NTU

2-17
Table 2.12 ONDEO Services, Gibraltar

Characteristics of

---
Pre-treatment Coagulant Problems during operation
seawater

*- The seawater of .... UF-RO pilot coagulation UF pre-treatment better than

~·
":

Gibraltar was line with with conventional pretreatment.

known as difficult <~ Three dual organic UF reduced SD 1 from 13-25 to
water because it media filters coagulant less than 0.8 .
was subject to (DMF), Floc 10 ·~ DMF filtrate SDI remained
,,..._
algae bloom 10 um between 2.7 and 3.4
·i- Conductivity of
48.7 mS/cm at
cartridge
filtration and
"*' UF permeate had a constant
quality
20°C then followed ~i- DMF filtrate quality fluctuated
i- Silt Density Index byaRO in respect with turbidity.
(SDI 1s) between pilot.
13 and 15 .

Table 2.13 Singapore SWRO

Characteristi cs Problems during

Pre-treatment Coagulant
of seawater operation
4- SDT: 6.1-·6.5 ~ gravity-driven single-medi um coagulant is 4- After sand fi lter,
sand filters and a three-stage dosed prior SDI1s 4.0±0.5 .
.J._ Turbidity ( 10-5-l um) polishing cartridge to the sand
1.5-3.0 NTU, fi ltration fi lter ~ MF pre-treatment
TSS 1.3 mg/L, S DI
i- TSS- 6 4- MF pre-treatment, four hollow- 2.0-3 .0,
mg/L fibre membrane poly-
vinylidene fl uoride (PVDF), '*"
for UF ,80o/o
I
citric aci d is used fo r cleaning rejection ofT SS ,
fo llowed by sodium 40% rejection of
hypochlorite cleaning. organics, SDI 2.5-
3 .0, TMP stable at a
J_ UF pre-treatment pore size filtrate flux of 4 7
O . Ol~m) LMH

i- T he UF pretreatment consisted '~ 16% removal of

of hollow-fibre membrane (pore organics with
size 0.01 ~m) applying the second UF
cross-flow mode (0.5 m/s) and pretreatment, SDil5
backwash water with 1 ppm of varied between 1.0-
sodium hypochlorite . 2.0 when flux is 57
LMH

2-18
Table 2.14 Ashdod, Mediterranean Sea

Characteristics Problems during

Pre-treatment Coagulant
of seawater operation
'*- surface
seawater
"*- coagulation and then
followed by media filtration * ferric
salt with
~ The turbidity was in
the range of 0.1 -
'*- turbidity in (velocity of the sand filters dosing 0.2 and SDI1s was
the range of was 6.5- 7.2 m/h. Backwash rate of reduced to 2.6- 3.8
1- 10 NTU, with air scouring was 0.3-0.7 for conventional
applied every 100 h. ppm filtration
~ TDS -40,500
ppm,
Chlorination in the level of
1.2 ppm) * turbidity 0.09-
0.16NTU and SDI
2.1-3.0 for UF
~ SDI1s was ·*- During the storm
consistently periods when there
6.5 4- UF membrane technology was a high
i- ss: 2 - 14 (The UF pre-treatment concentration of SS
ppm. consists of 50 urn screen in the feed water the
filter, capillary UF module, UF pre-treatment
addition of ferric coagulant performed
at a rate of 0.3 ppm and free significantly better
chlorine addition in the form than the
of hypochlorite at a level of conventional
20 ppm .) system.
i- ln regards to the
flux stability of the
RO units, the feed
water from both
conventional and
UF membrane pre-
I treatment gave
I similar performance.

2-19
Table 2.15 Addur SWRO Desalination Plant, Bahrain

Characteristics

t.
of
Pre-treatment Coagulant Problems during operation
seawater
'*- surface *- Conventional pre- Ferric ~ it could be concluded that
seawater treatment, backwash salt pre-chlorination
from gulf of with air scouring was (dosing demonstrated the negative
Eilat on the applied every 100 h. rate of effects on existing full
Red Sea (velocity of the sand 0.3 - plant and while giving
Shore filters 6.5- 7.2 m/h). 0.7 positive effect on pilot
~ Turbidity :1 ppm) plant
- lONTU, ~~ The dose of 0.25 ppm Fe
:J;._ TDS: 4- Chlorination in the level seems to be the optimum
40,500 ppm, of 1.2 ppm was applied dose for the UF
i- SDI15 was to remove the high level membranes
consistently of microorganisms. "*- it was found out that the
6.5 and chlorine dose at the intake
4- ss 2-14 ~ UF membrane must be raised to 2 ppm in
ppm technology (capillary UF summer to avoid
module, addition of bioactivity, whereas 1
ferric coagulant at the ppm was sufficient during
rate of 0.3 ppm and free winter
chlorine addition in the .... stable operation at a flux
form of hypochlorite at of70 LMH was achieved
the level of 20 ppm ) during the summer month
*- The Multi bore membranes
allow substantial reduction
of chemical consumption
and energy saving
compared with existing
spiral wound UF modules.

2.1.8 Fouling Indices

To assess membrane fouling, a rapid and reliable measurement is needed. The Silt
Density lndex (SDI) is the only standard method presently used. It has many
shot1comings and limitations the most important being the use of a MF membrane, the
characteristics of which are not precisely specified in the standard (Schippers and
Verdouw 1980). Some of these shortcomings were taken into account in the
development of the Modified Fouling Index (MFI) and the Mini-Plugging Factor Index.
However, all these indices neglect the role of colloidal and dissolved matter in water.
Boerlage et al (2002) recommended the use of UF membranes in establishing a new

2-20
MFI-UF index, which considers the effect of colloids. This index is suitable for the
fouling ofUF membranes used in the pretreatment process but not for the fouling ofRO
membranes. Based on recent studies, it seems that fouling of RO membranes is better
represented by the value of the specific resistance of the cake formed by the fouling
components on a NF membrane during a standard filtration test. Khirani et al. (2006)
developed a new method using nanofiltration (NF) membranes (NF-MFI) which is
applicable to most waters, including the ones which have a high fraction of small MW
(dissolved) matter. Their method is practical, as it requires only about one hour to
complete the measurement. However the choice of a standard NF membrane with high
organic rej ection and low salt rejection remains unresolved.

2.1.8.1 SDI and MFI

The most successful test is the silt density index (also known as fouling index),
followed by the silting index. These tests generally do not have a good theoretical basis
so that their value is limited. This applies to the silt density index even though it has
proved to be of great practica l use . The situation as outlined has led to the develo pment
of an index whi ch has a theoret ical basis and which is of practical use. The silt density
index has been taken as the basis, and the principle of the silti ng index has also been
taken into consideration .
The modified fouling index was first introduced by Schippers and Verdow (1 980). It is
derived from the s ilting index and the silt density index based on the occurrence of gel
filtration. Filtration of water containing coJloidal matter through a membrane fi lter (0.45
/1) is controlled by the followi ng mechan isms:
• in the begi nning blocking fil tration,
• afte r a short time gel fi ltration without compaction,
• foll owed by gelfiltration with compaction.
The mathemat ical description of gelfiltration w ithout compaction is simple and
applicable for the determination of an index related to the nature and con centrat ion of
colloids (S chippers and Verdouw, 1980).
MFI is an index by wh ich it is possible to pred ict the fouling rate of reverse osmosis.
However, it is not a completely faithful simulation because the water is conducted at a
relatively hi gh speed along the membrane in reverse osmosis. The effect of this on the
rate of de pos ition of particles of different sizes and types cannot be imitated with this
test. The density of the part icles on the membrane filter are much smaller than reverse

2-2]
osmosis. In view of these uncertainties, the MFI can serve only to a limited extent as an
index of the expected rate of fouling of reverse osmosis membranes by colloids
(Schippers and Verdouw, 1980) .
The most difficult form of membrane fouling to contend with is caused by colloids. This
situation is due significantly to the absence of a measuring method to predict how
rapidly water containing colloids can clog a reverse osmosis membrane. Generally,
known methods such as the weighing of the amount of material that can be filtered,
measuring the turbidity, and counting the number of particles, have long proved their
use in other fields, but they do not provide sufficient information for the reverse
osmosis process (Channabasappa 1975 and Schippers 1978).
Dead end membrane filtration is an efficient technology for the polishing of effluents
from wastewater treatment plants. Filtration characteristics largely depend on the
composition of the wastewater. MFI was used to predict the fouling potential of
different types of effluent that was collected from different wastewater treatment plants.
COD showed good correlation with MFI. However optical density (OD) also showed a
good correlation with MFI (Fuchs et al. , 2006).
It was mentioned by Fuchs et al. (2006) that the process of pore blocking is constantly
occurring and it is not only restricted to the initial filtration phase.

2.1.8.2 MFI-UF
To describe fouling behaviour more precisely, the 1'-AFI-UF was developed to include
smaller colloidal particles not measured in the existing Silt Density Index (SDI) and
MFI0.45 fouling indices by Boerlage (2003). This research investigates the application
of the MF1-UF to measure and predict the particulate fouling potential of reverse
osmosis (RO) feedwater and also to assess pretreatment efficiency. Moreover, it was
shown that cake resistance increased with ionic strength in MFT-UF tap water
experiments and therefore, a correction of the MFI-UF index is required for salinity
effects in RO concentrate (Boerlage et al., 2003).

2.1.8.3 MFI-NF
Based on recent studies, it seems that fouling of RO membranes is better represented by
the value of the specific resistance of the cake formed by the fouling components on a
NF membrane during a standard filtration test. Khirani et al. (2006) developed a new
method using nanofiltration (NF) membranes (NF-MFI) which is applicable to most
waters. including the ones hich have a high fraction of small MW (dissolved) matter.

2-22
Their method is practical, as it requires only about one hour to complete the
measurement. However the choice of a standard NF membrane with high organic
rejection and low salt rejection remains unresolved.

2-23
 ~UTS
University of Technology, Sydney

Faculty of Engineering

CHAPTER3

~EXPERIMEN,_f AL IN.V ESTIGATION

3-1
3.1 Introduction
An experimental study was conducted to determine the effect of different pre-treatment
methods on reverse osmosis desalination. Experiments were conducted both laboratory
and also onsite.

Initial experiments to evaluate fouling index were conducted with synthetic wastewater
in the laboratory. The aim of these experiments was to evaluate the relative merits of the
different indices. Lab scale experiment was also conducted with seawater. The seawater
was collected from Rose Bay, Sydney, Australia. On-site experiments were conducted
in Chowder Bay, Mosman, Sydney.

The water characteristics, experimental and anaiytical procedures are described in this
chapter.

3.2 Experimental Materials

3.2.1 Seawater (Rose bay)

In this study seawater was collected from Rose Bay, Sydney. The average
characteristics are given in Table 3.1.

Table 3.1 Characteristics of the seawater

pH 8.10

Conductivity (mS/cm 50.1

TDS(mg/L) 35000
~-

Turbidity (NTU) 1.01

DOC (mg/L) 1.85

--

3.2.2 Seawater (Chowder bay)

On-site experiments were conducted at Chowder Bay, Sydney, Australia. Seawater was
pumped from 1 m below the sea surface level and filtered using a centrifuge filtration
3-2
 system to remove the large particles. The filtered seawater had the following
characteristics as shown in Table 3.2.

Table 3.2 Characteristics of seawater used in this study

Analysis category Concentration Analysis category Concentration
pH 8.2 N02-N (mg/L) <0.01
Salinity (g/L) 37-40 Se (J.!g/L) <25
Conductivity 51.8-55.5 Cr (!lg/L) <25
(ms/cm)
Tss* (mg/L) 2-13 Fe (mg/L) <0.05
Turbidity (NTU) 0.5-0.7 Mn (J.!g/L) 2-3
Alkalinity (mg/L as 66-80 (mostly Ni (!lg/L) <10
CaC03) bicarbonate)
UY2s4 0.026 Cu (J.!g/L) <10
DOC .. (mg/L) <1 Pb (J.!g/L) <2
BOD (mg/L) <1 As (J.!g/L) <25
Col iforms/1 OOmL <2 Cd (!lg/L) <0.1
Total phosphorus <0.01-0.06 Hg (!lg/L) <1
(mg/L)
N03-N (mg/L) 0.01 Zn (J.!g /L) <25
'---·
NH4-N (mg/L) 0.02
........- -- - -- ...1...-.
* Total suspended solids, Dissolved organic carbon

3.2.3 Synthetic wastewater

Experiments were performed using synthetic wastewater which represents the

bio logically treated sewage effluent. The composition of wastewater is shown in Table
3.3

Tabl e 3.3 Composition of synthetic w astewater (Seo et al, 1996)

Compounds Concentration (mg/1)

Beef extract 1.8

Peptone 2.7

Humic acid 4.2

Tann ic ac id 4.2

Sodium lignin sulfonate 2.4

Sodium Iauryle sulfate 0.94

3-3
 Arabic gum powder 4.7

Arabic acid (polysaccharide) 5

(NH4)2S04 7.1

K2HP04 7

NH4HC03 19.8

MgS04.7H20 0.71

pH
Wastewater 7.3-7.5

3.2.4 Physical properties of Granular activated carbon (GAC) and Anthracite

Raw seawater was pretreated with granular activated carbon (GAC) biofilter and
anthracite biofilter. The physica l properties of the GAC and anthracite are shown in
Table 3 .4. The most important characteristics of GAC are its extremely large surface
area (more than 1000 m 2/g GAC) and high porosity. This property allows the GAC to
adsorb a large amount of organic substances from seawater. GAC and anthracite were
washed with distilled water then dried at 103 °C and desiccated prior to their use.

"l'able 3.4 Physical properties of Anthracite and GAC

Anthracite GAC
Specification Estimated Value Spec{fication Estimated Value
Effective Size Nominal size, 0.3
1.0-1.1
(mm) (mm}
Bulk Density Bulk density 748
660 to 720
(kg/m 3) 3
( kg/m )
Uniformity Iodine number 800
1.30 ( mg /(g.min))
Coefficient
Maximum 5%
Acid Solubility ] o/o
Moisture content

34
3.3 Experimental Methods

3.3.1 Flocculation as pretreatment

Flocculation was used as one of the pretreatment methods. Ferric ch loride (FeCb) was
chosen as flocculant in these experiments as it is capable of removing colloidal organic
matter. Flocculation was carried out using jar test procedures. The feed was placed in a
1-liter container and a predetermined amont ofFeCh was added. The sample was stirred
rapidly (in jar testing apparatus) for 1 minute at 100 rpm, followed by 20 minutes of
slow mixing at 30 rpm and 30 minutes of settling. Turbidity of the supernatant was
measured to determine the optimum dose of FeCb for the feed water. The fouling
indices of the clear supernatant water were measured.

Speed control

Solution
1 litre Jar

Figure 3.1 Schematic ofthe batch experiment using Jar test apparatus
3.3.2 Adso1ption using powdered activated carbon (PAC) as pretreatment

Batch adsorption experiments were carried out with PAC. The PAC was washed with
distilled water and dried in an oven at 103°C. Different PAC doses were added to the
feed water and the content was mixed at 100 rpm for one hour. The fouling indicies of
the supernatant solution were measured.

3-5
3.3.3 Deep bed filtration as pretreatment

Sand and dual media (sand and anthracite) were used as media in deep bed filter
experiments. The filter depth was kept at 80 em for both the sand filter and the dual
media filter. The velocity of the effluent was maintained at 10 m/h. Both media filters
were operated for a period of 6 hrs. Ferric chloride (FeCb) of 1 mg/L was used as
inline flocculant in some ofthe deep bed filter experiments.

3.3.4 Flocculation followed by nticrofiltration

Flocculation was carried with ferric chloride (FeCb), at a dose of 1 mg/L. The
flocculant together with the collected seawater was stirred for 1 min at 100 rpm
followed by slow mixing for 20 min at 30 rpm. The supernatant was collected to
determine the fouling indices and flux decline with a microfilter (MF) membrane. The
MF experiments are described in section 3.3.6.

3.3.5 Long term biofiltration

In this study, biofiltration experiments were conducted using transparent acrylic filter
columns (Figure 3 .2) .
Biofiltration column

3:
0
t ......
Q)
Q) U)
> co
0 3:
..c
U)

~
- ..::z::.
u
co
m

Raw water tank

with feed pump

Figure 3.2 Schematic diagram of biofiltration column

3-6
Initially, biofiltration experiment was conducted in laboratory. Seawater was collected
from Rose Bay, Sydney. Small columns were chosen for these experiments because a
small amount water is sufficient to operate long term biofilter experiments. These
columns had an internal diameter of 2 em and length of 80-150cm with outlet pipes
along the side and at the bottom of the column. Prepared filter media (GAC) was
packed in the columns up to depth of 30cm. The column was operated in downflow
mode. Feed water was pumped from a feeding water tank to the top of the columns and
then passed through the filter bed. The filtrate was collected at the bottom of the column
for analysis.

After successful operation of biofiltration experiments with laboratory, long term

biofiltration experiments were conducted on-site at Chowder Bay, Sydney. These
columns had an internal diameter of 9.5 em and a length of 150 em with sampling ports
along the length at the bottom of the column. Prepared filter media (GAC and
anthracite) were packed in 4 columns (2 anthracite and 2 GAC filter columns) up to a
depth of 80 em. The columns were operated in downflow filtration mode at two
diffe rent velocitie 5 and I 0 m/h. Biofiltration experiments were run conti nuously for a
duration of 8 weeks. The filters were backwashed each day for a period of 5 minutes to
control excessive biofilm growth. The filtrate was collected at the bottom of the column
for analysis.

3.3.6 Membran es and Flux decline experiments

MF membrane of 0.45 ~m (cellulose acetate, Whatman GM) were used in the

membrane filtration experiments. The permeability of the membrane with pure water
was measured initially.

A cross flow sample cell was employed to study the flux decline. A 1OL feed tank was
employed to provide a continuous supply of feed water, with a pressure of 60 kPa. The
crossflow velocity was maintained at 0.5 m/s. The permeate was recirculated to the feed
tank . Milli- Q water was filtered initially to stabilize the membrane. Pure water flux was
monitored until a constant flux was obtained. The feed water was then used in the
filtration unit to determine the flux decline.

3-7
 Flow rate indicator
Recirculate
permeate

By-pass Press.Jre
gauge

Feed pump Crossflow Unit

Feed Tank

Figure 3.3 Schematic drawing of cross flow unit

3.3. 7 Reverse osmosis (RO) as a post treatment

The pre-treatment efficiency was also assessed in-terms of reverse osmosis (RO) flux
decline.

Pressure Pressure Gauge

Flow Rate
Regulating Valve
Indicator
Concentrate

Permeate
Pressure Gauge
SWRO unit
Pump

Figure 3.4 Schematic drawing of cross-flow SWRO unit used in this study

Cross-flow Seawater Reverse Osmosis (SWRO) experimental set-up used in this study
is shown in Figure 3.4. In this study, RO flux decline was measured both for the

3-8
pretreated effluent and seawater. The characteristics of RO membranes were used in this
experiment are given Table 3.5. The raw seawater and pretreated seawater were
pressurized at 6000 kPa under 28 °C Temperature controller was used to keep the
temperature constant. The total volume of feed seawater before and after pre-treatment
used was 5 L and the retentate was continuously recirculated to the feed tank. The feed was
changed every 24 h of operation.
Table 3.5 Characteristics ofRO membrane used
Material MWCO* Contact Zeta potential PWP**at 6000
(dalton) angle( 0 ) at pH 7 (mY) kPa (m/d)

SR Aromatic 100 35 - 21 2.94

pol yam ides
..
"' MWCO: molecular we1ght cut-off. "' "' PWP: pure water permeability

3.4 Analytical methods

3.4.1 SDI and MFI
Silt Density Index (SDI) and Modified Fouling index (MFI) were measured after each
pre-treatment.
Pressure gauge

't '
,..JC~ {

'
I
,-----if"·""··""LL
'l ......-.m I
r-

(
_J-~·-,_. \ ~-=-.~~I -

i . -
I Feed tank

I Membrane I Permeate

'
/ N:1 gas ' •• .,. •• •.• . ...
·~ .... > " """ • > ...

L ,... .,... ., .......... ·«<--·~·--·-..-·~...... ~

I
.~~
.... jo QJ
""""~i

Data acquisition Balance

Figure 3.5 MFI and SDl experimental setup

3-9
A dead-end filtration unit was used to measure the MFI and SOL The schematic
diagram of filter experimental set-up is shown in Figure 3.5. New membranes were used
in each experiment to avoid the effect of residual fouling and to compare the results
obtained under different conditions. Feed water, with and without pretreatment, was
pressurized into a flat sheet membrane module (diameter of 47 mm). The operating
transmembrane pressure was controlled at 2 bars by means of pressure regulating valve.

SOl is the most common fouling index used in the industry. The SOl procedure is
described in the American Standard Testing and Methods (ASTM) 04189-95. SOl is a
simple correlation of variation in filtration time of a known volume of feed after a
certain period of filtration time (usually 15 minutes). The SOl is calculated from the
followin g equation

1- (t./ t)
1
Equation 3.1
SD/ 15 = ' x100
T,

Where
t1 = Initial filtrat ion time (to fi lter a fixed volume of 500 mL)
tr= Final filtration time (to filter the arne fixed volume of 500 mL)
T r = Elapsed time

MFI is an extension of SOl and was developed by Schippers in 1980.

t/V ls'IJ
1 cake filtrntion with
hJi)t; ·ing c,akc .j clogging and/or
filtration filtration 1 cake cvmprcs~iun

v [l]

Figure 3.6 Cake filtration curve (Boerlage, Kennedy et al. 1997).

The MFl is determined from the gradient ofthe general cake filtration equation at
constant pressure by plotting t/V versus V using the equation 3.2.
3-10
 !_ = 7]Rm + 7]aCb V
V MA 2MA 2 Equation 3.2
... )
MFI
Where,

V =total permeate volume (I)

Rm membrane resistance
filtration time ( s)
~p applied trans-membrane pressure (Pa)
2
11 water viscosity at 20°C (N s/m )

a the specific resistance of the cake deposited

Cb the concentration of particles in a feed water (mg/l)
2
A the membrane surface area (m ).

MFI is defined as the gradient of this linear region of t/V vs. V plot normalized to
standard reference values of 207±3 kPa transmembrane pressure, a feed water
temperature of 20°C and MF with a surface area of 47 mm diameter and a pore size of
0.45~m.

3.4.2 Pore blocking index

The pore blocking slope was determined from the gradient of the general filtration
equation at constant pressure using a plot oftN versus t.

t
- = spbt + b Equation 3.3
v
where,
v =total permeate volume (L)
=filtration time (s)
Spb =pore blocking slope by critical time- pore blocking index (1/L)
b =constant
Here, vc and tc are defined as the critical values below which we could obtain a linear
relation between t/v and t.
Spb was obtained with the slope of the straight line between t/v and t (from t = 0 to the
critical point) (Figure 3.6).

3-11
 600

-~ 400
~
+J
300
I
~
M

200
I
r
100

0
'
~
~
--,---_,tel------,---,-------,-----,
4000
0 500 1000 1500 2000 2500 3000 3500
t(sec)
- -- -J
Figure 3.7 t (time)/v (permeate volume) vs. t for feed water

In (CFS-N1FI), a cross-flow sampler was used . The membrane used in cross-flow

sampler was iso-porous membrane of 1.2 micron pore size. The seawater was pumped
through the cross-flow sampler and the retentate was collected into the feed water tank
at a cross-flow velocity of 50 ml I min (which corresponds to a velocity of 0.5 m/s).

3-12
 Flow rate indicator

Pressure
gauge

CF-MFr

l
r:::::l 0 0 0 0
/;;}
Data analysis

Balance
Figure 3.8 Schematic diagram of cross flow unit
The permeate from the cross-flow sampler was directed into the dead-end cell
containing 0.45~tm MF membrane at a constant TMP 2 bar. The time and mass of the
permeate from the dead end cell was recorded and CFS-MFI was calculated.

3.4.4 Molecular weight distribution (MWD) of organic n1atter

The seawater effluent after each pre-treatment was subjected to MWD measurement to
investigate seawater organic matter (S WOM) removal. High pressure size exclusion
chromatography (HPSEC, Shimadzu Corp., Japan) with a SEC column (Protein-pak
125, Waters Milford, USA) was used to determine the MW distributions of SWOM.
Standards of MW of various polystyrene sulfonates (PSS: 210, 1800, 4600, 8000, and
18000 daltons) were used to calibrate the equipment. The weight-averaged molecular
weight can be calculated from the following equation,
II 11

M," = 2_.(NiM/)IL)NiMJ Equation 3.4

i =l i =l

Where Ni is the number of molecules having a MW of Mi and i is an incrementing index

over all M W present.

3-13
 n n

M /1 = ICNiMJ('ICNJ Equation 3.5

i= l i= l

3-14
 ~UTS
University of Technology, Sydney

Chapter 4

Results an Discussion

4- 1
4.1 The effect of pre-treatment on the fouling propensity of
the feed
Traditional methods of water treatment such as coagu lation, floccu lation, sedimentation
and filtration are being replaced by membrane processes such as Microfi ltration (MF),
Ultrafiltration (UF), Nanofiltration (NF) and Reverse Osmosis (RO). The membrane
processes are economical, relatively less intensive in chemical usage, and
environmentally friendlier than the traditional methods (Mallevialle et al., 1996;
Huisman and Tragardh, 1999). However, membrane fouling is a major impediment in
successful use of membrane process for water treatment. Membrane fouling can be
defined as unwanted deposition of feed impurities on the membrane surface (Mulder,
1997;Cheryan, 1998).The consequences of membrane fouling are reduction in permeate
flux; increase in trans-membrane pressure (TMP) which results in the production loss.
Membrane fouling is inevitable and no membrane is immune to fouling. However,
membrane fouling can be minimized by adopting appropriate pretreatment prior to
membrane application.

In this section, the effectiveness of different pre-treatment on the fouling propensity of the
feed was studied using synthetic waste water. The fouling potential of the feed was
characterized by standard modified fouling index (MFI) and cross-flow sampler modified
fouling index (CFS-rvLFI). In CFS-MFI, a cross-flow sampler was used to simulate the
condition of a cross-flow filtration.

4.1.1 Fouling Indices

The fouling propensity of the feed can be characterized by its fouling index. The two
commonly used fouling indices in industry are Silt Density Index (SDI) and Modified
Fouling index (MFI) (Boerlage et al., 1997). The SDI procedure is described in
American Standards Testing and Methods D4189-95.

4.1.1.1 Silt Density Index (SDI)

SDI is a simple correlation of decrease in filtration time of a known volume of the feed
after a certain period of filtration time (usually 15 minutes). T he calculation procedure
is d iscussed in chapter 3, section 3.4.1.

4-2
SDI is usually applied to waters that are to be processed by reverse osmosis (RO). The
relationship between fouling of a microporous 0.45 ~m MF membrane (used in the test
method) and a non-porous RO membrane is different and not clear (Schippers and
Verdow, 1980; ASTM95D4189-95 1995; Kremen and Tanner, 1998; Braus et al.,
2002). SDI cannot predict the fouling rates and is not linear with the concentration of
the feed foulants (Braus et al. , 2002 ; Yiantsios and Karabelas, 2002).

A simplified mathematical hypothesis that shows the relationship between the measured
SDI value and the corresponding amount of foulants deposited on the test filter disc was
studied by Kremen and Tanner (1998). Increase in SDI values corresponds to the
geometric increase in the amount of foulants deposited. Such a hypothesis may not be
applied to different feeds especially feeds that contain different particle sizes. The study
of Javeed (2006) showed that the SDI was different in pure and mixed feeds for the
same feed concentration. The SDI of mixed feeds was higher due to different fouling
mechanisms .

4.1.1.2 Modified fouling index (MFI)

The tN versus V plot as shown in Figure 4. l typically shows three regions in a MFI test
us ing the 0.45 ~m membrane. Here V is the volume filte red in time t. T hese regions
correspond to (i) blocking filtra tion, (ii) cake filtration without compression and (iii)
cake plugging and/or cake compressi on.

The first sharp increase in slope is attributed to membrane pore blocking followed by
cake filtration , which is the linear region of the curve. The MFI is defined as the
gradient (tan8) of this linear region of t/V vs. V plot normalized to standard reference
values of 2 bar (207±3 kPa) transmembrane pressure, a feed water viscosity of 20 °C
and the surface area of the 47 mm diameter of 0.45~m (pore size) microfiltration test
membrane.

4-3
t/V s/1]

cake filtration with

blncking, clogging andfor
filtration cake Ct)mpression

v [1]

Figure 4.1 Cake filtration curve (Boerlage et al., 1997).

Both SDI and MFI are measured in dead-end filtration mode and use a micro-filtration
membrane of 0.45~m pore size. The experimental details and calculation procedure are
given in section 3.4 of chapter 3. In the dead-end filtration all the feed impurities (large
and small) are convected to the membrane surface. fn majority of the real applications,
cross-flow filtration mode is used. The larger impurities are seldom deposited on the
membrane surface due to the shear and inertial lift in cross-flow filtration. Fouling in
crossflow systems is therefore, predominantly due to the deposition of the smaller
particles. SDl and MFI therefore, have been criticized for their lack of fundamental
basis and the assumption of a relationship between a microfilter (used in SDI and MFI
tests) and reverse osmosis membrane (Javeed, 2006).

In this study, MFT and CFS-MFI test were performed on the same experimental rig with
slight modifications (as explained in section 3.4 of chapter 3). The feed (synthetic
wastewater) was pumped from the feed tank by a pump. The characteristics of the
synthetic wastewater used are given in table 3.2.3 of chapter 3. The outlet from the
pump was connected to a dead-end cell through a pressure gauge. The TMP of 207± 3
KPa was maintained through out the test. T ime and mass was recorded using an
el ectron ic balance (section 3 .4 .1 of chapter 3). MFI was then calculated from the

4- 4
volume of water filtered(V) at different times (t). MFI was determined from the slope of
the straight line obtained from the graph between t/v versus V.

=
y 400x +530
R
2
=0.99
800
700
600
::::- 500
in
-400
>
+::I
300
200
100
0
0 2 3 4 5 6
V (I)

Figure 4.2 t (time)/v (permeate volume) vs. v for feed water (0.45 Jlm membrane,
Pressure= 200 KPa, Temperature= 20 °C)

4.1.1.3 Cross-flow sampler MFI (CFS- MFI)

In CFS-MFL a cross-flow sampler was used (Figure 3.7, section 3.4.3 of chapter 3). The
membrane used in cross-flow sampler was iso-porous membrane of 1.2 micron pore
size. The synthetic wastewater was pumped through the cross-flow sampler and the
retentate was collected into the feed water tank at a cross-flow velocity of 0.5m/s. The
permeate from the cross-flow sampler was directed into the dead-end cell containing
0.45J.!m MF membrane at a constant TMP of 207±3 kPa. The time and mass of the
permeate from the dead end cel l was recorded and CFS-MFI was calculated from the
graph t/v versus V.

4.1.1.4 Pore Blocking Index (Spb)

As discussed earlier (Figure 4.1) the pore blocking occurs during the initial phase of
filtration . The methodology to determine pore blocking index is explained in chapter 3,
section 3 .4.2. Eq uation 3.2 is used to determine the pore blocking index (chapter 3).

4-5
 l I

~ 400
2:
.....
300

200

0 ---1 -- -~---~---' ---'

0 500 1000 1500 2000 2500 3000 3500 4000

t(sec)

Figure 4.3 t (time)/v (permeate volume) vs. t for feed water

4.1.2 Effect ofpre-treatment on the fouling propensity

In this study, the effectiveness of difTerent pre-treatment methods such as adsorption (with
povvdered activated carbon PAC) and flocculation (with ferric chloride FeCh) in reducing
the fouling propensity of the feed was investigated. Standard MFI and CFS- MF[ fouling
ind ices were used as an analytical tool to characterize the membrane fouling potential of
the wastewater.

The effect of pre-treatment of flocculation and adsorption was assessed using the standard
MFI and CFS-MFI (Table 4.1). The standard and cross-flow sampler MFI was determined
fr01n the slope oftN vs. V plots using the cake filtration equation (equation 3.2, chapter 3
sections 3.4.1). In CFS-MFI, as mentioned above, the wastewater was passed through a
cross-flow sampler and the permeate was directed to the dead-end cell and the standard
MFI was measured. The cross-flow sampler preferably allows the smaller particles to
reach the membrane (isoporous membrane 1.2 !lm pore size) surface and the depositions of
the larger particles is hindered due to back diffusive forces such as shear, cross-flow
velocity and inertial effects.

4-6
Table 4.1 MFI-CFS- MFI ofSWW (synthetic wastewater) for different pre-treatment

Pre-treatment type MFI (s/L 2) CFS-MFI (s/L 2)

SWW (None) 54095 1420

Floccu lation (FeCb 68 mg/L) 403 112
Adsorption (PAC 1 g/L) 142 46

In CFS-MFI the larger particles are recirculated with the retentate due to cross-flow shear
and the cake formed is predominantly by the smaller particles and will be a function of the
smaller particles concentration. Moreover, the membrane surface area occupied by the
smaller particles is considerably less compared to the larger particles and the particles
smaller than the membrane pore size may even pass through the membrane.

4.1.2.1 Effect of different pretreatments on MFI and CFS-MFI

The t/V vs. V curves w ith pre-treatment (flocculation and adsorption) and wi thout pre-
treatment are shown in Figures 4.4 a and b. The MFI value in CFS -MFI was much lower
than that of standard l\1Fl (Table 4.1 ). Thi reduction of MFI value in CFS-MFI can be
attributed due to the cross-tlow filtration geometry .

68 m g/1 FeCI3 ...-1 g-/~ PAC- -i l --

12000 ~--~:~I
I
1500
8000 I I
~
>
~ I
4000 I
500 1
0 ;
;;~
~ l'U' 'Md
4 6 8
o L--r-----.-
0 2 3
Volume (I) L_ Volume (I)

Figure 4.4 a) tN vs. V of standard MFI with b) tiV vs. V ofCFS-MFI with
different pretreatment different pretreatment

The higher standard MFI value in dead-end cell was due to the deposition of foulants of all
sizes (both larger and smaller) on the surface of the membrane. In dead-end filtration, the

4-7
larger particles occupies a considerable area on the membrane surface and the smaller
particles fills the voids of the cake formed thereby resulting in a very compact cake (with
higher specific cake resistance) which increase or overestimates the MFI (Javeed et al. ,
2006).

T he lower values of CFS-MFI in the above wastewater can be attributed to the above
mentioned factors. The decrease in MFI (standard) was higher for feed with a pretreatment
of adsorption ( as pre-treatment) instead of flocculation (Table 4.1). The organics in
synthetic wastewater are adsorbed on PAC very efficiently and removed from the solution
to a greater extent than the flocculation and hence the deposition of organics on the
membrane surface in standard MFI hence was lower (Figure 4.4).

4.1.2.2 Effect of FeCi} dose on MFI and CFS-MFI

T he FeCI 3 flo cculation process can be used to aggregate colloids and suspended solids
in the size range of 0. 1 -- 10 Jlm. T he effect of FeCh dose on MFI and CFS-MFI was
studied and shown in Figure 4.5. The MFI and CFS-MFI decreased with the increase in
FeCb dose. The difference between MFI and CFS-MFI values was pronounced at lower
dosages i.e. at 10 and 20 mg/l compared to higher dosages i.e at 30, 40 and 68 mg/l. The
DOC removal from synthetic wastewater by flocculation was found to be a function of
flocculant dose and was 78.6o/o at an optimum dose of FeCb. At a lower FeCh dose the
organic molecules were not flocculated to a sufficient amount which results in more severe
fouling . The colour of the supernatant indicated that organic molecule were not flocculated
when low dose ofFeCb was employed

4-8
 ----------------------------------------------~

IZIMFI EICFS-MFI

40000 .

30000

N'
::::::
~ 20000 '
LL
~

10000

0
10 20 30 40 68
FeCI 3 dosage (mg/1)
•

---~

Figure 4.5 the effect ofFeCh dosage on MFI and CFS-MFI

4.1.2.3 The effect of PAC dose

PAC adsorption can successfully remove the majority of small MW organic matter such
as refractory organic matter and hydrophobic organic matter in the range of 200 - 3500
Daltons and a small portion of the large MW organic matter (Shon et al., 2004).

4- 9
 16CXX)

EJ 1\/Fl • CFS-1\/Fl
12000 .

800() .

40()() ,

0.05 0.1 0.5 0.3 1

PAC dosage (g/1)

Figure 4.6 the effect of PAC dosage on MFI and CFS-MFI

The MFI and CFS-M.Fl values increased with the decrease in PAC dose (Figure 4.6).
There was significant reduction in MFI and CFS- NfFl value when the PAC dosage was
increased from 0.05 g/L to 0.1 g/L. However, the reduction of MFI and CFS-MFI was
not that significant when the dose was further increased from 0.1-1 giL as compared to
wen the dosage increased from 0.05 to 0.1 g/L PAC. The consistent values of MFI and
CFS-MFI with the PAC dosage suggest that the contribution to MFI and CFS-MFI was
not affected by the very porous PAC cake. Hence, the contribution to MFI and CFS-
MFI in PAC treatment is only from the foulants not adsorbed by the PAC.

4.1.2.4 Molecular weight distribution (MWD) of the effluents after

flocculation and adsorption

The weight-averaged molecular weight of organic matter was calculated before and
after the pre-treatment. The calculation procedure weight-averaged molecular weight is
discussed in chapter 3, section 3.4.4.

The MW distribution of the effluents without any pretreatment and with the
pretreatment of flocc ulation and adsorption is shown in Figure 4.7 a and b. Flocculation

4-10
with larger doses (closer to the optimum dose) from 68 mg/L to 50 mg/L FeCb removed
the majority of the large MW compounds. However, the smaller molecular weight
compounds in the range of 573 Daltons were not completely removed (Figure 4.5 a).
The phenomenon of the small MW organic matter removal (573 Daltons to 1002) by
FeCb flocculation may be due to the complexation of Fe (Shon et al. , 2004) . The FeCb
doses from 40-20mg/L removed the majority of large MW compounds, but not all of
them . The decrease of weighted average MWD of the effluent was linearly related to the
increase in FeCb i.e. a lower FeCb dose resulted in higher molecular weight fractions in
the effluent (Table 4.2).

ln1tial - Iuili•l
68 mg L·' flocculation 1 KfL PAC •dsorption
30 mg L·' flocculation - - - 0.115 giL PAC "~'"rpliun

10 mg L ' flocculation
> 5
MW:1110

E
MW: 36300
<.- MW. 36258
> 4

l
2.
4>

a:: 2

0~----~~~~=-~----~--~
500 600 700 800 900 500 600 700 800 900

Time {second) T1me Isecond)

a) b)

Figure 4.7 MWD of the effluent of(a) Flocculation and (b) Adsorption

The PAC adsorption preferentially removed smaller MW compounds compared to the

larger MW fractions of the feed (Figure 4.5 b). The PAC used had a pore radius ranging
from 1 to 5 nm with mean radius of 1.8 nm. The removal of some of the MW organics by
PAC can be explained as due to the adsorption onto the larger pores of PAC (macro pores)
and the characteristics and nature of the larger MW fractions of the feed. The larger
fractions are hydrophobic or non-polar that have a greater affinity for PAC (Shon et al.,
2004). The lower MW fractions (1000-500 Daltons) were not efficiently removed by PAC
(Figure 4.5b ). The smaller MW fractions are polar and hydrophilic and not attracted to
non-polar PAC particles.

4-11
 4.1.2.5 The effect of MWD on Spb, MFI and CFS-MFI

The weight-averaged MWD of the compounds and Spb, MFI and CFS-MFI values after
different FeCb doses are presented in Table 4.2. The weight-averaged NIW value of the
influent was 35800 Dalton. The weight-averaged MW value decreased with larger FeCh
doses which suggest that larger doses of FeCh decreased the MW by greater
agglomeration of the organic fractions (Table 4.2). The optimum dose of FeCb (50
mg/L to 68 mg/L) removed the majority of larger organic fractions (MW) leaving only
small weight-averaged MW (520 Daltons) as shown in Figure 4.7a and Table 4.2. The
optimum dose feed behaved as a pure feed with uniform particle size distribution in this
case, all smaller fractions (520 Daltons). Pure feeds yielded lower MFI values compared
to the mixed feeds in standard MFI tests (Javeed, 2006) The lowest MFI value (Table
4.2) with the optimum dose ofFeCb (mg/1) is consistent with the above discussion. The
weight-averaged MW and the standard MFI (dead-end) values were linearly related i.e.
the MFT values decreased with increase in FeCb dose (Table 4.2). This could be
attributed to higher specific cake resistance of the cake formed by a feed containing a
mixture of smaller and larger particles.

A correlation between the amount of PAC dose and the weight-averaged MW is

presented in Table 4.3. The weight-averaged MW values after different doses of PAC
were in the range 21000 - 34000 Daltons Table 4.3. The Spb, MFI and CFS-MFI
values were consistent with the PAC dose (Table 4 .3). Lower dose of PAC resulted in
higher MFI and CFS-MFI. The relatively consistent NlFl and CFS-MFI values with
MWD of the feed can be attributed to the adsorption that was function of PAC
concentration.

The change of pore blocking index is also consistent with ferric chloride and PAC dose.
The value decreased with the optimum pre-treatment.

4-12
 _,__
Table 4.2 Weight-averaged MW values of the effluent samples after flocculation
:,-..-.:.

\\!eight-averaged MFI with cross-flow MFI with dead-end Pore blocking index
FeCb dose mg/L
molecular weight (s/1 2) ( s/1 2) (1/L)

------·
68 520 115 407 0.7
40 26200 403 627 0.9
30 29300 138 256 0.8
20 29600 15151 17411 3.8
0 35800 2996 54095 6

Table 4.3 Weight-averaged MW values of the effluent samples after adsorption

Pore
Weight-averaged molecular 2 blocking
PAC dose IvlFI with cross-flow (s/1 2) MFI with dead-end ( s/1 )
Index (1/L)
weight
g/L

l 21000 129 44 0.33

0.5 27080 140 820 1.1
0.3 32580 190 1755 l.63
0.1 33000 289 2616 1.6

0.05
3964
13523 2.1
34523
0 35800 2996 54095 6

4-13
4.1.3 Conclusions

The effectiveness of different pretreatments (flocculation with FeCh and adsorption with
PAC) on the fouling propensity of the feed was studied using synthetic wastewater. The
fouling potential of the feed was characterized by standard modified fouling index (MFI)
and cross-flow sampler modified fouling index (CFS-MFI). The flocculation and
adsorption decreased the fouling propensity of the feed. MFI and CFS-MFI fouling indices
were effective in evaluating the pre-treatment efficiency. The MFI and CFS-MFI was
linearly related to the dosage ofFeCb. Both, MFI and CFS-MFI showed linear
relationship with PAC dosage. The MWD data has given very important insights in
understanding the fouling propensity of the feed depicted by MFI and CFS-MFI indices.

4-14
4.2 Effect of pre-treatment in reducing the fouling: A
Laboratory scale study with seawater
GAC biofiltration, adsorption and flocculation is used as pre-treatment for seawater.
Low dosage coagulant (2 mg/L FeCh) and adsorption (0.05 giL PAC) was used in this
study to assess the effect of low dosage coagulation/adsorption to alleviate the fouling
problem. The flocculation and adsorption is used as pre-treatment for removing large
and small molecular weight organic compounds. Different fouling indices are discussed
in detail as they are the key to assess the pre-treatment.
In this study, the reduction of the fouling potential of raw seawater arising from various
pre-treatment processes was studied in terms of fouling index (FI) and Molecular
Weight Distribution (MWD). Traditionally the cake filtration method is considered in
the calculation of the FI. To gain a better understanding of the phenomenon of fouling
potential as measured by FI, the Molec ular Weight Distribution (MWD) of organic
matter in the effluent of pre-treated seawater was also measured using high performance
s ize exclusion chromatography.

4. 2. 1 Seawater
Seawater was collected by "Seawater Transport" at Rose Bay, Sydney during the
incoming ti de (normally around high tide) . It underwent the followi ng two treatment
steps to elim inate the large particles present in the water.
The treatment steps used are as folio ws:
1. The rotating drum : Aquasonic RDF 100 with a mesh size 200 ~m was designed
to remove particulate matter. The drum was automatically back washed . It
needs maintenance every 6 months.
2. The bag filter of a pore size of 5 J.!m was used as post-treatment to the rotating
drum.
The Characteristics of seawater taken from Rose Bay are given in Table 4.4.

4-15
Table 4.4 characteristics of the seawater (Rose Bay, Sydney)
pH 8.10

Conductivity (mS/cm) 50.1

TDS(mg/L) 35000

Turbidity (NTU) 1.01

DOC (mg!L) 1.8

Although the organic content in the seawater is negligible in concentration (1.8 mg/L)
as compared to inorganic constituents, they pose acute fouling in reverse osmosis used
in desalination .
Molecular weight distribution of organic matter in the seawater (SWOM) was measured
using HPSEC. It showed peaks at 1066 Da (biopolymers), 346 Da (low MW acids) and
90 Da (low MW neutrals and amphiphilics) (Figure 4.8).

2.0
- - 9NOM

1.5 Low :rvl\?i/ .J.cids

>E
~~

-
:::::>
(I)
(I)
1.0 Biop olymets,
Fulvic acids,
c
0 humic substances
a.
en
~
0.5

0.0
600 800 1000 1200 1400

Time (sec)

Figure 4.8 MWD of SWOM (seawater organic matter)

4-16
4.2.2 Pretreatments

4.2.2.1 Comparison of different pretreatment in terms of Modified Fouling

Index (MFI)
The MFI was measured using dead-end and crossflow microfiltration (MF cells).
Experimental setup and calculation procedure for MFI, CF-MFI and Spb are discussed
2
in the section 3.4 in chapter 3 .The MFI of raw seawater was 91 s/L while after
pretreatment with PAC (of 0.05 mg/L) adsorption and FeCh (2 mg/L) flocculation , the
MFI was reduced to 75 s/L 2 and 60 s/L 2 respectively. Pretreatment with GAC biofilter
2
gave the highest reduction of MFI. The MFI was reduced to 14-20 s/L during the 30
days of operation which makes the GAC biofilter very attractive as pretreatment.

Table 4.5 MFI for different pre-treatment

Pre-treatment MFI CF-MFI Spb
(s/L 2) (s/L 2) (Pore blocking
index) (1-1)

Seawater 91 61 0.43

,____ _ _____ ---

Flocculation 60 45 0.36

(2 mg!L)
----
GAC biofiltration 14 3 0.24
I

(after 30 days II
of operation)
Adsorption 75 50 0.36

PAC (0.05 g/L)

The crossflow MFI results showed that the pre-treatment by GAC biofiltration reduced
2
the MFI from 61 to 3 s/L • GAC biofi ltration gave rise to the lowest fouling index value
as GAC has a larger surface area for the microorganism to grow, which biodegrades the
organic matter. Thus GAC filter can be one of the viable and economical pre-treatment
methods as there is no need to thermally regenerate the GAC. Pore blocking index (Spb)
also gave a lower index of 0.24 L- for the GAC biofilters than other pretreatments.
1

4-17
4.2.2.2 Comparison of pre-treatment in terms of SWOM removal efficiency

Figure 4.9 shows the SWOM removal by di fferent pretreatments. Here, SWOM was
measured in terms of di ssolved organ ic carbon (DOC) concentration.

r--
1.8 1 -

1.6 -

E 1.4 1-

I
~ 1.2 1 - -...,.,
'!\;'""".
0
~ I" . ~1
~ -
B ,,, '~{

c: 0.8 · - !}
8 '"'
~
0.6 -
~
0.4 1-- 1-
.. i
A
0 .2 -- -- -- r--------- 1----

0 .....--- -r-----...---'-· - -'--·

MF Flocculation Adsor ption GA C
filtration
Different pretreatments

Figure 4.9 SWOM removal by pre-treatment ofMF, FeC1 3 Floccu lation, PAC
ad -orption and GAC Biofiltration (seawater DOC = 1.8 mg/L,)

The initial SWOM concentration after passing through a 0.45 Jlm MF was 1.8 mg/L.
The SWOM removal by pretreatments such as PAC adsorption, FeCb flocculation and
GAC biofiltration was 34%, 35% and 68%; respectively. The GAC biofiltration resulted
in the highest removal of SWOM. Many studies showed that biotilter can remove the
majority of organic matters from water and wastewater with less operation and
maintenance requirement (Clark and Boutin, 2001; Me Kay, 1996). Small fractions of
organic matter which cannot be removed by other conventional treatment processes
such as flocculation, filtration can also be removed by biofilters.

4-18
4.2.2.3 MWD of SWOM after different pre-treatments

The MWD of SWOM in seawater was measured after each pre-treatment. The MWD of
SWOM was analyzed by using the response (mV) data ofHPSEC with elapsed time.

2.5 ,--------------~==================~
--Seawater
· · · .. · After GAC biofiltration
346 Da ---After FeCI 3 flocculation
2.0
- · · - After PAC adsorption

>E
<t.- 1.5
>
-
:::::>
Q)
(/)
h

i\
i\
1::
0 1 .0 1066Da 1\
c. ; : 1\
(/)
Q)
a:: I \1\
: .I \
0.5 \

... ..,.. ··;

1"'-:.-,l
---- .....,
...A.\ .. \..,_.:..:,-
.... ......)' ' ----------
~. . ..
~~ ·-•.:.·.·.:..:..: :::..:. :::::;./': ·· ··..._: ·. ..,.....··, I ....:,.. . ... ....... ...... .
- . - - - - - - - , - - - ·~-·---;..-· ·~......__~
-__;:_:_:··:..:::-=..<...:.·

600 800 10 00 120 0 140

Time (sec )

Figure 4.10 MWD ofSWOI\1 after FeCh flocculation, PAC adsorption and GAC
Biofiltration pretreatments (FeCb dose= 2 mg/L; PAC dose= 0.05 g/L, GAC column
depth of 30 em)

The MW of the initial SWOM ranged from about 1066 Da to 93 Da. Typical MW peaks
for the seawater was found at around 1066 Da, 346 Da, and 93 Da (Figure 4.1 0). Here,
it shou ld be noted that the seawater characteristics and the MWD of SWOM vary from
season to season and from place to place. However, the major type of SWOM is same
although their percentage varies. The MW fraction of 1066 Da, 346 Da, and 93 Da
found in this study represents biopolymers (polysaccharides and proteins), low MW
acids (hydrolysates of humic substances), low MW neutrals and amphiphilics,
respectively. This analysis was made by comparison with previous studies (Huber,
1998 ; Huber, 2007; Gaid and Treal, 2007). Figure 4.10 also shows that, FeCb
flocculation removed I 066 Da (bio polymers) while GAC biofiltration removed

4-19
biopolymers and low MW acids. However, GAC biofiltration removed the large MW
organic compounds and resulted in a lower fouling index.

4.2.3 GA C biofiltration as a pretreatment

In this study, a long term biological filtration experiment (30 days) was conducted using
transparent acrylic filter columns and was running for 30 days. Experimental details are
discussed in chapter 3, section 3.3.5.

4.2.3.1 MFI
Pre-treatment with GAC biofilter resulted in a MFI between 14 and 20 s/L 2 (with dead
2
end cell), 3-4 s/L (for CF-MFI) and 0.24 1/L (for Spb) during the 30 days of operation.

Table 4.6 MFI and CF-MFI after GAC filtration

Filtrate MFI CF-MFI Spb

collected s/L 2 s/L 2 L-l

from GAC
column
(Days)
>--------- - - - - - -
f-o---+,~ 61.3 0.44

2---- 61 30.6 0.38

12 14.04 4.3 0.26

30 20 3.4 0.24

4.2.3.2 DOC removal efficiency

GAC biofilter lead to 68% organic removal (in terms ofDOC) even with a shallow filter
depth of2 em .

4-20
 70
...

60

~ 50
10
E 40
~
g 30
.....

20

10

0 " - --

0 5 10 15 20 25 30 35
Time (days)

Figu re 4.11 DOC removal ofthe GAC biofilter (filtration rate = I m/h, GAC medium
depth= 30 em, average influent DOC = 1.8 mg/L)

4.2.3.3 MWD of the permeate of GAC filtration

2.5, I - Seawater influent '1

I - -- 12 days effl uent from GAC I
I ~ 20 days effluent from GAC J
2.0 I 346 Da - ... 30 days effluent from GAC

>E
<( 1.5
>
:::>
OJ
t/)
c:
0 1.0
c. 10~6 Da
t/)
OJ
o:=

600 800 1000 1200 1400

Time (sec)
Figure 4.12 MWD of SWOM after different days from GAC pretreatment

4-21
Figure 4.12 shows the MW of effluent from GAC biofiltration collected on different
days. Similar intensity of MW is observed for effluent collected on different days upto
30 days. GAC biofiltration removed large MW (biopolymers), and low MW acids.

4.2.4 Concluding remark

Pre-treatment reduced the organic matter (SWOM) concentration and resulted in a
lower fouling of the RO. Compared to flocculation and PAC adsorption, GAC
biofiltration removed a larhger amount of organics (DOC removal of 68o/o).

4-22
4.3 Assessment of pre-treatment to microfiltration for
desalination in terms of fouling index and molecular weight
distribution
Microfiltration as a pre-treatment is gaining importance in seawater desalination. It is
important to study whether MF can function as a sole pre-treatment prior to RO or
needs to couple with flocculation/ filtration. In this study, different processes such as
flocculation with ferric chloride (FeCh) and deep bed filtration (sand filtration and dual
media filtration) as a pre-treatment to microfiltration (MF) were used for seawater
desalination. The performance of these pre-treatments was determined in terms of silt
density index (SDI) modified fouling index (MFI) and flux decline in MF.

4. 3.1 Characteristics ofSeawater

The experiments were conducted on-site at Chowder Bay, Sydney, Australia. Seawater
was pumped 1 m below the sea surface level and filtered using a centrifuge filtration
system to remove the large particles. Characteristics of filtered seawater are discussed in
chapter 3 in section 3 .2 .2 .

4. 3.2 Comparison of different pretreatment methods

In this study. comparison was done for the following pre-treatment methods:- .

l. Flocculation followed by microfiltration

Flocculation was carried out with ferric chloride (FeCb), at a dose of 1 mg/L.
The flocculant together with the collected seawater was stirred for 1 min at 100
rpm followed by slow mixing for 20 min at 30 rpm. The supernatant was
collected to determine the SDI, MFI, MWD and flux decline with a MF
membrane.

2. Deep bed filtration followed by microfiltration

Sand and dual media (sand and anthracite) filtrations were used as media for
deep bed filters. The filter depth was kept at 80 em for both the sand and the
dual media filters. The velocity of the effluent was maintained at 10 m/h. The
effluent was collected when turbid ity removal became constant. Ferric chloride

4-23
 (FeCh) of 1 mg/L was used as an inline coagulant.

4.3.2.1 Effect of Pretreatment on microfiltration (MF) flux decline

The seawater after different pretreatment was passed through a crossflow microfiltration
unit to study the trend of its flux decline. The details of the cross flow microfiltration
used are discussed in chapter 3 (section 3.3.6). The flux decline of MF for pretreated
seawater was studied in terms of normalized permeates flux (J/J 0 ), where J and Jo are
the fluxes at a given time and clean water filter flux respectively. The flux decline (J/J0 )
in MF for seawater after 3 hrs of MF operation was very high and reached 45% (Figure
4.13). After a pretreatment of deep bed filtration where dual media filtration was used
(sand and anthracite, with a total height of 80 em) with an inline addition of FeCb (1
mg/L), the flux decline of MF reduced to about 22%. Filtration with sand (with FeCb at
a dose of lmg/L) gave a similar flux decline of 24%. The flux decline with only a pre-
treatment of flocculation with FeCh (1 mg/L) was 42%. These results indicate that deep
bed filtrati on with in line flocculant addition can remove a majority of SWOM and
reduce the fouling on MF membranes (when MF was used as post treatment to
filtration) . On the other hand, flocculation alone was not a good pretreatment and
requ ired a subsequent solid liquid separation step.

I.O Q;lllf-'._~~-
- .......
- ..- " ' - - - - - - - - - - . . - - -
. --_ -s-
ea_w_a-t-
e r--------~

• '- ......_ .... ··O . sand (flocculation with I mg/ L FeCI3)

. '--:--
'- - - --y- - - dua l (fl occu lati on with 1 mg/L FeC I3)
0.9 ~'-.
'-. - . ----6 · - · fl occul ation with l mg/L FeCl 3
'-.
'-.
0.8 ~ .......
0
.......
.......
.......
.......
T- - ------..,__
0.7 0
.. 0 · ··o ·· ··· O ·
. ... 0 . ..

____ ·-.
.......__
--.
0.6 ·-c:,.. - · -· · -·· ~ . ..........

1
..........
·JC:,.._

• •
0.5 --r--

0 20 40 60 80 100 120 140 160 180

Time (min)
Figure 4.13 Variation of CFMF flux for seawater with and without of pre-treatment
(membrane pore size= 0.45 11m, Cross flow velocity = 0.5 m/s, Pressure= 60kPa)

4-24
 4.3.3.2 Effect of pre-treatment on Turbidity removal
Turbidity of initial seawater varied from 0.5 to 0.7 NTU. All pre-treatments used in this
study lowered the turbidity to a value of 0.2-0.3 NTU except the case of flocculation
with FeCb. Turbidity of the feed water increased to 1.31 NTU after the addition of
FeCb.

4.3.3.3 Pre-treatment and change in molecular weight distribution of organic

matter (MWD)
The MWD of S WOM in seawater was measured after each pre-treatment. The MW of
the untreated seawater ranged from about 1510 Da to 130 Da. Typical MW peaks for
the seawater were found at around 1510 Da, 1180 Da, 530 and 130 Da (Figure 4.14).

0·8 ~-------------~-=vv~:-5~3-o--~----------------------------------~
seawater
.. . . . . . . . .. . . . .. . Flocculation with 1 mg/L FeCl3
------ after Sand (with 1 mg/L FeCl3)
0.6 - ··- ··- ·· after Dual media (with 1 mg/L FeCI3)

>E
._,
~ 0.4
·~
...c
~

-1

0.2

10 12 14 16 18 20 22 24

Time (min)
Figure 4.14 MW distribution of SWOM (seawater organic matter) of seawater and with
pre-treated seawater

The MW fraction of 1510 Da, 1180 Da, 530 and 130 Da found in this study represents
biopol ymers (po lysaccharides and proteins), fulvic acid, low MW acids (hydrolysates of
humic substances), and amphiphilics, respectively (Huber, 1998; Shon et al., 2009). Fig
4.14 shows the MWD of SWOM with and without pre-treatment. All pre-treatments

4-25
used in this study removed polysaccharides type organic compounds that are
responsible for membrane fouling (Huber, 1998). In this study, flocculation with 1 mg/L
FeCb removed the majority of large MW SWOM (1510-1180 daltons) as observed by
Shon et al. (2005) for wastewater. However, flocculation could not remove the small
range MW (530-130) daltons. Furthermore, deep bed filtration with inline coagulation
removed both the large (1510-1180 daltons) and the majority of small MW compounds
(530 daltons) .

4.3.4 Pre-treatment and Modified Fouling Index (MFI)

The relative merits of different pre-treatments were studied in terms of fouling potential.
MFI and SDI 15 measurements were made to compare the different pre-treatments. MFI
and SDI 15 was measured using dead end cell. The details of the apparatus and the
methodology are given in Figure 3.5 and section 3 .4.1 in chapter 3. The calculation
procedure ofMFI and SDl are given in section 3.4.1 in chapter 3.The MFI and SDI1sof
raw seawater were 214-256 s/L 2 and 5.8, respectively. After the pre-treatment of
2
flocculation with PeCb (of 1 mg/L), the MFI was increased to 455 s/L . This may be
due to the fi rmation of floes of different sizes during flocculation. On the other hand, a
pre-treatment with sand and dual media filtration with inline flocculation of 1 mg/L
FeCh gave rise to higher organic removal and also resulted in a very low MFI and SDI1s
2
value of 1··2 s/L and 1.9-2 respectively. MF alone as a pre-treatment reduced the MFI
to 2.6 s/L 2 as it could not remove the dissolved organic matter present in the seawater.
The weigh, average MWD and the corresponding fouling index values after different
pre-treatment methods are shown in Table 4.7. The weight average MW for seawater
was 1420 Da. After the pre-treatment of deep bed filtration with in-line flocculation,
MW of organic matter was decreased. The weight average MWD for sand and dual
media filter (w ith 1 mg/L FeCh) were 1270 and 1160 Da. Deep bed filtration packed
with both media removed the majority of larger SWOM leaving only small weight
average M\V (130 daltons) as shown in Figure 4.14 and Table 4.7. As a result, the MF
flux decline was also not significant for media filtration with flocculation (Figure 4.13).

4-26
Table 4.7 Comparison of different pre-treatment methods
Weight- Flux Pore
averaged MFI decline blocking
Types of feed water 2 SDits
MW (Da) (s/L ) (o/o) index
(Spb)
Seawater after MF alone 1420 214-256 5.8 45 0.22
Flocculat ion (with 1mg/1
1310 455 6.2 42 .04
FeCb)
Effluent from sand filter with
1270 1.8 2 24 .01
1 mg/1 FeCb flocculation
Effluent from dual media
(sand+ant hracite) w ith 1 mg/1 1160 <1 1.9 22 .01
FeC b flocculation

4.3.5 Conclusion
The effectiveness of pre-treatment of sand and dual media fi ltration to M F treatment
was eval uated in term s of fl ux decline, MFl, SDI 15, and MWD. The following
conclusio ns were obtained:
1. Dual media filtration with in-line coagulation gave the lowest value ofMFI and

SDI1 s·
2. Flocculation with 1 mg/L FeCb removed relatively large MW such as l 51 0 Da
and 1180 Da while it cou ld not remove the re latively small MW organic
compounds of 530 Da and 130 Da. Deep bed media fi ltration with inl ine
coagul ation gave better removal of SWOM of MW range of 1510 Da- 530 Da.
3. The flu x decline in MF was minimum when the pre-treatment of dual media
fi ltration w ith in-line coagulation was adopted. Sand filtration with in-line
coagulat ion also gave similar flux decline in MF.
This resu lt indi cates that the combination of deep bed filtration (either sand or dual)
with fl occulation is an attractive pre-treatment to MF used for desalination prior to the
appl icatio n of RO .

4-27
4.4 Biofilter as Pretreatment to Membrane Based
Desalination: Evaluation in terms of Fouling Index
Microfiltration (MF) or ultrafiltration (UF) is an excellent technique to remove
particulate matter as well as reduce the organic fouling of RO membrane. MF provides
generally good quality of water but cannot remove the dissolved organic matter from
the feed water. By UF microorganisms, macromolecules and colloids can be removed.
However, because of higher applied pressure, UF cost is higher than MF and non
conventional pre-treatment. Despite the above advantages of MF and UF, organic
foulin g re main s a problem both for the pre-treatment (MFIUF) and also the downstream
process (RO) due to the existence of small organic molecules which pass even through
UF membranes. For th is reason, it is necessary to go for a new generation of pre-
treatment methods to reduce dissolved organic matter and thus reduce the operational
and energy costs of RO . It is found in many studies that biofilter can remove the greater
part of organi c matters from water and wastewater (McKay, 1996; Loan Hoang, 2007) .
Visvanathan et al., (2003) observed that, in cont inuous experiments, MBR gave better
DOC re moval effi ciency than control membrane reactor. Hu et al., (2005) studied the
biofi ltration (activated clay, zeolite) and found out that biofilter can reduce biofouling
for RO . The use of GAC and anthracite as biofilter media has several advantages. GAC
2
possesses an extremely large and irregular surface of the order of several hundred m /g
of carbon th at provides a large number of available sites for the adsorption of organic
substrates and microorganisms (McKay, 1996). During the biofilter operation the GAC
structure can protect microbes fro m shear loss. On the other hand anthracite as med ium
is cheaper and prov ides similar advantages like GAC.
T he obj ective of this section is to compare t he two biofiltration (analys is of anthracite
and GAC as a media) as a pre-treatment method in terms of the reduction in membrane
foulin g. The reduction of the foulin g potenti al of raw seawater by the use of GAC and
anthracite biofi ltration processes was studied in tenns of modified fouling index (MFI),
silt density index (SDI), turbidity removal and headloss development with filter bed. A
post-treatment of seawater reverse osmosis (SWRO) was also investigated to determine
the extent of red uction in flu x decline by the pre-treatment.

4-28
4.4.1 Characteristics of seawater
In this study, biofilter experiments were conducted on-site at SIMS (Sydney marine
institute), Chowder Bay Sydney. During the experiments, the characteristics of seawater
were monitored regularly. The seawater characteristics are presented in Table 4.8.
Detailed characteristics of seawater are discussed in chapter 3 section 3.2.2.

Table 4.8 characteristics of the seawater

pH 8.10

Conductivity (mS/cm) 50.1

TDS(mg/L) 35000

Turbidity (NTU) 0.5-0.7

4.4.2 Pre-treatment
Raw seaw ater was pre-treated with granular activated carbon (GAC) biofilter and
anthracite biofilter. The physical properties of the GA C and anthracite used this study
are discussed in chapter 3, section 3.2.4. SDI and MFI were measured each day to
assess the memb rane fouling red uction by biofiltration.

4.4.2.1 Variation of seawater Characteristics during experiments

Biofiltration experiments were conducted on-site at Chowder Bay, Sydney from May,
2008 to September 2008 . The variation of seawater turbidity and temperature during
thi s period was monitored as shown in Figure 4.15 (a). Apart from the period of rain,
seawater temperature was fairl y uniform (around 15 °C). The turbidity was also
consistent in the range of 0.5-0.7 NTU. Turbidity increased during rainy period up to
1. 10 NTU .

4-29
 b) variation of SDI10 with turbidity
. a) variation of turbidity and temperature 1.8 10.0
18 19
-+- Tw-bidity -+- Tw-bidity
1.6 1.6 -o- SDJ 10
-D- Terq>erature °C 9.5
18
1.4 1.4
u
-=
9.0

-
£ 1.2 17
0
~ .0 1.2
;a
-s -=
.....

-=
0
"'0 ......
:.0 1.0 ~ :.0 1.0 8.5 ~
~
Q.
1JJ

E-o 0.8 16 E-o 0.8

~
f-. 8.0
0.6 0.6
15
7.5
0.4 0.4

0.2 14 0.2 7.0

Mly Jun Jul Aug Sep Mly Jun Jut Aug Sep

liliE 'fiiiE
F igure 4.15 Seawater characteristics during the experimental period

The SDI of 10 min (SDI 10) was also monitored for seawater during the test period. Here,
SDI 10 was measured instead of SDI 15 because all the 10 L of water used was filtered
with in 10 minutes. 1n this particular experiments larger volume of water was necessary
to measure the SDI 15 and was not possible w ith the equipment used for these
experiments. Figure 4.15 b presents the turbidity and SDI 10 of seawater. SDI 10
fluctu ated in the range of 7.5 ~ 9.2 during this period. It was observed that the SDI 10
values increased w ith the increase of seawater turbidity. SDI 10 increased up to 9.2 when
the turbidity was high with the value of 1.10 NTU d uring the rainy period .

4.4.2.2 Effect of filtration velocity to turbidity removal

The performance of GAC and anthracite biofilters were closely monitored during the
experimental period at two different velocities 5 and 10 m/h. The biofilter experimental
set-up is di scussed in section 3.4.1 of chapter 3.
For the filter operation at a filtration velocity of 5 m/h, anthracite column resulted in
slight ly lower filtrate turbidity than GAC biofiltration (at the initial stage). The filtrate
turbidity value for anthracite and GAC filters was 0.2-0.3 NTU and 0.28-0.31 NTU
respectively (Figure 4.16) . Irrespective of influents seawater turbidity variation, a
consistent filtrate turbidity of 0.2-0.22 NTU observed for both GAC and Anthracite

4-30
biofiltration column even after 55 days when these columns were operated at a filtration
velocity of 5 m/h (figure 4.16).
It can also be noticed that the filtrate turbidity was inferior at higher filtration velocity
of 10m/h. Similar trend was also observed in an earlier study reported in the literature
(Tenzer, 1999).

1.4
• GAC 5 m/h

1.2 • ...
0 GAC 10 m/h
Anthracite 10 m/h

-z • Anthracite 5 m/h
6.

• •

... . ..
~ 1.0 Seawater

--.c
~
• •
0.8
• ••
:.a
:.c;... 0.6
•
•• • • • •• .. •
= • • •• •
. •
~
0.4 ...... ... 0
•
•
0.2 ~~~.~~ ~~~~~ ~~

0.0 ----,-
0 10 20 30 40 50 60
Tirne (day}

F igure 4 . 16 Effect of filtration velocity on filtrate turbidity (GAC and anthracite column
depth: 80 em, ve locity: 5 and 10 m/h

4.4.2.3 SDI 10 and MFI

Figure 4 .15 presents the profiles of MFI and SDI10 of GAC and Anthracite biofilter
operated at different filtration velocities (5 and 10m/h). The average SDI 10 and MFI of
seawater were 7.5 -9.2 and 250 s!L 2 respectively. SDI 10 of the filtrate fluctuated during
the initial period for both GAC and anthracite biofilters. Initial SDI 10 value was 5.5-7 .5
for Anthrac ite at both velocities (Figure 4.15a) . SDI 10 fluctuated more when it was
operated at hi gher filtration velocity of 10 m/h.

For GAC biofilter, SDI 10 ranged at 8-8 .8 during the first 5-15 days. The value of SDI10
dropped to 5-5.5 on day 5 for both filters (which was only a one-off event). After the
maturation stage (after 15 days of operation) both biofilters functioned operated in a

4-31
consistant manner and the SDI 10 values were low at 3.5-4 and 3-4 for GAC and
anthracite columns respectively. As anticipated, lower filtration velocity (5 m/h)
provided a better filtrate quality in terms ofSDI.

10 10
___._ Anthracite 5 m/h __._ GACS m/h
9 . ·0· .. Anthraci te 10 m/h ··0-·· GACIOm/h
9

8
8

- -
7
0
...... 0
...... 7
6
~ ~
rJJ rJJ 6
5 c;P··o
oO 5
4
..o.o
3 4

2 3
0 20 40 60 80 0 10 20 30 40 50 60

Time (day) Time (day)

a) b)

300

250
rr-
J 1
__.__ Anthracite 5 m/h
·· ·O ·· · Anthracite 10 m/h

~ 200~
~ 10 /
0
8
6 40
4
20
2
0 --'-,--'-----,------,------,------,------,--------' 0
0 10 20 30 40 50 0 10 20 30 40 50 60

Time (day) Time (day)

c) d)

Figure 4.17 SDI and MFI profiles for Anthracite and GAC biofilters at 5 m/h and 10
m/h

The modified fouling index results also indicated a similar pattern . MFI value decreased
during the first 5 days of operation and was stable after 10 days operation for both GAC
and anthracite biofilters . During the initial period, the MFI value was found to be very
high i.e . 176 and 312 s/L 2 for anthracite biofiltration at 5 and 10 m/h respectively. After

4-32
 2
5 days of operation MFI reduced to 5 and 10 s/L for anthracite biofilter operated at 5
m/h and 10 m/h respectively. A similar trend was also noticed for GAC biofiltration.
However for GAC filter, it took longer time to stabilize (10 days). From the period of
10 days on-wards the MFI value was low and stable up to the end of experimentation
period of 55 days of operation (for both GAC and anthracite). This suggests that it is
possible to decrease the fouling potential to the RO membrane using a biofilter operated
at 5-10 m/h. However, it is important to wait till the ripening time/ maturity period to
obtain steady solid/organic removal in terms of MFI and SDI.

4.4.2.4 Correlation between different fouling indices

It is important to study the relationship between different fouling indices to identify the
representative FJ for assessing the efficacy of the pretreatment. Table 4.9- 4.12 shows
the relationship between Silt density index (SDI 10), pore blocking index (Spb) and
modified fouling index (MFI) for different filtration conditions studied. Although SDI
measurement is very simple and quick it has many shortcomings. Silt density index only
gives an indication of particulate content of the feed water. Pore blocking index (Spb)
describes the first step of the fouling of membranes while MFI represents the cake
filtration section .

Table 4.9 Comparison of different fouling indices for Anthracite biofilter (filtration
velocity= I 0 m/h)

I Time (day) SDI1o Spb (1/L) MFI (s L -2)

1 8.75 0.13 12.27
5 5.6 0.05 5.72
8 --r--
8.1 0.11 10.24
13 5 0.04 4.4
19 4.3 0.03 3.2
23 3.84 0.03 3.18 --
28 4.2 0.03 2.9
33 4.2 0.04 3.872

-
41
- - -- - - - - -- 4.42 0.04 3.825
57 3.7 0.03 2.532

Table 4.10 Comparison of different fouling indices for GAC biofilter (filtration velocity
4-33
= 10m/h)

Time (days) SDI1o Spb (1/L) MFI (s/L 2 )

1 7.36 0.095 7.3

5 8.48 0.103 9.6

8 8.46 0.1 64 20

13 7.25 0.07 4.1

-- 19 5.16 0.042 4.5

23 5 0.042 4.5

28 5.07 0.043 5
33 4.5 0.036 3.6
41 3.65 0.02 2.4

57 3.5 0. 02 2.4

Tabk 4.11 Comparison of different fouling indices for Anthracite biofi lter (filtration
velocit)' = 5 m/h)

r----

Time(da~ 50110 Spb (1/L) Mf!is/L~---------

l 8.7 0.25 32
5 5.36 0.05 5.3
8 4.9 0.04 4.3
]3 4.9 0.04 4.3
19 5.54 0.05 6.3
23 3.92 0.03 3.3
28 4.9 0.04 3.3
33 4.4 0.03 2.5
41 4.3 0.03 2.8
57 2.85 0.02 2.1

4-34
Table 4.12 Comparison of different fouling indices for GAC biofilter (filtration velocity
= 5 m/h)

Time (days) 50110 Spb (1/L) Mt:.!Js/L

2
)

1 7.9 0.125 78.7

5 7.82 0.103 9.6
8 6.8 0.10 9.4
13 7.51 0.09 7.9
19 5.08 0.04 4.9
23 3. 88 0.03 3.1
28 4.78 0.04 12.6
33 3.81 0 .03 3
41 4.54 r--
0.03 3.2
57 4 0. 029 4

4.4.2.5 Head build up

Figures 4.16 a) and 6 b) present the headloss development for anthracite and GAC
biofilters. As expected, headloss development was faster for higher fi ltration velocity
and finer grain size.

a) GAC b) Anthracite
30

-----
5 m/h --.- 5 m/h
50 c)\ c9. b ···0·· 10 m/h o_ ... o ..
lOm/h
o: --- 25
.o
o ··.
6\
Q :;?
-- 40
E ·.
0 0
5 20 - :o 0
0 :·. ::
~
"-'
0
00
'c)
C)cP ~
"-'

.2
Cll

30 o: Cll

.9 15
Cll

"C c9. .· "'0

~
QJ . . ·o· o ~
QJ

:::::: 20 <P b :I: 10

5
10
0
0 10 20 30 40 20 40 60 80
Time (day) Time (day)

4-35
Figure 4. 18 Effect of filter media and filtration velocity on head loss development (filter
medium depth= 80 em)
When the b iofilt ers were operated at 5 m/h, the headloss development was not
significant. C ompared to anthracite, headloss in GAC biofilter was higher. This may be
due to the smaller size of GAC (Boller and Kavanaugh, 1995).The daily fluctuation of
headloss was due to the backwash ofbiofilter which was performed once per day.

4.4.3 Reverse Osmosis as post-treatment after pretreatments

The pre-treatment efficiency was also assessed in-terms of reverse osmosis (RO) flux
decline. The cross-flow Seawater Reverse Osmosis (SWRO) experimental set-up was
used to determine the RO flux decline. The details on the experimental set-up and the
RO membrane characteristics are presented in chapter 3 section 3.3.7 (also in figure 3.4
and table 3. 5). The RO was operated continuously for 3 days. 5 L of feed water was
used everyday to run the RO.

0.40 T --e- seawater

··· anthracite effluent
0.35 .
- GAC effluent
...-., ---------
..~'-
0
0.30 \
~
..._,
~
'- ........
~ 0.25 '-

"0
' ........
........
QJ ~........
.~ - - - y - - - - - - - · - - - -.- - - - -,.-.-- ~ -- --
-;
s:...
z 0.15
. ··· ··· ····0 ····· ··· ·· ······· ··· ··

0.10

0.05 -t---·-----r---------.-------~------

0 20 40 60 80

Time (h)

Figure 4.19 Temporal variation of RO filtration flux for seawater with and without
pretreatment (SR membrane, crossflow velocity= 0.5 m/s, operating pressure 6000 kPa,
feeding volume: 5 Leach day)

4-36
Reverse osmosi s showed a reduced normalized flux decline (J/Jo) from 0.22 to 0.12 for
pretreated feed with GAC biofilter and 0.35 to 0.21 for pretreated feed with anthracite
biofilter during the first 20 hours. After this period of 20 hrs, there was no significant
decline in flu x. On the other hand , seawater without any pretreatment showed steeper
flux decline and the decline continued even after 3 days of operation.

4.4.4 Concluding remarks

The detailed experimental results obtained indicates that biofiltration as a pre-treatment

reduces a significant amount of organic matter and leads to lower fouling of RO. Fouling
potential in terms of MFI values decreased to 10 s/L 2 within the first 10-15 days of
operation and kept constant upto the remaining experimental period of 55 days of
operation fo r both GAC and anthracite biofilter. The filtrate turbidity was steady after
10 days and remained iow at a value of 0.2-0.3 NTU and 0.28-0.3 1 NTU for anthracite
and GAC biofilter respectively. The headl oss development was low for both the filters.
A post treatment of reverse osmosis after a pretrea tment of GAC and anthracite
biofilters showed a reduction in normalized flu x decline (J/Jo) from 0.22 to 0.12 and
0.35 to 0.2 1 during the first 20 hours respectively. The RO flux for seawater declined at
a faster rate and continued ev en after 20 days when no pretreatment was provided .

4-37
University of Technology, Sydney
Faculty of Engineering

CHAPTERS

CONCLUSIONS

5-1
Membrane based desalination is widely used process to produce fresh water either from
wastewater or seawater. However, membrane fouling increases the energy consumption
as well as operating cost for the water treatment plant. A pre-treatment before reverse
osn1osis (RO) desalination can significantly reduce the membrane fouling. In this study
different pretreatments, such as biofiltration, flocculation, adsorption and microfiltration
are compared in tem1s of fouling reduction to the post treatment of reverse osmosis. The
efficiency of different pretreatments was assessed in terms of different fouling indices,
molecular weight distribution of seawater organic matter after each pre-treatment, and
reverse osmosis (RO) flux decline after each pre-treatment.

Applications of modified fouling index (MFI) and cross-flow sampler modified

fouling index (CFS-MFI) in the assessment of pretreatment of wastewater

The effectiveness of different pretreatments (flocculation with FeCh and adsorption with
PAC) on the fouling propensity of the feed was studied using synthetic wastewater. The
fouling potential of the feed with and without pre-treatment was characterized by standard
n1odified fouling index (MFI) and cross-flow sampler modified fouling index (CFS-MFI).
The flocculation and adsorption decreased the fouling propensity of the feed. Both MFI
and CFS-MFJ were effective in evaluating the pretreatment efficiency. The MFI and CFS-
MFI was linear with the dosage of FeCh. Both, I\1FI and CFS-MFI showed linear
relationship with PAC dosage. '"fl1e MFI and CFS-MFI values for synthetic wastewater
2 2
were 54095 s/L and 1420 s/L • After FeCb flocculation (optimum dose of 68 n1g/L) MFI
and CFS-MFI reduced to 403 s/L 2 and 112 s/L2 . After PAC adsorption with the optimum
dose of 1 g/L the MFI and CFS-MFI reduced to 142 s/L2 and 46 s/L 2.

Comparison of different pretreatment for seawater

Different pre-treatment namely flocculation, adsorption and biofiltration were compared.

Fron1 the results it is clear that the pre-treatment reduces the organic matter
concentration, thus fouling index value. Compared with flocculation and PAC
adsorption, GAC biofiltration removed a higher proportion (68%) of DOC from
seawater. Detailed investigation of MW distribution showed that GAC biofiltration
removes a majority of the large MW organics.

5-2
The MFI reduced from 91 s/L 2 (raw seawater) to 75 s/L 2 and 60 s/L 2 after pre-treatment
with PAC (of 0.05 mg/L) adsorption and FeCb (2 mg/L) flocculation respectively.
Pretreatment with GAC biofilter gave the highest reduction of MFI. The MFI was
reduced to 14-20 s/L 2 during the 30 days of operation which makes the GAC biofilter
very attractive as pretreatment.

Deep bed Filtration as a pretreatment to MF

The effectiveness of pre-treatment of sand and dual media filtration to MF was

evaluated in tem1s of flux decline, MFI, SDI 15 , and MWD. The following conclusions
were obtained:
1. Dual media filtration with in-line coagulation gave the lowest value of MFI and
SDI 15 . The MFI and SDI 15 of raw seawater were 214-256 s/L 2 and 5.8,
respectively. After the pre-treatment of flocculation with FeCb (of 1 mg/L), the
MFI was increased to 455 s/I} . On the other hand, a pre-treatment with sand and
dual media filtration with inline flocculation of 1 mg/L FeCh gave rise to higher
organic removal and also resulted in a very low MFI and SDI 15 value of 1-2 s/L2
and 1.9-2 respectively.
2. Flocculation with 1 mg/L FeCh removed relatively large MW such as 1510 Da
and 1180 Da while the relatively small MW that was 530 Da and 130 Da could
not be removed. Deep bed media filtration with inline coagulation gave better
removal of SWOM (151 0 Da- 530 Da).
3. The flux decline in MF was the lowest (22%) with pre-treatment of dual media
filtration with in-line coagulation. Sand filtration with in-line coagulation also
gave sin1ilar flux decline (24%) . The flux decline with only a pre-treatment of
flocculation with FeCh (1 mg/L) was 42%.
This result indicates that the combination of deep bed filtration (either sand or dual)
with flocculation is an attractive pre-treatment to MF used in desalination as
pretreatJ.nent.

5- 3
Biofilter as Pretreatment to Membrane Based Desalination

The detailed experimental results obtained indicated that biofiltration as a pre-treatment

reduced a significant amount of organic matter and led to lower fouling of RO. Fouling
potential in terms of MFI values decreased to 10 s/L 2 within the first 10-15 days of
operation and kept constant during the remaining experimental period of 55 days of
operation for both GAC and anthracite biofilter. The filtrate turbidity was steady after
10 days and remained low at a value of 0.2-0.3 NTU and 0.28-0.31 NTU for anthracite
and GAC biofilter respectively. The headloss development was low for both the filters.
A post treatment of reverse osmosis after a pretreatment of GAC and anthracite
biofilters showed a reduction in normalized flux decline (J/Jo) from 0.22 to 0.12 and
0.35 to 0.21 during the first 20 hours respectively. The RO flux for seawater declined at
a faster rate and continued even after 3 days when no pretreatment was provided.

5-4
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22 9-238

R-4
 APPENDIX A
Sample calculation to detem1ine Modified fouling index

Step 1: A Curve was drawn using Volume (L) vs. t/v (s/L).
Step 2: A tangent was drawn in the linear section of the graph which represents the
cake filtration. Tangent of the graph represent the modified fouling index.

Data Set

1
"'2
3 0.4ooo:. :ncnoc:o
4 0.41800 ?V,ri\Qt;
·-----~---- 0.4290{1 1552,;4,(:; i
700 ~
6 0.4400 \! 0000000 I
.....,'!' . 0.44707 /7Dfif(.;5
. a· 0.4540 4:-;;hflDG I
9-- 0.4970 1 D1086b2 ~j .t
10 0.5160£ i'\:;?441? Linear Fit foL Data Set l Y
-ff" I y =mx+b
"f2' i m {Slope): 879.6
l
ff' 500-l1 b (Y-Intercept). -132.2
Correlation 0.9963
14 RMSE· 3.989
'15''
16
' ' 17'''
' 18"'
19
20- 300~
21' !
-22 .
'23
24 0.5960, ' ,· •[
25 0 t3030 ;
26
21
28 .

1::a=::::~::~~.J · ··· · ····iJ 1.1

Sample calculation for Silt density index (SDI)

Step 1: Record the initial filtration time (to filter a fixed volume of 500 mL)
Step 2: record final filtration time (to filter the same fixed volume of 500 mL)
Step 3: from the equation SDI was calculate

1- (t It 1 ) Equation 3.1
SD1 15 = l xlOO
T,

Where, ti = 34 sec
tr = 571 sec

A-1
Tt = 15 min

So, from the equation SDI Is= 6.2

A-2
 APPENDIXB

List of Publications based on This Research

Submitted Journal Articles

1. Khorshed, C., Johir, A. H., Vigneswaran, S., Shon, H. K. and Kandasamy, J.,
(2008), "Biofilter as Pretreatment to Membrane Based Desalination:
Evaluation in terms of Fouling Index". Will be published in the peer
reviewed Journal of Desalination in 2009.

2. Khorshed, C. , Johir, A. H., Vigneswaran, S., Shon, H. K. and Kandasamy, J.,

(2008), "Assessment of Pretreatment to Microfiltration for Disalination in
Terms of Fouling Index and Molecular Weight Distribution". Will be
published in the peer reviewed Journal of Desalination in 2009.

3. Javeed, M.A. , Chinu, K. , Shon, H.K., and Vigneswaran, S., (2009). "Effect of
pre-treatment on fouling propensity of feed as depicted by the modified
fouling index (MFI) and cross-flow sampler-modified fouling index (CFS-
M:F I)." Desalination, 23 8, 98-108 .

4. Johir, A. H., Khorshed, C., Vigneswaran, S., and Shon, H. K. (2008), "In-line-
flocculation- Filtration as Pre-treatlnent to Reverse Osmosis
Desalination". Will be published in the peer reviewed Journal of Desalination
in 2009.

5. Lee, J. J., Johir, M . A. H ., Chinu, K. H ., Shon, H. K., Vigneswaran, S.,

Kandasamy, J., Kim, C. W. , Shaw, K. (2008), "Hybrid Filtration Method
for Pr e-treatntent of Seawater Reverse Osmosis (SWRO)". Will be
published in the peer reviewed Journal of Desalination in 2009 .

6. Lee, J. J ., Johir, M . A. H., Chinu, K. H. , Shon, H . K., Vigneswaran, S.,

Kandasamy, J., Kim, C. W . , Shaw, K. (2008), "Novel Pre-Treatment
Method for Seawater Reverse Osmosis: Fibre Media Filtration". Will be
publ ished in the peer reviewed Journal of Desalination in 2009.

7. Laszlo Erdei, Saravanamuthu Vigneswaran, Roger Ben Aim, and Khorshed

Chinu, (2008), "Membrane Fouling Indices Revisited". Will be published in
the peer reviewed Journal of Desalination in 2009 .

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Conference Papers

7. Khorshed J Chinu. "Comparison of different pretreatment methods for ro

desalination in terms of fouling index and mw distribution" .Engineering
Showcase 2008, 4 June, University of Technology, Sydney.

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