ENG 470: ENGINEERING HONOURS THESIS
FINAL REPORT
BIOFOULING IN REVERSE OSMOSIS PROCESSES
BY
AMAR ZAGHY
BACHELOR OF ENVIRONMENTAL ENGINEERING
HONOURS
SCHOOL OF ENGINEERING AND INFORMATION
TECHNOLOGY 2016
SUPERVISORS
DR. LINDA LI EMERITUS PROFESSOR GOEN HO
A report submitted to the school of Engineering and Information Technology in partial fulfilment of requirements for the unit ENG470 Engineering Honours Thesis, at Murdoch University, Semester 1, 2016.
i
Author’s declaration
I declare that this submission is my own account of my research unless stated otherwise and
excluding references and appendices.
Amar Zaghy
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Executive Summary
Reverse Osmosis (RO) is a water purification technology that uses a semi-permeable membrane
to remove salt and other particles from drinking water. It is the dominant technology which has
overtaken many conventional systems in recent years. Membrane biofouling is the main
disadvantage of using RO technology which can result in reducing the system’s efficiency. The
rejected microorganisms on the surface of the membrane form a fouling layer (biofouling) which
leads to a decline in permeate flux, increase of hydraulic resistance, increase in operating
pressure, and shortening of the membrane life. Polysaccharides, produced by microorganisms,
are the main substances responsible for membrane biofouling. In this study, two types of
polysaccharides (alginate and pullulan) were used to investigate their individual fouling effects as
well as their fouling effects coupled with sodium chloride and calcium chloride. 50 mM of ionic
strength (27.5 g NaCl + 1.47 g CaCl2) and 0.2 g/L of polysaccharides were used in the fouling
experiments conducted with a laboratory-scale reverse osmosis system.
It was found that alginate lead to more reduction in system’s efficiency in comparison with
pullulan. The effect of alginate on the efficiency of the system was much more severe in the
presence of salt, namely sodium chloride and calcium chloride, compared to its individual effect
in the absence of salt. The addition of salt led to an increase in membrane fouling and a decrease
in system’s efficiency. On the other hand, it was found that pullulan enhanced the system’s
efficiency when it is combined with salt.
To support the above findings, a Confocal Laser Scanning Microscopy (CLSM) analysis, a Total
Organic Carbon (TOC) test, and an estimation of the weight of produced fouling layers were
performed. In general, analysing the results of the tests supported the findings.
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Acknowledgement
I would like to acknowledge Emeritus Professor Goen Ho, and Dr. Linda Li who made this work
possible with their continuous support throughout the course of this project.
I also appreciate the help and support provided by PhD candidate Zhangwang Xie (John) on the
instruction of experimental setup and supervision of this project.
Lastly, I would like to show gratitude to Murdoch University institution for giving me the
opportunity to work on this project.
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List of Abbreviation & acronyms DI: Deionised
RO: Reverse Osmosis
EPS: Extra-cellular Polymeric Substances
MSF: Multi-Stage Flash
CA: Cellulose Acetate
TFC: Thin Film Composite
NaCl: Sodium Chloride
CaCl2: Calcium Chloride
CLSM: Confocal Laser Scanning Microscopy
CP: Concentration Polarization
TOC: Total Organic Carbon
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Contents
Executive Summary ...................................................................................................... ii
Acknowledgement ...................................................................................................... iii
List of Abbreviation & acronyms .................................................................................. iv
List of Figures ............................................................................................................. vii
List of Tables ............................................................................................................. viii
1. Introduction .......................................................................................................... 1
1.1. Objectives....................................................................................................... 2
1.2. Project Management Plan ............................................................................... 2
2. Background ........................................................................................................... 3
2.1. Reverse Osmosis System ................................................................................. 3
2.2. Membrane Fouling ......................................................................................... 5
2.2.1. Concentration Polarisation .............................................................................. 6
2.2.2. Back Diffusion .................................................................................................. 7
2.2.3. Biofilm Formation ............................................................................................ 8
2.3. Polysaccharides .............................................................................................. 9
2.3.1. Alginate ............................................................................................................ 9
2.3.2. Pullulan .......................................................................................................... 11
3. Methodology & Research Design ......................................................................... 11
3.1. Experimental Methods.................................................................................. 12
3.1.1. System Design ................................................................................................ 12
3.1.2. Chemical Parameters and Operating Conditions .......................................... 16
3.2. Confocal Laser Scanning Microscopy (CLSM) Methodology ............................ 17
3.3. Total Organic Carbon (TOC) measurement .................................................... 18
3.4. Polysaccharides weighing methodology ........................................................ 19
3.5. Salt Concentration using “The Standard Curve” Method ................................ 19
4. Modelling ............................................................................................................ 20
4.1. Modelling permeate flux ............................................................................... 20
4.2. Modelling Hydraulic Resistances at the membrane surface ........................... 21
4.3. Modelling Osmotic Pressure & Concentration Polarisation at the membrane
surface .................................................................................................................... 23
4.4. Salt Rejection Rate ........................................................................................ 24
4.5. Back Diffusion Rate ....................................................................................... 24
5. Results and Data Analysis .................................................................................... 25
5.1. Permeate Flux............................................................................................... 25
5.1.1. Concentration Polarisation Effects ................................................................ 26
5.1.2. Polysaccharides Effects.................................................................................. 27
5.1.3. Concentration Polarisation and polysaccharides Combined Effects ............. 29
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5.1.4. Flux Comparison ........................................................................................... 31
5.2. Total Hydraulic Resistances ........................................................................... 33
5.2.1. Comparison of Total Resistance due to Alginate Fouling ............................. 34
5.2.2. Comparison of Total Resistance due to Pullulan Fouling ............................. 35
5.3. Concentration Polarisation Vs Osmotic Pressure at the Membrane Surface ... 36
5.4. Conductivity ................................................................................................. 38
5.5. Fouling Layers Weight Estimation ................................................................. 39
5.6. CLSM Analysis ............................................................................................... 41
5.7. Results Summary and Comparison ................................................................ 45
6. Conclusion ........................................................................................................... 47
7. Future Research Opportunities ............................................................................ 48
8. References .......................................................................................................... 50
9. Appendices: ......................................................................................................... 54
Appendix A: Gantt chart .......................................................................................... 54
Appendix B: HTI OsMEMTM CTA-NW Membrane Specification Sheet ...................... 55
Appendix C: Performed RO experiments.................................................................. 56
Appendix D: TOC results .......................................................................................... 57
Appendix E: Estimation of the weight of produced fouling layers ............................. 58
Appendix F: Results of “The Standard Curve” method ............................................. 58
Appendix G: Comparison of permeate fluxes with highest and lowest membrane
resistances .............................................................................................................. 59
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List of Figures Figure 1: Reverse osmosis principle. Left: osmosis; Right: reverse osmosis (Fritzmann et al. 2007).4
Figure 2: Concentration Polarisation (CP) phenomenon in RO processes. ........................................ 7
Figure 3: Structural formula of sodium alginate molecule (Katsoufidou, Yiantsios and Karabelas 2007). ............................................................................................................................................... 10
Figure 4: The egg-box model for binding divalent cations to sodium alginate molecules (Katsoufidou, Yiantsios and Karabelas 2007). .................................................................................. 10
Figure 5: Schematic chemical structure of pullulan with maltotriose as repeating unit (Singh, Saini and Kennedy 2008). ......................................................................................................................... 11
Figure 6: Laboratory-sale reverse osmosis system used to conduct the experiments. ................... 13
Figure 7: Schematic Diagram of the laboratory-Scale RO system used to conduct the experiments. .......................................................................................................................................................... 13
Figure 8: Sterlitech CF042 membrane cell with its components.Experimental Setup and procedure .......................................................................................................................................................... 14
Figure 9: The procedure of RO experiments conducted in this study. A) Control experiments; B) Fouling experiments without salt; and C) Fouling experiments in the presence of salt.................. 15
Figure 10: Picture of the Nikon C2 Confocal Microscope. ............................................................... 18
Figure 11: Effects of concentration polarisation (NaCl and CaCl2) on permeate flux. .................... 26
Figure 12: Effects of sodium alginate on permeate flux. ................................................................. 27
Figure 13: Effects of pullulan on permeate flux. .............................................................................. 28
Figure 14: Effects of alginate on permeate flux in the presence of NaCl and CaCl2. ...................... 29
Figure 15: Effects of pullulan on permeate flux in the presence of NaCl and CaCl2. ...................... 30
Figure 16: Comparison of permeate fluxes caused by individual and combined effects of salt and alginate foulant. ............................................................................................................................... 31
Figure 17: Comparison of permeate fluxes caused by individual and combined effects of salt and pullulan foulant. ............................................................................................................................... 32
Figure 18: Comparison between total hydraulic resistances in alginate experiments. ................... 34
Figure 19: Comparison between total hydraulic resistances in pullulan experiments. ................... 35
Figure 20: Correlation between concentration polarisation and osmotic pressure at the membrane surface. .......................................................................................................................... 37
Figure 21: Confocal image of the baseline foulaed membrane (NaCl + CaCl2). .............................. 41
Figure 22: Confocal image of the fouled membrane due to alginate fouling. ................................. 42
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Figure 23: Confocal image of the fouled membrane due to pullulan fouling. ................................ 42
Figure 24: Confocal image of a fouled membrane due to the interaction of salt and alginate. .... 43
Figure 25: Confocal image of a fouled membrane due to the interaction of salt and pullulan. ..... 44
List of Tables
Table 1: The average measured conductivity of the permeate and the feed solution during all performed experiments. .................................................................................................................. 38
Table 2: Estimation of mass and density of the fouling layers in the performed experiments. ...... 39
Table 3: Comparison between the performed RO experiments. .................................................... 45
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1. Introduction
Today, reverse osmosis (RO) membrane technology is considered as an important tool for
sustainable growth in desalination industry because of its simplicity in concept and operation.
However, like most other technologies is not free of some concerns (Matin et al. 2011).
Membrane biofouling is an inevitable phenomenon in reverse osmosis systems which can cause a
decrease in system’s efficiency (NG and Elimelech 2004). It results in several deleterious effects,
including a decrease in water production because of a gradual decline in flux, an increase in applied
pressure required for a constant rate of water production, a gradual membrane degradation which
reduces membrane life, and decreases the permeate quality (NG and Elimelech 2004). Despite the
enormous research and investigation, membrane biofouling is still a major technical hurdle that
needs to be addressed to enhance the efficiency and cost-effectiveness of operating reverse osmosis
system (Zhao, Song and Ong 2010). Biofilms, the major type of fouling in RO membranes, are formed
by bacterial extra-cellular polymeric substances (EPS) with polysaccharides play a significant role in
EPS (Vu et al. 2009). For this main reason the individual fouling effects of sodium alginate, as the
most common polysaccharide used in membrane biofouling research, along with less used
polysaccharide pullulan, have been studied in this work. The interaction between Sodium Chloride
(NaCl) and Calcium Chloride (CaCl2) with polysaccharides (Sodium alginate and pullulan) also have
been investigated. Previous studies have indicated that the presence of cations such as Ca2+ and Na+
and their interactions with polysaccharides can significantly aggravate the fouling process (Alazmi,
Nassehi and Wakeman 2010). Also, the physical properties of polysaccharides and their viscosity in a
solution are highly affected by ionic strength (Lee and Mooney 2012).
In this study, a laboratory-scale reverse osmosis system has been employed to conduct the fouling
experiments and demonstrate the fouling effects on RO processes.
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1.1. Objectives
With guidance from the assigned supervisors, a set of objectives has been developed to elucidate the
mechanisms of biofouling in reverse osmosis processes. The purpose of this study is to investigate
the following main objectives systematically.
1. To discover the effects of membrane biofouling on permeate flux and hydraulic resistance
and consequently the system’s efficiency.
2. To investigate and compare the fouling behaviour of alginate and pullulan, both individually
and when coupled with salt (NaCl and CaCl2).
3. To generate a model which would explain cake layer formation, cake-enhanced
concentration polarisation as well as the relationship between osmotic pressure and
concentration polarisation?
4. To determine if variation in cross-flow velocities has any effect on membrane biofouling.
Three different cross-flow velocities have been applied to address any knowledge gaps in RO
membrane studies.
These objectives have been carefully developed to maintain and possibly improve the performance
of reverse osmosis systems.
This study also aims to demonstrate the following competencies for engineering students:
To demonstrate the ability to undertake the necessary research and design practice to
produce an outcome for the assigned task; and
To be able to inspect, analyse and deliver the findings of the subject area.
1.2. Project Management Plan
During this project, a management plan has been devised to keep track of all activities for this
project. Consequently, a Gantt chart has been constructed using Microsoft Excel spreadsheet to
illustrate the progression of all relevant tasks involved throughout the course of this project. This
chart provides a means of organising weekly tasks and its time scale and identifies the order in which
tasks are to be completed (Gantt.com 2016). The progress of some of the listed tasks has been varied
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due to the rising of unexpected problems and therefore, the chart has been amended and modified
from its original version (refer to Appendix A).
2. Background
2.1. Reverse Osmosis System
Reverse osmosis is a common technology used for changing saline or contaminated water to a
drinkable water source (Li, Xu and Pinnau 2007). This technology has become increasingly popular
since it is the most efficient tool for wastewater reclamation (tertiary treatment) and is one of the
best performing technologies for desalting brackish water and seawater (Matin et al. 2011).
Membrane-based reverse osmosis is today the leading desalination technology which has overtaken
conventional thermal technology such as multi-stage flash (MSF) desalination and is expected to
maintain its leadership in the near future, though new technologies such as membrane distillation
and forward osmosis have been recently proposed (Lee, Arnot and Mattia 2011). It is a process that
is inherently easy to design and operate compared with many traditional separation methods and
considered as the simplest and most efficient technique for water purification purposes (Prakash
Rao, Desai and Rangarajan 1997). Reverse osmosis is the process of forcing a solvent from a high
solute concentrated region (feed side) through a membrane to a low solute concentrated region
(permeate side) by applying a pressure excess of the osmotic pressure (Figure 1) (Rathore et al.
2013). The applied pressure in excess of osmotic pressure reverses water flow direction and
due to this reason it is referred as “Reverse Osmosis”.
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Figure 1: Reverse osmosis principle. Left: osmosis; Right: reverse osmosis (Fritzmann et al. 2007).
This process is the reverse of normal osmosis process in which natural movement of solvent from an
area of low solute concentration, through a membrane, to an area of high solute concentration. The
RO membrane is the heart of the process in separating the undesired constituents from the feed to
obtain the desired pure product (Matin et al. 2011). It acts as a semi-permeable barrier that allows
the passage of a particular species (solvent, usually water) while partially or completely blocking
other species (solutes, such as salt) (Matin et al. 2011). In practice, as the saline/contaminated feed
water is pumped and pressurised against the membrane, a portion of water passes through the
membrane while the remaining water is diffused back causing an increase in salt content of the feed
water. While no heating or phase change is necessary for this separation, the major energy required
for desalting is for pressurising the feed water (Buros 2000).
Reverse osmosis membrane technology is relatively new which has developed over the past 40 years
to a 44% share in world desalting production capacity, and an 80% share in the total number of
desalination plants installed worldwide (Greenlee et al. 2009). Commercial interest in RO technology
has increased globally due to continuous process improvements, which in turn lead to significant cost
reductions (Lee, Arnot and Mattia 2011). The greatest efficiency gains have arisen from the
improvement of the membranes. The first major breakthroughs in membrane improvement came
from Loeb- Sourirajan in early 1960s when he developed the first asymmetric reverse osmosis
membranes which showed up to 100 times higher flux than any other known membranes (Loeb and
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Sourirajan 1964). In early 1970s, the first commercially available reverse osmosis membrane,
cellulose-acetate (CA) membrane was introduced (Li 2008). A CA asymmetric membrane was formed
with a dense 200nm thin layer over a thick micro-porous body. This new morphology produced a
water flux of at least an order of magnitude higher than the initial symmetric membrane (Liu 1981).
Later on, in the 1980s, composite membranes with more stability in physical and chemical properties
were introduced (Lee, Arnot and Mattia 2011). In recent years, the structure, material, and
morphology of RO membranes have improved functionally (permeability and selectivity) and
applicability (mechanical, chemical and biological stability (Lee, Arnot and Mattia 2011). Among the
existing membranes currently available, thin film composite (TFC) membranes are considered the
most efficient for desalination (Ismail et al. 2015). These membranes enhance both selectivity and
productivity with less energy consumption as compared to typical asymmetric membranes. The
continuous enhancement of membranes over the past decade has resulted in substantial reduction
of both membrane cost and energy consumption in RO systems.
The overall efficiency of a reverse osmosis system also depends on how well the system is designed.
Several factors including feed water characterisation, pre-treatment options, membrane choice,
operating conditions, and system cleaning can significantly affect the efficiency of RO systems
(Fritzmann et al. 2007). Types of elements exist in the feed water such as salt ions, or organic
elements can assist in choosing the suitable pre-treatment option. The feed water is diluted by pre-
treatment processes prior entering the RO system to prevent severe membrane fouling (Henthorne
and Boysen 2015). Using an appropriate membrane type is important in achieving high efficiency in
RO systems. Furthermore, applying optimal operating conditions such as temperature, pressure, and
cross-flow velocity can extend the lifetime of RO systems (Mickols et al. 2005).
2.2. Membrane Fouling
Membrane fouling is an inevitable phenomenon in reverse osmosis systems and causes a decrease in
water production because of gradual decline in permeate flux, an increase in applied pressure
required for a constant rate of water production, a gradual membrane degradation which results in a
6
shorter membrane life, and a decrease in salt rejection (NG and Elimelech 2004). It occurs as a result
of the accumulation of particles on the surface of the membrane or within the pores of the
membrane through the filtration of feed water (Matin et al. 2011).It is recognised that there are four
major types of reverse osmosis membrane fouling: inorganic or crystalline salt precipitation
(concentration polarisation), organic fouling caused by deposition of organic substances such as oil or
proteins, colloidal fouling (build-up of colloidal cake layers caused by deposition of clay, silt, debris,
or silica), and microbiological (adhesion and accumulation of bacteria forming biofilms) (Herzberg
and Elimelech 2007). Generally, three factors affecting the membrane fouling: (i) the membrane
properties including surface properties, membrane material, and morphological structure; (ii) the
feed solution chemistry and composition such as concentration of the substances and pH; and (iii)
the operating conditions including applied hydraulic pressure, temperature, and cross-flow rate (Li
and Chen 2010).
Membrane fouling imposes a large economic burden and is still a major technical problem in RO
operations that needs to be addressed to improve the cost-effectiveness of the system (Zhao, Song
and Ong 2010). For this reason, one of the major goals of membrane research has been to enhance,
or at least maintain, water flux and ultimately increase efficiency and reduce operational cost in RO
systems.
2.2.1. Concentration Polarisation
In all membrane separation processes, as water from the feed area reaches the membrane surface,
the dissolved material (salt ions) are rejected by the semi-permeable membrane resulting in
accumulation of these substances in front of the membrane. Consequently, the concentration in this
boundary layer exceeds the concentration of the bulk water (feed side) (Fritzmann et al. 2007). This
phenomenon is called concentration polarisation (CP) (Figure 2).
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Figure 2: Concentration Polarisation (CP) phenomenon in RO processes.
Concentration polarisation increases the potential for membrane fouling by increasing the osmotic
pressure at the membrane surface leading to (i) reduction in permeate flux (ii) decrease in rejection
because of increased salt concentration at the membrane surface; and (ii) hindrance of mass transfer
through the membrane due to precipitation layer on the membrane surface (Fritzmann et al. 2007).
In addition, the build-up of cake layer on the membrane surface due to the accumulation of rejected
particles reduces the efficiency in RO processes (Hoek and Elimelech 2003). The severity of
concentration polarisation in RO processes is not only determined by the size of the particles that
exist in the feed solution, but it also depends on the applied cross flow rate in the system (Hoek and
Elimelech 2003). Therefore, increasing the feed velocity is considered as the primary method of
minimising the influence of concentration polarisation in membrane based RO systems.
2.2.2. Back Diffusion
Diffusion is defined as the movement of a solution or air from a higher concentrated region to a
lower concentrated region and is influenced by the kinetic properties of the particles (Marie
Helmenstine 2016). The diffusion process will continue until an equilibrium concentration is achieved
in the two regions. In membrane-based reverse osmosis systems, the unavoidable phenomenon of
concentration polarisation can severely reduce the permeate flux due the gel layer formation. In such
8
systems, back diffusion occurs from the membrane surface back to the bulk (feed solution)
(Abdelrasoul et al. 2015). As solution from the feed side flows towards the membrane, a fraction of
solute (salt) starts to accumulate at the membrane surface while the remaining flows with the bulk
solution back to the feed with the help of back diffusion. The amount of salt runs back to the feed
during this period is usually lower than the amount of salt accumulates at the membrane surface (Ye
et al. 2005). Once sufficient number of salt ions accumulate at the membrane surface, the number of
salt ions return to the bulk solution due to back diffusion will equal the number of salt ions
accumulate at the membrane surface. At this time point, the system reaches a steady state (Ye et al.
2005). Back diffusion is hindered as the thickness of the fouling layer on the membrane surface
increases. Therefore, the thicker the fouling layer, the lower back diffusion is, and it is insignificant
once the fouling layer reaches certain thickness (Ye and Wang 2007). The theoretical principles of
cross-flow filtration in RO processes are derived from Fick’s law of diffusion which addresses the
migration of suspended solids/macromolecules in a flowing stream towards a filtration surface, and
the potential back-diffusion into the bulk stream (Abdelrasoul et al. 2015).
2.2.3. Biofilm Formation
Biofouling, a major type of membrane fouling, is caused by the adhesion and accumulation of
microorganisms and biological matter on the membrane surface resulting in biofilm formation (Matin
et al. 2011). Biofilms are a group of surface-associated microbial cells that are irreversibly linked to
the surface and enclosed in a matrix of extracellular polymeric substances (EPS), namely
polysaccharides (Flemming 1997). The biofouling phenomenon in RO processes leads to the use of
higher operating pressure, more frequent chemical cleaning, and shorter membrane life and, can
never be prevented through pre-treatment alone (Fritzmann et al. 2007). In the Middle East, the
region which produces the largest amount of desalted water in the world, about 70% of the seawater
RO membrane installations suffer from biofouling problems (Matin et al. 2011). Donlan (2002)
explains that the formation of a biofilm in RO processes starts with the transport and attachment of
the microorganisms on the membrane surface. The attachment of microorganisms on any surface is
facilitated by physical, chemical, and biological factors and, it is more likely for microorganisms to
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attach to hydrophobic and non-polar surfaces (Donlan 2002). Surface irregularity, hydrodynamics,
and feed water characteristics also influence the formation of biofilms.
2.3. Polysaccharides
One of the main causes of membrane fouling in RO processes are the extracellular polymeric
substances (EPS) (Tarnacki et al. 2005). They are produced by microorganisms as part of the
metabolism and due to biological stress and they are mainly composed of polysaccharides, nucleic
acids and proteins (Katsoufidou, Yiantsios and Karabelas 2007). Polysaccharides are a form of
carbohydrates within which there are simple sugars and its derivatives, cellulose, starches, gums and
chitosan (Talens, Fabra, and Chiralt 2010). Polysaccharides, as the main constituents of EPS, play an
important role in membrane fouling and because of this reason; they are used as model substances
of EPS in membrane fouling research (Frank and Belfort 2003). In addition, studies have revealed that
these substances seem to simulate EPS behaviour during filtration better than other EPS constituents
(Ye, Chen and Fane 2006). Furthermore, many studies have shown that polysaccharides exhibit
enhanced binding for calcium (divalent cation exist in seawater and wastewater) leading to the
formation of a stable gel network (Katsoufidou, Yiantsios and Karabelas 2007). In this project, two
main types of polysaccharides have been studied. Sodium alginate was chosen because previous
studies have shown that alginate forms a thick fouling layer on the surface of the membrane
particularly, in the presence of salt ions such as calcium and sodium. Pullulan was also used in this
study since its behaviour on the membrane fouling has not been fully understood.
2.3.1. Alginate
Sodium alginate is a hydrophilic microbial polysaccharide, mainly produced by brown algae, which is
often used as a model for EPS (Lee, Ang and Elimelech 2006). It consists of a linear copolymer
composed of 1-4 linked β-D-mannuronic acid, C-5 epimer and α-L-guluronic acid in varying properties
as shown in Figure 3 (Ye et al. 2005).
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Figure 3: Structural formula of sodium alginate molecule (Katsoufidou, Yiantsios and Karabelas 2007).
Several studies have indicated that in the presence of cations such as sodium and calcium, alginate
forms complexes of unique structure, resulting in a highly compacted gel network explained by “egg-
box” model as it is seen in Figure 4 (Katsoufidou, Yiantsios and Karabelas 2007).
Figure 4: The egg-box model for binding divalent cations to sodium alginate molecules (Katsoufidou, Yiantsios and
Karabelas 2007).
In this model, calcium ions bind to the carboxylic groups of alginate in a highly organised manner and
form bridges between adjacent alginate molecules, producing egg -box-shaped gel network
(Steinbuchel and Rhee 2005). In general, alginate is broadly used for various applications including
food industry and medical products due to its high viscosity (Lee and Mooney 2012).
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2.3.2. Pullulan
Pullulan is a linear homopolysaccharide of glucose that is often described as α-(1-6) linked
maltotriose, secreted primarily by strains of the polymorphic fungus A. Pullulans (Figure 5) (Leathers
2003). Although this unique biopolymer has a broad range of commercial and industrial applications
in many fields like food science, health care and pharmacy however, only a few of these potential
uses have been widely adopted due to its relatively high cost (Singh, Saini and Kennedy 2008).
Pullulan has a low viscosity and is unaffected by heating, changes in pH, and most metal ions
including sodium chloride (Leathers 2003). To the best of my knowledge, there has been little study
on pullulan behaviour in membrane separation processes particularly in the presence of cations such
as calcium and sodium.
Figure 5: Schematic chemical structure of pullulan with maltotriose as repeating unit (Singh, Saini and Kennedy 2008).
3. Methodology & Research Design This chapter has been set out to provide detailed information of all necessary materials, techniques,
and procedures used in this study to understand the effects of biofouling in reverse osmosis systems.
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3.1. Experimental Methods
3.1.1. System Design
For this study, a laboratory-scale reverse osmosis system has been pre-arranged to conduct the
fouling experiments as shown in figure 6 with its schematic diagram in figure 7. The system is made
up of a feed tank where the feed solution is placed, an electrical pressure pump to push the solution
through the membrane, a pressure gauge to maintain the assigned pressure value, membrane cell,
and a temperature control system (water-bath). It also includes a flow meter to maintain the
assigned cross flow velocity, a bucket for collecting treated water, a balance for weighing the water
of the permeate, and finally a computer program where it records the weight of the permeate in a
one-minute interval. A commercial forward osmosis membrane supplied by Hydration Technologies
Inc. was used to conduct the fouling experiments. The membrane was made up of cellulose
triacetate (CTA) and cast onto a non-woven backing consisting of polyethylene-coated polyester
fibres. As illustrated in figure 7, while the system is running, the feed solution is pushed through the
membrane cell by the pressure pump after entering the water-bath. Once the solution reaches the
membrane surface, the solvent (water) passes through the membrane into the permeate side and is
collected in a bucket placed on a balance. The semi-permeable membrane rejects other particles
(solute) where some accumulate on the membrane surface, while the rest flow back into the feed
solution.
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Figure 6: Laboratory-sale reverse osmosis system used to conduct the experiments.
Figure 7: Schematic Diagram of the laboratory-Scale RO system used to conduct the experiments.
The membrane cell used in the designed system was supplied by Sterlitech Corporation. A detailed
design specification of the membrane cell is available in Appendix B. The membrane cell consists of
Pressure gauge
Membrane Cell
Feed Tank
Water-bath
Pressure pump
Flow meter
Balance
Permeate flux
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an upper component (a porous stainless steel plate) and a base component (feed inlet and
concentrate outlet) as shown in figure 8. The membrane is placed between these two components
with non-active side facing the upper part of the cell. Before use, the membrane was cut into a
sample with a size suitable to fit the cell and stored in DI water for a minimum of 24 hours.
Figure 8: Sterlitech CF042 membrane cell with its components.
3.1.2. Experimental setup and procedure
At the start of this project and with help from research assistant (Zhangwang Xie), preliminary
experiments were conducted to gain an insight of the subject matter and become familiar with the
way the designed RO system works and operates. Following the completion of the preliminary
experiments, a set of designed experiments was carefully formulated. They were divided into three
main categories. The procedure of each type is illustrated in figure 9.
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A) Control experiment (baseline)
B) Fouling experiment without salt
C) Fouling experiments in the presence of salt
Figure 9: The procedure of RO experiments conducted in this study. A) Control experiments; B) Fouling experiments without salt; and C) Fouling experiments in the presence of salt.
Control experiments were designed to investigate the effects of concentration polarisation by adding
merely salt to the feed solution. On the other hand, fouling experiments were set to study the effects
of polysaccharides (alginate/pullulan) by adding alginate and pullulan to the feed solution. Lastly, to
examine the behaviour of the enhanced fouling layer on the membrane surface, salt (calcium
chloride and sodium chloride) and foulants (alginate and pullulan) were added to the system as
illustrated in Figure 9 (C).
Every experiment lasted for 28 hours with only DI water was used as a feed in the first two hours of
experiments to allow for membrane compaction and ensure the stability of all operating conditions.
Following the addition of salt/foulant to the feed at time= 2 hours, the system operated for another
Compaction
Addition of salt
Cross-flow velocity
12.75cm/s
Cross-flow velocity
5.23cm/s Stabilisation
Start (0h) End (28h) 4
h
12h 20h
Cross-flow velocity
8.5cm/s
2h
Compaction
Addition of foulant
Compaction
Addition of salt
Cross-flow velocity
12.75cm/s
Cross-flow velocity
5.23cm/s Stabilisation
Start (0h) End (28h) 4
h
12h 20h
Cross-flow velocity
8.5cm/s
2h
Addition of foulant
Cross-flow velocity
12.75cm/s
Cross-flow velocity
5.23cm/s Stabilisation
Start (0h) End (28h) 4
h
12h 20h
Cross-flow velocity
8.5cm/s
2h
16
2 hours with the same initial conditions to allow for membrane stabilisation and equilibrium. Cross-
flow velocity was manually set at 8.5 cm/s (identical to initial cross flow velocity) at time= 4 hours
before it was increased to 12.75 cm/s at time= 12 hours and finally it was dropped to 5.23 cm/s at
time= 20 hours. The system operated for eight hours under each assigned cross-flow velocities.
A total of 12 experiments were conducted over the course of this project with every type of
experiment was performed at least twice to ensure reliability and reproductively of the results (Refer
to Appendix C for details of the performed RO experiments). The conductivity of both feed solution
and permeate was measured periodically in all experiment at time= 4 hours, time= 12 hours, time=
20 hours, and time= 28 hours for determination of salt rejection. Membranes that showed significant
deviations from the measured average values of clean permeate flux and salt rejection in the
compaction stage were considered defective and discarded. At the end of every experiment, the
system was back washed with 20 L of DI water using a recyclable membrane to ensure the removal of
foulant or salt from the system.
3.1.2. Chemical Parameters and Operating Conditions
50 mM of ionic strength was added to the feed solution to investigate the behaviour of
concentration polarisation in RO processes. This amount of concentration was achieved by adding
27.5 g sodium chloride (NaCl) and 1.47 g calcium chloride (CaCl2) (with a similar ratio in artificial
seawater) (Demicco et al. 2005). Two types of foulant- sodium alginate and pullulan were also used
to study the behaviour of polysaccharides on membrane fouling. As mentioned in chapter 2,
polysaccharides are used as common model substances of EPS in membrane fouling research. A
concentration of 0.2 g/L of the available polysaccharides, in the form of powder, was applied in
fouling experiments. This concentration was prepared by adding the foulant to a small amount of DI
water (approximately 300 mL) and stirring until dissolved before adding the solution into the feed. In
experiments involving pullulan, two different types of pullulan products supplied by SIGMA
(Germany) and RONGSHENG Biotechnology Co. LTD (China) was used in the system. Consequently,
three fouling experiments (pullulan with no salt- two experiments using SIGMA products and one
17
experiment using RONGSHENG product) were conducted, and the behaviour of the two products was
compared (refer to “Results and Data Analysis” section).
All operating conditions were kept consistent throughout all experiments with the following
parameters:
Initial feed volume: 10L of DI water
Hydraulic pressure difference: 400 psi
Temperature: 25 ± 1 °C
Initial cross-flow velocity: 8.5 cm/s
3.2. Confocal Laser Scanning Microscopy (CLSM) Methodology
At the end of each type of experiments (experiments 2 (baseline), 5 (alginate only), 7 (pullulan only),
9 (salt+ alginate), and 10 (salt+ pullulan)), fouled membranes were carefully removed from the
membrane cell. The samples were then stored in containers with sufficient moisture levels using DI
water and kept in the fridge for CLSM analysis. With guidance from Dr. Lucy Skillman (staff technical
specialist in Murdoch University), fouled membranes were carefully removed from containers and at
a randomly chosen area was cut into <2 cm x 2 cm pieces. All samples were then put on clean
microscope glass slides, cautiously stained using a DTAF solution (approximately 75 mL), and secured
with cover slips to prevent the transportation of the stain. A pH value of 9 was used in the pre-
prepared stain solution provided by Dr. Lucy for the purpose of highlighting the fouling layer under
the microscope (Ahmed, Stal and Hasnain 2010). The samples were then put in a container, covered
with an aluminium foil to avoid the penetration of light intensity into the stain, and left overnight. All
samples were analysed by a Nikon C2 Confocal Laser Scanning Microscope (CLSM) (Figure 10) at 20x
magnification using associated software (NIS-Elements) to collect z-stacks of at least three areas per
membrane.
18
Figure 10: Picture of the Nikon C2 Confocal Microscope.
A series of 3D images was captured from the microscope so the thickness and the uniformity of the
fouling layer on the membrane surface could be analysed.
3.3. Total Organic Carbon (TOC) measurement
Polysaccharides, the main components of EPS, may account for 50-90 % of the total organic carbon
of biofilms and can be considered the primary matrix material of the biofilm (Matin et al. 2011).
Therefore, the total organic carbon (TOC) measurement helps to identify the concentration of these
foulants at various times of the experiment. The results from this test provide a better understanding
of the amount of polysaccharides being deposited on the membrane surface in fouling experiments.
In experiments involving foulant, samples (approximately 100 mL) from the feed solution were
collected at predetermined times (at times 4 h, 12 h, 20 h, and 28 h) for analysis of TOC. The samples
were stored in the refrigerator under a controlled temperature (between 0-4 :C) prior to the test.
The TOC analysis was completed by an external source in “Marine and Freshwater Research
Laboratory” located at Murdoch University. The result of this test is found in Appendix D. In addition,
19
two extra samples from the feed and permeate were collected at the end of the fouling experiment
involving combined alginate and salt to ensure the reproductively of the used analytical method.
3.4. Polysaccharides weighing methodology
Determining the weight of polysaccharides on the membrane surface provides a good indication of
the extent of the fouling layers in fouling experiments. Stored fouled membranes were cut to 2.2 cm
x 2.2 cm pieces (same size as the microscope cover glass) and left in an incubator with a controlled
temperature at 55 :C overnight to remove the excess of moisture. Prior to this practice, every
microscope cover glass used in the procedure was weighted on the available scale (W1). A new,
unused membrane was also identically cut and stored as a control (W2) for comparing the difference
in weight with fouled membrane samples. All dried samples were then measured (W3) to determine
the weight of biofilms deposited on the membrane surface. The procedure applied for calculating the
weight of biofilms on the membrane surface is as follows:
W2 – W1: weight of fresh membrane without glass
W3 – W1: weight of sample membrane without glass
(W3 – W1) – (W2 – W1): weight of fouling layers and salt particles
The result of above procedure can be found in Appendix E.
3.5. Salt Concentration using “The Standard Curve” Method
The measured conductivity during experiments was used to determine the concentration of salt in
the feed, permeate, and ultimately at the membrane surface. To obtain the corresponding salt
concentration from the measured conductivity, “The Standard Curve” method was applied. The
curve was constructed by diluting the initial salt concentration used in experiments (50 mM) which
was achieved by mixing 27.5g NaCl and 1.47g CaCl2 to a small portion of DI water. As this ratio was
added to 10L of DI water, it was scaled down to 0.275g NaCl and 0.015g CaCl2 dissolved in 100mL DI
water to meet the purpose. The dissolved solution was further diluted using the following steps.
The 100mL solution was put in a 100mL volumetric flask and labelled as 50mM in
concentration.
20
The solution in step 1 was put into a 50mL volumetric flux using a funnel. The excessive of
the solution was then put into an empty 100mL volumetric flux and supplemented with DI
water to reach 100mL volume. The flux was then labelled as 25mM in concentration.
The procedure was repeated to achieve 10mM and 5mM concentration.
The conductivity of each solution was recorded, and a graph of conductivity vs.
Concentration was produced.
Finally, the measured conductivity during experiments was applied to the curve so
corresponding concentration could be estimated.
The result of this process is found in Appendix F.
4. Modelling
The permeability, the hydraulic resistances, the concentration polarisation, and the salt rejection rate
and back diffusion rate in the performed experiments have been assessed on the basis of following
considerations.
4.1. Modelling permeate flux
To study the influence of fouling experiments on permeate flux (J), a model of the permeate flux has
been constructed. This model was based on a model developed by PhD candidate Zhangwang Xie
(John). As the weight of permeate flux (in grams) was recorded on a computer at a one-minute
interval, the difference in weight over ten minutes was calculated. The produced values, in grams,
were then converted to litres per square meter per hour (LMH). Lastly, the corresponding values to
every thirty minutes were used to develop the permeate flux model.
𝐽 =(𝑉𝑛+10 –𝑉𝑛 )
𝐴.𝑇 (Eq. 1)
Where J is the permeate flux over ten-minute interval (LMH or L/m2.h), Vn+10 is the recorded volume
of permeate (L) at time n+10, Vn is the recorded volume of permeate (L) at time n, A is the effective
membrane area (42x10-4 m2), and T is the time (h).
21
4.2. Modelling Hydraulic Resistances at the membrane surface
Based on John’s modelling structure, a model of the hydraulic resistances at the membrane surface
has been developed to investigate the effects of resistances on the resulting permeate flux. Using
Darcy’s Law (the flow of fluid through a porous medium) as a basis, the hydraulic resistances caused
by the fouled membranes can be calculated during the process (Dreszer et al. 2013).
𝐽 = ∆𝑃
𝜇 .𝑅𝑡 (Eq. 2)
Where J is the water permeate flux (in m/s), ΔP is the applied transmembrane pressure (in Pa), 𝜇 is
the viscosity of DI water (in Pa.s), and Rt is the total hydraulic resistance (in m-1). The following
procedure was then applied to obtain the membrane resistance (Rm), the resistance due to
concentration polarisation (Rcp), and the resistance of the cake layer (Rc).
A. Membrane Resistance (Rm)
During the membrane compaction between time= 0h and time= 2h when only DI water was
presented in the feed, the resistance of the membrane was calculated. As no foulant or salt was
added to the feed, the only hydraulic resistance exists in the system was the membrane resistance
(Rm).
𝑅𝑚 = 𝑅𝑡 = ∆𝑃
𝜇 .𝐽 (Eq. 3)
In every experiment, Rm was measured four times during membrane compaction (every half an hour)
however, only the third or fourth value was assumed as the constant (Rm).
B. Resistance due to Concentration Polarisation (Rcp)
Once the salt is introduced to the system, the accumulation of salt ions at the boundary of the
membrane surface causes an increase in concentration polarisation which in turn adds to the
22
hydraulic resistance in the process. Hence, the concentration polarisation resistance was calculated
by altering Eq. 2.
𝑅𝑡 = 𝑅𝑐𝑝 + 𝑅𝑚 → 𝑅𝑐𝑝 = 𝑅𝑡 − 𝑅𝑚 = ∆𝑃
𝐽 ∙𝜇− 𝑅𝑚 (Eq. 4)
C. Cake Resistance (Rc)
In experiments where foulant (alginate or pullulan) is introduced to the system, the gradual
formation of the fouling layer on the membrane surface results in additional non-membrane
resistance. The resistance of this fouling layer was obtained by:
𝑅𝑡 = 𝑅𝑐 + 𝑅𝑚 → 𝑅𝑐 = 𝑅𝑡 − 𝑅𝑚 = ∆𝑃
𝐽 ∙𝜇− 𝑅𝑚 (Eq. 5)
D. Combined Cake resistance and Concentration Polarisation Resistance (Rc + Rcp)
In the case where foulant and salt are added to the system, both the cake layer resistance and
concentration polarisation resistance contribute to the non-membrane resistance in the process.
Sometimes, this combined resistance is referred as cake-enhanced layer resistance. The cake-
enhanced layer resistance is calculated as follows:
𝑅𝑡 = (𝑅𝑐 + 𝑅𝑐𝑝 ) + 𝑅𝑚 → (𝑅𝑐 + 𝑅𝑐𝑝 ) = 𝑅𝑡 − 𝑅𝑚 = ∆𝑃
𝐽 ∙𝜇− 𝑅𝑚 (Eq. 6)
The above equations have been developed on the basis of the following considerations to reduce the
complicity of the produced model.
Membrane blockage resistance (Rb) was not considered in the calculation as it was concluded
to be insignificant in the performed experiments.
The resistance of membrane was assumed to remain steady after membrane compaction in
all experiments.
The increase in osmotic pressure due to the addition of foulant was negligible and hence was
ignored.
23
4.3. Modelling Osmotic Pressure & Concentration Polarisation at the membrane surface
In experiments where salt has been used, as the salt ions start to accumulate at the membrane
surface, the osmotic pressure (𝜋cp) begins to increase resulting in a reduction of permeate flux. The
increase of the osmotic pressure is therefore deducted from the applied transmembrane pressure.
∆𝑃 = 𝑃 − 𝑃0 − 𝜋𝑐𝑝 (Eq. 7)
The calculation of the osmotic pressure at the membrane surface has been illustrated by using Eq.2
and Eq.6.
𝐽 = ∆𝑃− 𝜋𝑐𝑝
𝜇 .𝑅𝑚 → 𝜋𝑐𝑝 = 𝛥𝑃 − (µ. 𝐽. 𝑅𝑚) (Eq. 8)
By applying De Van’t Hoff’s Law for the osmotic pressure, the concentration polarisation at the
membrane surface has been estimated (Fritzmann et al. 2007).
𝜋𝑐𝑝 = 𝑖 ∙ 𝐶𝑐𝑝 ∙ 𝑅𝑔 ∙ 𝑇 → 𝐶𝑐𝑝 =𝜋𝑐𝑝
𝑖 .𝑅𝑔 ∙𝑇 (Eq. 9)
Where 𝑖 represents the van’t Hoff’s factor which is equal to the number of ions per mole of solute (2
was used in the above equation), 𝐶𝑐𝑝 is the salt concentration at the membrane surface (mol/L), 𝑅𝑔
is the gas constant (0.08206 L.atm/mol.K), and 𝑇 is the temperature in Kelvin.
The estimation of concentration polarisation has also been modelled based on the measured
conductivity at a different time interval during the experiments. Referring to “The Standard Curve”
graph, the concentration polarisation in the feed and permeate was estimated from the
corresponding measured conductivity. The total mass in the permeate and feed can be calculated by
multiplying the concentration with related volume. Using the effective membrane area and the
estimated thickness of the deposition of salt at the membrane surface (from CLSM images), the
volume at the membrane surface can be estimated.
By applying the total mass equation in the process, the salt concentration at the membrane surface
was determined.
24
𝑇𝑜𝑡𝑎𝑙 𝑚𝑎𝑠𝑠 = 𝑇𝑜𝑡𝑎𝑙 𝑚𝑎𝑠𝑠 𝑖𝑛 𝑡𝑒 𝑓𝑒𝑒𝑑 + 𝑇𝑜𝑡𝑎𝑙 𝑚𝑎𝑠𝑠 𝑖𝑛 𝑝𝑒𝑟𝑚𝑒𝑎𝑡𝑒 +
𝑇𝑜𝑡𝑎𝑙 𝑚𝑎𝑠𝑠 𝑎𝑡 𝑡𝑒 𝑚𝑒𝑚𝑏𝑟𝑎𝑛𝑒 𝑠𝑢𝑟𝑓𝑎𝑐𝑒 (Eq. 10)
4.4. Salt Rejection Rate
The rate of salt rejection has been estimated in experiments where salt was added to the system. It
was calculated based on the measured conductivity to determine the efficiency of the membranes
used in experiments.
𝑅𝑒𝑗𝑒𝑐𝑡𝑖𝑜𝑛 % = 1 − 𝐶𝑝
𝐶𝑓 × 100% (Eq. 11)
Where 𝐶𝑝 is the permeate conductivity and 𝐶𝑓 is the conductivity of the feed.
4.5. Back Diffusion Rate
In the absence of fouling, the rejected salt ions result in high concentration of the salt at the surface
of the membrane. Consequently, a back diffusion of these ions occurs from the layer adjacent to the
membrane back to the feed solution (Abdelrasoul et al. 2015). The rate of back diffusion can be
explained by the Fick’s Law. This law relates the diffusive flux to the concentration under the
assumption of steady state (Abdelrasoul et al. 2015).
𝐽 = 𝐷𝛥𝐶
(Eq. 12)
Where 𝐽 is the rate of back diffusion (mol/m2.s), D is the diffusion coefficient (1.58 x 10-4 m2/s), 𝛥𝐶 is
the difference in permeate concentration and feed concentration (mol/m3), and h is the thickness of
the concentration polarisation layer (m).
25
5. Results and Data Analysis
Based on the developed model and experimental procedures, results have been obtained and
analysed. In order to make the results comparable, a normalised flux was used based on the
following formula.
𝐽𝑁 = 𝐽
𝐽0 (Eq. 13)
Where JN is the normalised flux, J is the flux at a given time, and J0 is the initial flux.
Moreover, for the baseline experiments, the rate of salt rejection was calculated based on Eq. 11.
A high rejection rate ranging between 97.8 and 99.3 percent was achieved by the membranes
used in the experiments. The high salt rejection rate is an indication of an excellent efficiency of
the used membranes in the system.
5.1. Permeate Flux
The performed experiments in this study have been divided into three main categories as
mentioned previously. The baseline experiments were set to study the effects of concentration
polarisation, the fouling experiments were designed to investigate the effects of polysaccharides
(alginate and pullulan), and the fouling experiments in the presence of salt aimed to explore the
effects of salt and polysaccharides in combination. The addition of salt and polysaccharides in RO
processes usually cause a flux decline. Therefore, in his section, the effects of conducted
experiments on the resulting permeate flux have been analysed.
26
5.1.1. Concentration Polarisation Effects
Figure 11: Effects of concentration polarisation (NaCl and CaCl2) on permeate flux.
Three baseline experiments, with 50mM of salt concentration (NaCl and CaCl2) added to each
experiment, have been conducted during this study. These experiments have been conducted to
study the effects of concentration polarisation individually so it could be compared with the
fouling experiments. Figure 11 is demonstrates the fluctuation of normalised permeate flux
during the experiments. As it is seen from the graph, the permeate flux expresses a sudden
decline at time= 2h soon after the salt was added to the feed solution. After membrane
compaction, at time=4h, the flux remains relatively steady until time= 12h although a minor
increase in permeate flux was noticed at some points due to the increase in applied pressure
which was observed during the experiments. At time= 12h when the cross-flow velocity was
increased to 12.75 cm/s, a flux showed a slight decrease before it levelled until time= 20h. A
similar trend was observed in the final 8 hours when the system was operating with a cross-flow
velocity of 5.23 cm/s. Overall, the addition of salt caused an average of 15.9% decline on the
resulting permeate flux. Clearly, concentration polarisation due to the addition of NaCl and CaCl2
to the system leads to a decline in the permeate flux. Also, it appears that variation in cross-flow
0.6
0.7
0.8
0.9
1
1.1
1.2
00
.5 11
.5 22
.5 33
.5 44
.5 55
.5 66
.5 77
.5 88
.5 99
.5 10
10
.5 11
11
.5 12
12
.5 13
13
.5 14
14
.5 15
15
.5 16
16
.5 17
17
.5 18
18
.5 19
19
.5 20
20
.5 21
21
.5 22
22
.5 23
23
.5 24
24
.5 25
25
.5 26
26
.5 27
27
.5
Stage 1
Stage 2
Flow rate 8.5cm/s Flow rate 12.75cm/s Flow rate 4.25cm/s
No
rmal
ise
d P
erm
eat
e F
lux
Time (h)
Control Exp
Flow rate 5.23 cm/s
27
velocities had an insignificant effect on the resulting permeate flux as the increase or the
decrease in cross-flow velocities resulted in permeate flux decline.
5.1.2. Polysaccharides Effects
Two main polysaccharides- alginate and pullulan have been used to study the fouling effects
on the resulting permeate flux.
I. Alginate Fouling
Figure 12: Effects of sodium alginate on permeate flux.
Two fouling experiments have been conducted with alginate polysaccharide to explore its effect
on permeate flux. The average of the two experiments has been graphed as it is seen in Figure 12.
As the error bars in the graph suggest, the result shows a close correlation between the two
experiments. According to the figure, soon after the addition of alginate to the feed solution at
time= 2h, a fast decline in permeate flux was observed. The effect of alginate on permeate flux
remained relatively steady after time= 4h until the end of experiments despite the change in
cross-flow velocities. Overall, alginate has resulted in an average of 16.8% decline in permeate
flux. It is suggested that after the addition of alginate to the system, a fouling layer is built on the
0.6
0.7
0.8
0.9
1
1.1
00
.5 11
.5 22
.5 33
.5 44
.5 55
.5 66
.5 77
.5 88
.5 99
.5 10
10
.5 11
11
.5 12
12
.5 13
13
.5 14
14
.5 15
15
.5 16
16
.5 17
17
.5 18
18
.5 19
19
.5 20
20
.5 21
21
.5 22
22
.5 23
23
.5 24
24
.5 25
25
.5 26
26
.5 27
27
.5
Stage 1
Stage 2
Flow rate 8.5cm/s Flow rate 12.75cm/s Flow rate 4.25cm/s
No
rmal
ise
d P
erm
eat
e F
lux
Time (h)
DI + Alginate
Flow rate 5.23 cm/s
28
membrane surface causing a rapid decline in permeate flux. The effects of this layer on permeate
flux decreases as the time increases during the experiments.
II. Pullulan Fouling
Figure 13: Effects of pullulan on permeate flux.
Two fouling experiments where pullulan was used have been performed to study the effect of
this type of polysaccharide on permeate flux. The average of the two experiments is shown in
Figure 13. An average decline of 8.9% in permeate was recorded from the normalised data which
indicates an insignificant reduction caused by pullulan. The major permeate decline was noticed
in the final step of the experiments where the system was operating with a cross-flow velocity of
5.23 cm/s. It is suspected that the reduction in permeate flux during this period was due to the
decrease in the applied pressure which was observed to be lower than the assigned value
(approximately 360psi).
Due to limited availability of pullulan product supplied by SIGMA (Germany), a different
pullulan brand supplied by RONGSHENG Biotechnology Co. LTD (China) was used for the
remaining fouling experiments involving pullulan and salt in combination. Thus, to compare the
0.6
0.7
0.8
0.9
1
1.1
1.2
00
.5 11
.5 22
.5 33
.5 44
.5 55
.5 66
.5 77
.5 88
.5 99
.5 10
10
.5 11
11
.5 12
12
.5 13
13
.5 14
14
.5 15
15
.5 16
16
.5 17
17
.5 18
18
.5 19
19
.5 20
20
.5 21
21
.5 22
22
.5 23
23
.5 24
24
.5 25
25
.5 26
26
.5 27
27
.5
Stage 1
Stage 2
Flow rate 8.5cm/s Flow rate 12.75cm/s Flow rate 4.25cm/s
No
rmal
ise
d P
erm
eat
e F
lux
Time (h)
DI + Pullulan
Flow rate 5.23 cm/s
29
effects of the new pullulan product on permeate flux with the old product, an additional
experiment (with same conditions and parameters) was conducted. The result of the additional
experiment indicated that the fouling behaviour of the new pullulan product was closely related
to experiments where the old pullulan product was used.
5.1.3. Concentration Polarisation and polysaccharides Combined Effects
In this section, the fouling behaviour of alginate and pullulan in combination with salt has been
analysed.
I. Alginate and salt
Figure 14: Effects of alginate on permeate flux in the presence of NaCl and CaCl2.
Two experiments with alginate and salt in combination have been conducted to study the
effects of NaCl and CaCl2 interaction with alginate on the permeate flux. According to Figure 14,
as salt was introduced to the system at time= 2h, a fast decline in flux was noticed. After adding
the alginate at time= 4h, the permeate flux continued to decrease gradually until the cross-flow
velocity was increased to 12.75 cm/s. A small increase in flux was noticed during the period
between time= 12h and time = 20h due to the slight increase in the applied pressure. The
permeate flux was further reduced in the last period where the system was running with low
0.6
0.7
0.8
0.9
1
1.1
00
.5 11
.5 22
.5 33
.5 44
.5 55
.5 66
.5 77
.5 88
.5 99
.5 10
10
.5 11
11
.5 12
12
.5 13
13
.5 14
14
.5 15
15
.5 16
16
.5 17
17
.5 18
18
.5 19
19
.5 20
20
.5 21
21
.5 22
22
.5 23
23
.5 24
24
.5 25
25
.5 26
26
.5 27
27
.5
Stage 1
Stage 2
Flow rate 8.5cm/s Flow rate 12.75cm/s Flow rate 4.25cm/s
No
rmal
ise
d P
erm
eat
e F
lux
Time (h)
DI + Salt + Alginate
Flow rate 5.23 cm/s
30
cross-flow velocity (5.23 cm/s). Overall, the interaction of salt and alginate resulted in an average
decline of 36.9% in the permeate flux.
II. Pullulan and salt
Figure 15: Effects of pullulan on permeate flux in the presence of NaCl and CaCl2.
The final two experiments conducted during this study were the combined salt and pullulan
together. The effects of the interaction of salt and pullulan on permeate flux have been graphed
and shown in Figure 15. It is seen from the figure that as the salt was introduced to the system at
time= 2h, a rapid reduction in flux was observed. As the pullulan was added to the system at
time= 4h, the permeate flux remained relatively steady for the entire duration of experiments
despite the changes in cross-flow velocities. It seems that pullulan has a minimum effect on
permeate flux particularly in a case where it interacts with salt. Overall, the fouling caused by
pullulan and salt together resulted in an average reduction of 18.1% in permeate flux.
0.6
0.7
0.8
0.9
1
1.1
1.2
00
.5 11
.5 22
.5 33
.5 44
.5 55
.5 66
.5 77
.5 88
.5 99
.5 10
10
.5 11
11
.5 12
12
.5 13
13
.5 14
14
.5 15
15
.5 16
16
.5 17
17
.5 18
18
.5 19
19
.5 20
20
.5 21
21
.5 22
22
.5 23
23
.5 24
24
.5 25
25
.5 26
26
.5 27
27
.5
Stage 1
Stage 2
Flow rate 8.5cm/s Flow rate 12.75cm/s Flow rate 4.25cm/s
No
rmal
ise
d P
erm
eat
e F
lux
Time (h)
DI + Salt + Pullulan
Flow rate 5.23 cm/s
31
5.1.4. Flux Comparison
5.1.4.1. Alginate Fouling Comparison
Figure 16: Comparison of permeate fluxes caused by individual and combined effects of salt and alginate foulant.
In Figure 16, the resulting permeate flux due to individual effects of concentration polarisation
(Control experiments), the resulting permeate flux due to individual effects of alginate fouling (DI
+ Alginate), and the resulting permeate flux due to the combined effects of concentration
polarisation and alginate fouling (DI + salt + Alginate) are plotted. Concentration polarisation has
resulted in 15.9% decrease in flux followed by alginate fouling which resulted in 16.8% reduction,
and the interaction of salt and alginate have resulted in 36.9% decline in flux. Based on the
produced results, although both concentration polarisation and alginate have affected the
permeate flux and consequently the efficiency of the system however, the interaction of salt and
alginate have resulted in a major deficiency in the system. It is suggested that the presence of salt
(NaCl and CaCl2) in the feed solution may enhance the formation of the fouling layer on the
membrane surface. Van den Brink et al. (2009) explains that the presence of ionic strength in the
solution promotes alginate gel formation by compaction of the electric double layers on the
membrane and the alginate molecule, which results in a lower electrostatic repulsion and a
denser fouling layer (van den Brink et al. 2009). In another study conducted by Alazmi, Nassehi
0.6
0.7
0.8
0.9
1
1.1
1.20
0.5 1
1.5 2
2.5 3
3.5 4
4.5 5
5.5 6
6.5 7
7.5 8
8.5 9
9.5 10
10
.5 11
11
.5 12
12
.5 13
13
.5 14
14
.5 15
15
.5 16
16
.5 17
17
.5 18
18
.5 19
19
.5 20
20
.5 21
21
.5 22
22
.5 23
23
.5 24
24
.5 25
25
.5 26
26
.5 27
27
.5
Stage 1
Stage 2
Flow rate 8.5cm/s Flow rate 12.75cm/s Flow rate 4.25cm/s
No
rmal
ise
d P
erm
eat
e F
lux
Time (h)
Control Exp
DI + Alginate
DI + Salt + Alginate
Flow rate 5.23 cm/s
32
and Wakeman (2010), it was shown that the binary solution of alginate-calcium caused the
highest irreversibility among the tested solutions and it was due to the ‘egg-box’ structure of the
alginate-calcium and its deposition on and interaction with the membrane surface (Alazmi,
Nassehi and Wakeman 2010). In the presence of divalent cations, such as Ca2+, alginate forms
complexes of unique structure, resulting in a highly compacted gel network (Egg-box)
(Katsoufidou, Yiantsios and Karabelas 2007).
5.1.4.2. Pullulan Fouling Comparison
Figure 17: Comparison of permeate fluxes caused by individual and combined effects of salt and pullulan foulant.
In Figure 17, the resulting permeate flux due to the individual effects of concentration
polarisation (Control experiments), the resulting permeate flux due to individual effects of
pullulan fouling (DI + Pullulan), and the resulting permeate flux due to the combined effects of
concentration polarisation and pullulan fouling (DI + salt + Pullulan) are plotted. As mentioned
previously, concentration polarisation has resulted in 15.9% decrease in flux. The effects of
pullulan fouling have resulted in 8.9% reduction, and the interaction of salt and pullulan have
resulted in 18.1% decline in flux. Based on illustrated results, while salt and pullulan affect the
permeate flux and in turn the efficiency of the system, the interaction between the salt and
0.6
0.7
0.8
0.9
1
1.1
1.2
00
.5 11
.5 22
.5 33
.5 44
.5 55
.5 66
.5 77
.5 88
.5 99
.5 10
10
.5 11
11
.5 12
12
.5 13
13
.5 14
14
.5 15
15
.5 16
16
.5 17
17
.5 18
18
.5 19
19
.5 20
20
.5 21
21
.5 22
22
.5 23
23
.5 24
24
.5 25
25
.5 26
26
.5 27
27
.5
Stage 1
Stage 2
Flow rate 8.5cm/s Flow rate 12.75cm/s Flow rate 4.25cm/s
No
rmal
ise
d P
erm
eat
e F
lux
Time (h)
Control Exp
DI + Pullulan
DI + Salt + Pullulan
Flow rate 5.23 cm/s
33
pullulan result in less effect on permeate flux in comparison with the sum of individual effect. As
the effects of pullulan on membrane fouling has not been extensively studied in the past, it is
suspected that the improve in permeability caused by the interaction of salt and pullulan is due to
the chemical and physical characteristics of pullulan and the low binding strength between
pullulan and salt ions. It is suggested that pullulan in the presence of salt may enhance the
permeability of the solution.
5.2. Total Hydraulic Resistances
In this section, the total hydraulic resistances due to concentration polarisation, the total
resistances caused by polysaccharides (alginate and pullulan), and the total resistances due to the
interaction of salt and polysaccharides have been analysed and compared. The membrane
resistance was calculated during the compaction stage of each experiment (first two hours) and
assumed to remain consistent throughout the course of the experiments. Interestingly, the two
fouling experiments involving salt and alginate had the lowest and the highest membrane
resistance values (8.49 x 1014m-1 and 1.03 x 1015m-1 respectively). It is expected that the higher
the membrane resistance is, the more water is permeating through the membrane into the
permeate flux. This was later approved after the permeate flux in the referred experiments was
calculated (Refer to Appendix G for further details).
34
5.2.1. Comparison of Total Resistance due to Alginate Fouling
Figure 18: Comparison between total hydraulic resistances in alginate experiments.
In above figure, the total hydraulic resistances due to the individual effects of concentration
polarisation (salt) and alginate, and the total resistances due to the combined effects of
concentration polarisation and alginate have been compared. As illustrated, the interaction
between salt and alginate resulted in higher resistances (31.7%) in the system in comparison with
their individual effects. Concentration polarisation due to the addition of NaCl and CaCl2 to the
feed solution caused an average increase of 9.7% in total resistances, followed by the alginate
fouling in the absence of salt which caused an increase in total resistances by 15.2%. As expected,
the formation of a thick fouling layer in a case where alginate and salt are used in combination
resulted in greatest total resistances in the system. Matin et al. (2011) stated that in water
purification membrane systems, biofilms act as a secondary membrane and give rise to many
deleterious consequences that include increased hydraulic resistance resulting in reduced
permeate flux, and enhanced concentration polarisation resulting in decreased salt rejection
(Matin et al. 2011). It was also found that alginate fouls the membrane quickly and the fouling
process is aggravated in the presence of divalent cations such as Ca2+ and Mg2+ (Li, Xu and Pinnau
2007). In addition, the formation of the fouling layer on the membrane surface caused by alginate
0.8
0.9
1
1.1
1.2
1.3
1.4
1.52
2.5 3
3.5 4
4.5 5
5.5 6
6.5 7
7.5 8
8.5 9
9.5 10
10
.5 11
11
.5 12
12
.5 13
13
.5 14
14
.5 15
15
.5 16
16
.5 17
17
.5 18
18
.5 19
19
.5 20
20
.5 21
21
.5 22
22
.5 23
23
.5 24
24
.5 25
25
.5 26
26
.5 27
27
.5
Rt
(x1
0^1
5 m
-1)
Time (h)
Salt
Alginate
Salt + Alginate
35
reduces back diffusion of the ions salt at the membrane surface which in turn increases the
concentration polarisation and osmotic pressure at the membrane surface (Kim et al. 2006).
Alazmi, Nassehi and Wakeman (2010), in their research on calcium cation interactions with
polysaccharides, found that almost all the calcium cations were absorbed by the alginate in the
solutions. They also concluded that the highest increase in membrane resistance was due to high
calcium concentrations and low alginate concentration in the feed (Alazmi, Nassehi and
Wakeman 2010).
5.2.2. Comparison of Total Resistance due to Pullulan Fouling
Figure 19: Comparison between total hydraulic resistances in pullulan experiments.
In figure 19, the “salt” represents the total hydraulic resistance due to concentration
polarisation; the “pullulan” represents the total hydraulic resistance due the pullulan fouling; and
the “salt + pullulan” illustrates the total hydraulic resistance due to pullulan and salt interaction.
The comparison between the plots shows that NaCl and CaCl2 have increased the total resistance
in the system by 9.7%. Pullulan in the absence of salt have resulted in an increase in total
resistance by 14.6% and the increase in resistance due to the interaction of salt and pullulan was
at 12.4%. Surprisingly, the results show that pullulan reduces the total resistance in the system
when combines with the salt. Previous studies have shown that membrane fouling caused by
0.8
0.85
0.9
0.95
1
1.05
1.1
1.15
1.2
1.25
1.3
22
.5 33
.5 44
.5 55
.5 66
.5 77
.5 88
.5 99
.5 10
10
.5 11
11
.5 12
12
.5 13
13
.5 14
14
.5 15
15
.5 16
16
.5 17
17
.5 18
18
.5 19
19
.5 20
20
.5 21
21
.5 22
22
.5 23
23
.5 24
24
.5 25
25
.5 26
26
.5 27
27
.5
Rt
(x1
0^1
5 m
-1)
Time (h)
Salt
Pullulan
Salt + Pullulan
36
polysaccharides is a major hurdle in RO processes which results in the increase of hydraulic
resistances (Zhao, Song and Ong 2010). It is suspected that pullulan does not form a strong
binding with the salt ions on the membrane surface. The thin fouling layer produced by pullulan
in the presence of salt was evident when the fouled membrane was removed from the
membrane cell at the end of experiments. The behaviour of pullulan in the presence of salt and
its effect on permeate flux and hydraulic resistances in RO processes require further investigation
and analysis to support the produced results in this study.
Based on the results from figures 18 and 19, it was concluded that the interaction of salt
and alginate in the solution lead to the highest increase in total resistance (31.7%). Therefore,
alginate in the presence of salt poses a great deficiency in RO processes.
5.3. Concentration Polarisation Vs Osmotic Pressure at the Membrane Surface
Where salt has been used in experiments, the increase in concentration polarisation and osmotic
pressure has been analysed. Based on the developed model (Eq. 8, and 9), the osmotic pressure
(𝜋𝑐𝑝 ) and concentration polarisation (𝐶𝑐𝑝 ) at the membrane surface was estimated as it is seen in
figure 20. The figure indicates the progression of osmotic pressure and concentration
polarisation of NaCl and CaCl2 at the membrane surface over a 28 hours period. It is noted from
the figure that both osmotic pressure and concentration polarisation have increased
proportionally over time. As more salt ions deposit at the membrane surface due to the natural
membrane separation process, the osmotic pressure at the membrane surface would also
increase. The increase would suggest that less water would permeate through the membrane due
to the accumulation of salt which reduces the resulting permeate flux over time and in turn
increases the total hydraulic resistance in the system. It has been established (in sections 5.1.1.
and 5.2.1.) that the addition of NaCl and CaCl2 resulted in 15.9% reduction in permeate flux and
9.7% increase in total hydraulic resistance in the system. The growth of concentration
polarisation and osmotic pressure seem to become relatively steady in the last 8 hours of the
37
experiments. The trend in the final hours suggests that the amount of salt accumulating at the
membrane surface is close to the amount of salt being diffused from the membrane surface to
the bulk solution.
Figure 20: Correlation between concentration polarisation and osmotic pressure at the membrane surface.
0.02
0.04
0.06
0.08
0.1
0.12
0.14
0.2
0.25
0.3
0.35
0.4
0.45
0.5
0.55
0.6
0.65
0.7
22
.5 33
.5 44
.5 55
.5 66
.5 77
.5 88
.5 99
.5 10
10
.5 11
11
.5 12
12
.5 13
13
.5 14
14
.5 15
15
.5 16
16
.5 17
17
.5 18
18
.5 19
19
.5 20
20
.5 21
21
.5 22
22
.5 23
23
.5 24
24
.5 25
25
.5 26
26
.5 27
27
.5
CP
(m
ol/
L)
πfe
ed
,m (
x10
^6 P
a)
Time (h)
πfeed,m CP
38
5.4. Conductivity
Table 1: The average measured conductivity of the permeate and the feed solution during all performed experiments.
Measured Conductivity
time Baseline exp Alginate exp Alginate+salt exp Pullulan exp Pullulan+salt exp
Feed Permeate Feed Permeate Feed Permeate Feed Permeate Feed Permeate
(h) (µs)
4 2910.00 30.15 32.00 4.13 3115.00 23.11 1.46 1.16 3025.00 20.33
12 3240.00 39.95 34.80 1.58 3480.00 42.90 2.20 1.41 3485.00 40.85
20 3495.00 46.10 34.50 1.32 3575.00 50.10 2.51 1.65 3600.00 43.15
28 3600.00 49.95 36.70 1.25 3640.00 56.90 2.96 1.90 3715.00 47.65
Average feed and permeate conductivity have been measured periodically at times= 4h, 12h, 20h,
and 28h in all conducted experiments. The results of the measured conductivity have been
summarised in Table 1. As illustrated in the table, all the measured conductivity in the feed
solution and the permeate flux have increased over the course of 28h except in alginate
experiment where a high permeate conductivity was recorded at time= 4h. The high measured
conductivity in alginate experiment was due to the salt left in the system from the previous set of
experiments (baseline experiments with salt added in the system). The increase of feed and
permeate conductivity is an indication of an increase in salt concentration in the permeate and
the feed solution. As water moves through the semi-permeable membrane to the permeate side,
the volume of the feed solution declines which leads to an increase of the salt concentration in
the feed solution explaining the increase of measured conductivity. The salt concentration in the
permeate flux also increases over time because of the build-up of concentration polarisation and
the fouling layer on the membrane surface which allow a small proportion of salt ions to go
through the membrane into the permeate. The permeate conductivity has increased over time in
all experiments which would suggest that the water quality in the permeate decreases over time.
The interaction of salt with alginate has resulted in the highest reduction in the quality of the
treated water due to the formation of a compact fouling layer on the membrane surface which
allow more salt to go through the membrane into the permeate side.
39
5.5. Fouling Layers Weight Estimation
Table 2: Estimation of mass and density of the fouling layers in the performed experiments.
Experiment type Deposit on the
membrane (g)
Thickness (cm) Density of deposit
(g/cm3)
Baseline (salt) 0.026 0.0047 0.13188
Alginate 0.035 0.034 0.02431
Pullulan 0.026 0.018 0.03444
Salt + Alginate 0.095 0.062 0.03666
Salt + Pullulan 0.009 0.021 0.00984
Based on the methodology explained in section 3.4 of this report, the weight of the fouling
layers caused by concentration polarisation, polysaccharides, and combined polysaccharides and
concentration polarisation has been estimated. Table 2 summarises the weight, the thickness
(using CLSM images), and the density of each fouling layer. The density of the deposit was
estimated by applying the following formula:
𝐷𝑒𝑛𝑠𝑖𝑡𝑦 = 𝑚𝑎𝑠𝑠
𝑎𝑟𝑒𝑎 ∙𝑡𝑖𝑐𝑘𝑛𝑒𝑠𝑠 (Eq. 14)
40
Where density is estimated in g/cm3, “mass” is the mass of deposit on the membrane (g), “area”
is the effective membrane surface area (cm2), and “thickness” is the estimated fouling layer from
CLSM images (cm). As illustrated, the fouling layer in salt+ alginate experiment has the highest
mass (0.095g) as opposed to the fouling layer in salt+ pullulan experiment with a small mass of
0.009g. The interaction between salt and alginate also resulted in a thick fouling layer (0.062 cm)
while concentration polarisation resulted in a thin layer at the membrane surface (0.0047cm).
These findings support the earlier discovery in sections 5.1.3. and 5.2.1. about the reduction in
flux and increase in total resistance caused by the cake-enhanced fouling layer due to the
interaction of salt and alginate. Due to the high density of salt ions, the baseline experiment
recorded the highest density (0.1319 g/cm3). The small mass (0.009g) and low density
(0.00984g/cm3) of the fouling layer in the salt+ pullulan experiment would suggest that pullulan
does not bind well with NaCl and Cacl2 resulting in a thin fouling layer on the membrane surface.
41
5.6. CLSM Analysis
The stored membranes have been examined by Nikon C2 microscopy, and 3D images of the
fouled membranes were produced. The images were analysed with a purpose of estimating the
thickness and the uniformity of the fouling layers deposited on the membrane surface.
Figure 21: Confocal image of the baseline foulaed membrane (NaCl + CaCl2).
Figure 21 is a confocal image of a fouled membrane due to concentration polarisation resulted by
the addition of NaCl and CaCl2 to the system. The green colour represents the fouling due to
concentration polarisation, and the white colour is the surface of the membrane. The thickness of
the fouling layer is estimated to be 47 µm based on the scale provided in the image. Since the
surface of the membrane is clearly visible (white colour), it is unlikely that the fouling layer is
evenly distributed across the membrane surface. Also, the salt particles seem to be compact and
dense as the dark green colour suggest. It is predicted that the darker the colour of the fouling
layer is, the more compact and dense the fouling layer becomes.
42
Figure 22: Confocal image of the fouled membrane due to alginate fouling.
Figure 22 is the confocal image of the fouled membrane due to alginate fouling. Based on the
provided scale in the image, the thickness of the fouling layer is estimated to be 340 µm. Only a
few white points can be seen in the image which is an indication of a uniform distribution of the
fouling layer across the membrane surface. The alginate fouling layer seems to be sparse with low
density as the light green colour indicates.
Figure 23: Confocal image of the fouled membrane due to pullulan fouling.
43
Figure 23 is a confocal image of the fouled membrane resulted from pullulan fouling. The
thickness of the fouling layer is approximately 180 µm. The fouling layer seems to be uniformly
distributed across the surface of the membrane as very few white patches are seen in the image.
The colour of the image suggests that the resulted fouling layer has a uniform density.
Figure 24: Confocal image of a fouled membrane due to the interaction of salt and alginate.
Figure 24 shows the resulted fouled membrane caused by the interaction of salt and alginate in
RO processes. Based on the provided scale in the image, the fouling layer seems to have the
greatest thickness compared to other images (approximately 620 µm). The fouling layer is evenly
distributed across the surface of the membrane. Although the fouling layer seems to be very thick
however, the density of the fouling layer seems to be low as the bright green colour suggests. It is
observed from the image that the top of the fouling layer is level due to the reason that the
fouling layer was covered by the cover glass at the time of inspection under the microscope.
44
Figure 25: Confocal image of a fouled membrane due to the interaction of salt and pullulan.
Figure 25 represents a confocal image of the fouled membrane due to the addition of salt and
pullulan to the feed solution. It is estimated that the fouling layer has a thickness of 210 µm. An
evenly distributed fouling layer across the membrane surface is observed from the image. Also,
the bright green colour is an indication of a thin fouling layer being formed on the membrane
surface.
45
5.7. Results Summary and Comparison
Table 3: Comparison between the performed RO experiments.
Comparison between Performed RO experiments
Experiment Type Experiment
number
Initial flux
Final Flux
Flux reduction
Flux reduction
Rm Rt
increase CLSM
thickness Deposit on membrane
Density of deposit
(LMH) (LMH) (LMH) % (x1015
m-1
) (x1015
m-1
) (µm) (g) (g/cm3)
(DI Water + Salt) Exp 2 9.41 8.14 1.27 13.5% 0.95 6.1% 47 0.026 0.1319
(DI Water + Alginate)
Exp 5 10.71 8.89 1.83 17.1% 0.90 15.9% 340 0.035 0.0243
(DI Water + pullulan)
Exp 7 10.01 9.29 0.73 7.3% 0.91 14.1% 180 0.026 0.0344
(DI Water + Salt + Alginate)
Exp 9 9.27 5.99 3.29 35.4% 1.03 27.9% 620 0.095 0.0367
(DI Water + Salt + Pullulan)
Exp 10 9.41 7.70 1.71 18.2% 1.01 12.0% 210 0.009 0.0098
Table 3 summarises different type of RO experiments conducted during this study. It only includes experiments which had their fouled membranes
stored for the CLSM analysis. The table shows the initially recorded flux (LMH), the final recorded flux (LMH), the reduction of the fluxes, the membrane
resistance, and the total hydraulic resistance in each performed experiment. It also demonstrates the estimated thickness of each fouled membrane and
the approximation of weight and density of the substances deposited on the membrane surfaces. As illustrated, the initial flux starts between 9.27 to
10.71 LMH, mainly depending on the resistance of the used membrane. Higher membrane resistance in experiment 9 (1.03 x 1015m-1) has resulted in a
lowest initial flux (9.27 LMH) for the same experiment. In contrast, the lowest measured membrane resistance (0.90 x 1015m-1) in experiment 5 has led to
the highest initial flux (10.71 LMH) for the same experiment. Experiment 7 (DI water+ pullulan) recorded the lowest flux reduction (0.73 LMH or 7.3%) in
46
opposed to experiment 9 (DI water+ salt+ alginate) which expressed the highest flux reduction
between all experiments (3.29 LMH or 35.4%). The lowest total resistance occurred in baseline
experiment, where NaCl and CaCl2 were used, due to the reason that the accumulation of salt
molecules at the membrane surface has an insignificant influence on total resistance of the
system. On the other hand, in the experiment where salt and alginate were used in combination,
the highest total resistance was recorded. Based on Darcy’s Law used in the calculation, the
permeate flux inversely proportional to the total hydraulic resistance. Therefore, it was expected
that experiment 7 with the lowest permeate flux reduction (7.3%) would have the least total
resistances. The total resistance of the system also depends on the resistance of the membrane,
the thickness of the fouling layer, and the amount and density of the deposited substances on the
membrane surface. Baseline experiment (Experiment 2) recorded the lowest fouling layer
thickness (47 µm), the least deposit of salt (0.026 g), and the highest density (0.1319 g/cm3)
among all RO experiments. The interaction of salt and alginate not only resulted in the greatest
flux reduction (35.4%) and the highest total resistance (27.9%) among all experiments but, it also
resulted in a formation of a thick (620 µm), heavy (0.095 g), and relatively dense (0.0367 g/cm3)
fouling layer on the membrane surface. The correlation between these findings support are
consistent and support the previous studies on the salt and alginate interaction in membrane
separation processes. Conversely, the interaction of salt and pullulan (Experiment 10) has
resulted in a relatively thin (210 µm), light (0.009 g), and a very sparse (0.0098 g/cm3) fouling
layer on the surface of the membrane. Pullulan in combination with salt seems to enhance the
weight and the density of the fouling layer based on the calculation. In general, alginate results in
more fouling on the membrane surface compared with pullulan.
47
6. Conclusion
This study aimed to investigate the behaviour of two types of polysaccharides, alginate and
pullulan, in RO processes. Their individual effects, as well as their effects in the presence of
sodium chloride and calcium chloride, were analysed and compared.
Following the analysis of the results obtained from the performed experiments by using the
developed model, it was found that concentration polarisation due to the accumulation of salt
ions at the surface of RO membranes slightly affected the overall efficiency of the system by
increasing the hydraulic resistances and reducing the permeate flux.
Furthermore, pullulan fouling insignificantly reduced the permeate flux, slightly increased the
total hydraulic resistance in the system, and ultimately had a minor effect on the efficiency of the
system. The total hydraulic resistance was further improved when pullulan interacted with the
salt. As it was clear from the conducted experiments that increase of hydraulic resistances leads
to a major reduction of system efficiency, it is concluded that pullulan enhances the efficiency in
RO systems.
In contrast, alginate fouling of RO membranes resulted in more deficiency in the system due to
higher flux reduction and greater hydraulic resistances. In the presence of sodium and calcium
ions, alginate had much greater effect on fouling. The severe alginate fouling in the presence of
salt resulted in a formation of a thick, dense, and heavy fouling layer at the surface of the
membrane. The estimated fouling thickness using CLSM analysis and the weight estimation
methodology of fouled membranes supported these findings. It is concluded that alginate causes
more fouling and higher deficiency in RO processes in comparison to pullulan particularly when it
is mixed with sodium chloride and calcium chloride. These findings indicate that alginate has a
much stronger tendency to bond with sodium and calcium ions, compared to pullulan, resulting in
a formation of a thicker fouling layer on the membrane surface.
48
Variation in the applied cross-flow velocities during each experiment had little effect on the
extent of the resulted fouling. As the cross-flow velocity increased during the experiments, higher
flux decline and greater hydraulic resistance were observed.
By analysing the Confocal Laser Scanning Microscopy (CLSM) images, it was found that the thicker
the fouling layer is, the greater hydraulic resistance in the system becomes. For instance, in the
experiment where salt interacted with alginate, the estimated fouling layer thickness was closely
correlated to the hydraulic resistance in the system.
The findings in this study provide an indication of improving the membrane fouling in RO
processes.
7. Future Research Opportunities
After a comprehensive study on the behaviour of membrane fouling in RO system using salt
including NaCl and CaCl2, polysaccharides including alginate and pullulan, and the interaction of
salt and polysaccharides, the following research areas have been identified for further study:
The interaction of salt and alginate causes a major deterioration of the efficiency in RO
systems. Therefore, research on ways to improve or at least maintain the same efficiency
in RO system is vital. In particular, research on reducing the salt concentration before
using RO treatment through pre-treatment processes can help with improvement of
membrane fouling in RO system.
Forward Osmosis system is a growing technology which has been used recently for water
purification purposes. Similar to RO system, forward osmosis uses a semi-permeable
membrane to treat contaminated water (HTI 2010). The performed experiments in this
study can be reapplied to forward osmosis system with identical experimental conditions
and chemical parameters so a comparison between the two technologies can be made.
49
Previous studies have found that the divalent calcium cation in the presence of alginate
intensifies the formation of the fouling layer on the membrane surface. Since a mixture of
sodium chloride and calcium chloride was used in this study, the effect of sodium ion on
membrane fouling is ambiguous. In future, sodium chloride can be used solely so the
effect of sodium on membrane fouling can be further investigated.
Factors such as membrane type, applied pressure, pH, temperature, cross-flow velocity
and chemical concentration play an important part on the severity of the produced
fouling layer on the membrane surface. Conducting the same experiments with different
variables can provide answers on applying optimal conditions in RO processes to prevent
worsening the membrane fouling.
Magnesium ions are more abundant in seawater and according to previous studies; they
can trigger the gel formation on the surface of the membrane once they are mixed with
polysaccharides. On the other hand, xanthan is an important polysaccharide used in
membrane fouling research. It would be motivating to study the behaviour of these
chemicals both individually and when they are mixed together on the membrane fouling.
50
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54
9. Appendices:
Appendix A: Gantt chart
21
91
12
42
1425
121
4326
71
31
4614
101
38
45
22-Feb 7-Mar 21-Mar 4-Apr 18-Apr 2-May 16-May 30-May 13-Jun 27-Jun
Review & confirm thesis topicOrganise meeting with Supervisors for Topic Brief
Conduct Preliminary researchAttend the Safety in Research & Teaching Induction
Laboratory introduction & system design familiarisationDesign & conduct preliminary experiments
Systematic calculation method to obtain experiments result (ongoing)RAMP form submission
Conduct in depth researchCreate Gantt Chart
Start project plan write upDraft Project Plan Submission
Draft review and editFinalised Project Plan Submission
Design and conduct experiments (ongoing)Conduct Further research
Start Progress Report write upDraft Progress Report Submission
Draft review and editFinalised Progress Report Submission
Start Final Report Write UpData Compilation and analysis
Compile Draft Final ReportDraft Final Report Submission
Draft review and editPresentation Preparation
PresentationFinal Report Amendment
Final Report Submission
Date (2016)
Task
s
Gantt Chart
55
Appendix B: HTI OsMEMTM CTA-NW Membrane Specification Sheet
Features:
The OsMemTM CTA-NW Membrane is HTI’s fouling resistant and most chlorine resistant FO membrane cast on a weldable nonwoven support.
The OsMemTM CTA-NW Membrane is used in all hydration pouches (HydroPack, LifePack, X-Pack, etc.).
The OsMemTM CTA-NW Membrane is cast on 40’’ (1-m) wide rolls and “dried,” where vegetable-based glycerine replaces the water.
The OsMemTM CTA-NW Membrane coupons are shipped “dry,” where vegetable-based glycerine replaces the water
Typical FO Performance (Rejection Layer Contacting Feed):
Water Permeation : 2.4GFD (gallons per square foot each day) (4.0 LMH – litres per square meter each hour)
Salt Rejection: 99% as defined in Test Conditions Test Conditions:
Feed: 1 gpm (4 1 pm) tap water feed at 77F (25C) fed at the bottom into a 4” (100 mm) by 0.2 “ (5 mm) open channel with an initial volume of 0.40 gal (1.5 L) and an exit pressure of 5 psi (35 kPa).
Draw: 7 gph (26 lph) 1 M NaCl (58.5 g/L) at the bottom at 2 psi (15 kPa) feed into a 4” (100 mm) by 0.055” (1.4 mm) channel of two 30-mil (0.76 mm) diamond-type polypropylene feed spacers (strands spaced at 11 strands per inch (25.4 mm)) with an initial volume of 0.13 gal (0.5 L)
Membrane Area: 0.22 ft2 (0.020 m2) Typical uPRO* Performance (Rejection Layer Contacting Draw Solution):
Water Permeation: 5.3 GFD (gallons per square foot each day) (9.0 LMH – litres per square meter each hour)
Salt Rejection: 99% as defined in Test Conditions Test Conditions:
Feed: 7 gpm (26 1 pm) tap water at the bottom at 2 psi (15 kPa) feed into a 4” (100 mm) by 0.055” (1.4 mm) channel of two 30-mil (0.76 mm) diamond-type polypropylene feed spacers (strands spaced at 11 strands per inch (25.4 mm)) with an initial volume of 0.26 gal (1.0 L).
Draw: 7 gph (26 lph) 1 M NaCl (58.5 g/L) at 77F (25C) fed at the bottom into a 4” (100 mm) by 0.2” (5 mm) open channel with an initial volume of 0.2 gal (0.8 L) and an exit pressure of 5 psi (35kPa).
Membrane Area: 0.22 ft2 (0.020 m2)
Rejection: {1 – [(mol NaCl transferred to feed )/(L water removed)/(1 M]}
*uPRO: unpressurized Pressure Retarded Osmosis membrane orientation Operating Limits and Guildlines:
Membrane Requirements: Membrane coupons are shipped in glycerine. Should be soaked in water for 30 minutes prior to use. After glycerine extraction, membrane must be kept moist at all times. Do not allow to freeze. Exercise care in handling
Membrane Type: Cellulose Triacetate (CTA) on heat- or RF-weldable nonwoven support
Maximum Operation Temperature: 160F (71C)
Maximum Transmembrane Pressure: 10 psi (70 kPa), if supported
pH Range: 3 to 8
Maximum Chlorine: 2ppm
Cleaning Guidelines: use only cleaning chemicals approved for CA/CTA RO membranes
56
Storage Guidelines: Store out of direct sunlight with a couple of mL of water FO Membrane Notes The membrane in initially cast on rolls. On a roll, the rejection layer is to the inside of the roll is the shiny side away from the nonwoven backing. FO membranes behave similarly to RO membranes in that dissolved gases are not rejected well. Their ions are rejected, but the (often small) fraction that exists as a dissolved gas is not rejected. Small polar, water-soluble organics, such as urea, methanol, and ethanol, are also not rejected well. Brief Start-up Description If the process is being run with the draw solution contacting the rejection layer (uPRO), make sure that there is water in the cell on the supported side to draw from. Start the pump on the unsupported side. Adjust the flowrate with the inlet valve and the exit pressure to 5 psi (35 kPa) with the exit valve. Start the side with the membrane support and adjust to the desired inlet pressure of 2 psi (15 kPa). Monitor volume or weight changes, temperature, and concentrations with time. Brief Shutdown descriptions Turn off the pumps and drain the high osmotic pressure solution first. Then drain the low osmotic pressure solution. Rising is recommended. The membrane can be stored in the cell – preferably drained.
Source: OsMemTM membrane specification sheet
Appendix C: Performed RO experiments
Laboratory-scale Reverse Osmosis Experiments
Category Description Experiments Start Date End Date
Control Experiments
DI Water + Salt
Exp 1 31-03-2016 01-04-2016
Exp 2 04-04-2016 05-04-2016
Exp 3 07-04-2016 08-04-2016
Fouling Experiments Without salt
DI Water + Alginate Exp 4 11-04-2016 12-04-2016
Exp 5 14-04-2016 15-04-2016
DI Water + Pullulan (old)
Exp 6 18-04-2016 19-04-2016
Exp 7 21-04-2016 22-04-2016
DI Water + Pullulan (new)
Exp 12 09-05-2016 10-05-2016
Fouling Experiments in the Presence of Salt
DI Water + Salt + Alginate
Exp 8 25-04-2016 26-04-2016
Exp 9 28-04-2016 29-04-2016
DI Water + Salt + Pullulan (new)
Exp 10 01-05-2016 03-05-2016
Exp 11 03-05-2016 04-05-2016
57
Appendix D: TOC results
58
Appendix E: Estimation of the weight of produced fouling layers
Appendix F: Results of “The Standard Curve” method
Sample number FO/RO Experiment type
Glass weight, W1
(g)
Glass + fresh membrane
weight, W2 (g)
Glass + sample,
W3 (g)
Fresh membrane
weight, W2 - W1
Sample membrane
weight, W3 - W1
Gross fouling layer weight,
(W3 - W1) - (W2 - W1)
1 FO Baseline 0.194 0.248 0.255 0.048 0.061 0.013
Trial 1 0.197 0.248 0.253 0.048 0.056 0.008
Trial 2 0.2 0.248 0.261 0.048 0.061 0.013
3 FO Salt + alginate 0.196 0.248 0.264 0.048 0.068 0.02
4 FO Xanthan 0.198 0.248 0.269 0.048 0.071 0.023
5 FO Salt + xanthan 0.196 0.248 0.283 0.048 0.087 0.039
6 FO Pullulan 0.197 0.248 0.258 0.048 0.061 0.013
7 RO Baseline 0.192 0.248 0.243 0.048 0.051 0.003
8 RO Alginate 0.18 0.248 0.232 0.048 0.052 0.004
9 RO Pullulan 0.201 0.248 0.252 0.048 0.051 0.003
10 RO Salt + alginate 0.2 0.248 0.259 0.048 0.059 0.011
11 RO Salt + pullulan 0.195 0.248 0.244 0.048 0.049 0.001
12 - Fresh membrane 0.2 0.248 - 0.048 - -
AlginateFO2
y = 0.0168xR² = 0.9951
0
10
20
30
40
50
60
0 500 1000 1500 2000 2500 3000 3500
Co
nce
ntr
atio
n (
mM
)
Conductivity (us)
Standard Curve of Salt Concentration Vs Conductivity
59
The R2 value in above figure is greater than 0.995 which indicates a close correlation between concentration polarisation and the measured conductivity. The relationship between concentration polarisation and conductivity has been illustrated by the following equation.
𝑦 = 0.0168𝑥
Where x is the measured conductivity and y is the concentration of salt in the solution.
Appendix G: Comparison of permeate fluxes with highest and lowest membrane resistances
5
6
7
8
9
10
11
12
13
0 1 2 3 4 5 6 7 8 9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
Pe
rme
ate
Flu
x (L
MH
)
Time (h)
Alginate fouling experiemtns in the presence of salt
lowest Rm
Highest Rm
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