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Handbook of Membrane Separations

Chemical, Pharmaceutical, Food, and Biotechnological
Applications
Anil K. Pabby, Syed S.H. Rizvi, Ana Maria Sastre

Reverse Osmosis Membrane

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https://www.routledgehandbooks.com/doi/10.1201/b18319-5
Dipak Rana, T. Matsuura, Mohd Azraai Kassim, A.F. Ismail
Published online on: 09 Apr 2015

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 3 Reverse Osmosis Membrane
Dipak Rana, T. Matsuura, Mohd Azraai Kassim, and A.F. Ismail

CONTENTS
3.1 Introduction........................................................................................................................................................................ 35
3.2 Membrane Preparation....................................................................................................................................................... 36
3.2.1 Integrally Skinned Asymmetric Membrane and Thin-Film-Composite Membrane............................................. 36
3.2.2 Membrane Surface Modification............................................................................................................................ 37
3.2.3 Development of Membranes for Boron Removal, Chlorine Tolerance, and Antibiofouling.................................. 38
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3.2.4 Membrane Development with Low Pressure and High Flux................................................................................. 39

3.2.5 Membrane Development for High Operating Pressure.......................................................................................... 39
3.3 Reverse Osmosis Transport................................................................................................................................................ 40
3.3.1 Single Component System...................................................................................................................................... 40
3.3.2 Multicomponent System......................................................................................................................................... 41
3.4 Commercial Modules......................................................................................................................................................... 42
3.5 Recent Operational Examples of Large-Scale RO Modules.............................................................................................. 42
3.6 Future Directions of the Research Agenda......................................................................................................................... 48
3.7 Conclusions......................................................................................................................................................................... 48
References.................................................................................................................................................................................... 48

3.1 INTRODUCTION of branched poly(ethylene imine) and 2,4-diisocyanate on a

The fastest growing desalination process is a membrane
separation process called reverse osmosis (RO). The most
remarkable advantage of RO is that it consumes little energy
since no phase change is involved in the process. RO employs
hydraulic pressure to overcome the osmotic pressure of the
salt solution, causing water-selective permeation from the
saline side of a membrane to the freshwater side as the mem-
brane barrier rejects salts [1–4]. Polymeric membranes are
usually fabricated from materials such as cellulose acetate
(CA), cellulose triacetate (CTA), and polyamide (PA) by the
dry–wet phase inversion technique or by coating aromatic PA
via interfacial polymerization (IFP) [5].
In the early 1960s, Loeb and Sourirajan developed asym-
metric CA membrane by the phase inversion method for sea-
water desalination [6]. The fundamental principle underlying
their RO membrane development is the preferential sorption-
capillary flow mechanism. According to the Gibbs adsorp-
tion isotherm, a thin (about 0.5 nm) layer of pure water exists
at the surface of seawater. By analogy, a pure water layer
should also exist at the membrane/salt water interface, which
can be collected through the membrane pore by applying a
pressure gradient, as depicted in Figure 3.1 [7]. Later, it was
found that the Loeb–Sourirajan membrane had an asymmet-
ric structure with a top thin layer that governs the salt rejec-
tion and the water flux and a porous sublayer that provides
the mechanical strength (see Figure 3.2) [7]. In 1968, Cadotte
was able to prepare a new type of RO membrane called a
thin-film-composite (TFC) membrane that consisted of a thin
layer of PA formed by an in situ polycondensation reaction
porous polysulfone (PS) membrane [8]. Since then, the focus
has been shifted to the development of TFC membranes with
a thin skin layer, mostly made of aromatic PA material, and
it has provided the major platform to fabricate novel RO
membranes for seawater desalination. Nowadays, TFC mem-
branes are manufactured by IFP of trimesoyl chloride (TMC)
and m-phenylene diamine (MPD) at the surface of a porous
PS support. Although the first practical PA-TFC membrane
appeared nearly 40  years ago, there is still considerable
uncertainty regarding the molecular mechanisms of their
function, selectivity, and molecular structure–performance
relationship. The main feature of the TFC membrane is that
the material of the top thin layer (PA) is different from that
of the porous support layer (PS), while, for the CA mem-
brane, the material of both layers is the same. Therefore, the
membrane of the latter type is called an integrally skinned
asymmetric membrane to be distinguished from the TFC
membrane, which also has an asymmetric structure.
Another noticeable development in RO membrane fab-
rication was that of the PA membrane with an integrally
skinned asymmetric structure. It was made by DuPont in
1971 both in flat-sheet and hollow-fiber configurations [9,10],
which established a novel membrane fabrication technology
of hollow-fiber spinning. According to the patent disclo-
sure, approximately 10% of the linear aromatic PA rings are
substituted by sulfonic acid groups. As the aromatic ring is
easily attacked by the chlorine in water, the presence of the
sulfonate group is necessary to render the material chlorine
resistant.

35
 36 Handbook of Membrane Separations: Chemical, Pharmaceutical, Food and Biotechnological Applications
Seawater
Pure water layer
ti
Membrane Membrane
Pore (r = ti) Pore (r > ti)
FIGURE 3.1  Preferential sorption-capillary flow mechanism of
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RO. (From Matsuura, T., Synthetic Membranes and Membrane
Separation Processes, CRC Press, Boca Raton, FL, 1994.)
Less than
1 μm Dense skin layers
About
0.1 mm Porous sublayer
FIGURE 3.2  Asymmetric structure of the membrane. (From
Matsuura, T., Synthetic Membranes and Membrane Separation
Processes, CRC Press, Boca Raton, FL, 1994.)
Compared with CA or PA membranes of integrally
skinned asymmetric structure, the PA-TFC membrane enjoys
superior permeation flux. However, the PA-TFC membranes
are more susceptible to halogens compared to the CA mem-
branes that are, in general, resistant to halogens. But accord-
ing to the data reported, the permeate flux, antifouling, and
antichlorine ability of the RO membrane are still not as good
as desired, by either the CA membrane of integrally skinned
structure or the PA-TFC membrane, and efforts to improve
membrane performance are continuing. One such example
is the asymmetric co-PA membrane with piperazine moiety,
which was developed by Toyobo in hollow-fiber configura-
tions [11]. The rejection of the TFC flat-sheet membrane starts
to decrease at around 4000  h and drops almost completely
at around 8000 h, whereas the rejection retention of Toyobo
hollow-fiber membrane is quite stable, up to an 8000 h test
period. The representative chemical structures of the conven-
tional TFC of Dow, DuPont, Toray, and Toyobo membranes
are represented in Figure 3.3. It is noted that the m and n
values of the Dow TFC-co-PA are approximately 0.7 and 0.3,
respectively. The chemical components of the DuPont and
Toyobo materials are copolyamidohydrazide and co-PA con-
taining piperazine as well as diphenylsulfone, respectively.
It is worth mentioning that the commercial TFC membranes
manufactured by Dow, DuPont, Toray, and Toyobo are called,
for example, FT-30 (aromatic PA), PPPH8273 (aromatic
copolyamidohydrazide), UTC-70 (cross-linked aromatic PA),
and 4T-PIP(30) (chlorine-resistant co-PA), respectively.
3.2  MEMBRANE PREPARATION
3.2.1 Integrally Skinned Asymmetric Membrane
and Thin-Film-Composite Membrane
The phase inversion technique is used to prepare integrally
skinned asymmetric membranes [12]. This is a process in
which a polymer is transformed from a liquid to a solid state.
The dry–wet phase inversion technique and the temperature-
induced phase separation (TIPS) are most commonly
used in the industrial membrane manufacturing. Loeb and
Sourirajan applied the dry–wet phase inversion technique
in their development of the first CA membrane for seawa-
ter desalination, which is often called the Loeb–Sourirajan
method. According to the Loeb–Sourirajan method, polymer
solutions are prepared by mixing polymer, solvent, and some-
times even nonsolvent. The solution is then cast on a suitable
surface with a doctor blade to a thickness of about 250 μm.
After partial evaporation of the solvent, the cast polymer
solution film is immersed in a bath of nonsolvent medium,
often called coagulation (gelation) medium. Solidification of
the polymer film takes place in two steps, that is, evapora-
tion of the solvent and the solvent–nonsolvent exchange in
the gelation bath. It is often preferable to choose a solvent of
strong dissolving power with high volatility. During the first
step of desolvation by solvent evaporation, a thin skin layer
of solid polymer is formed instantly at the top of the cast
film due to the loss of solvent. In the next solvent–nonsolvent
exchange step, the nonsolvent diffuses into the polymer solu-
tion film, while the solvent diffuses out through the thin solid
layer. The composition of the polymer solution changes dur-
ing the solvent–nonsolvent exchange process.
As already mentioned, TFC membranes are fabricated by
in situ polymerization. This method, developed by Cadotte and
coworkers of Filmtec in the 1970s, is currently most widely
used to prepare high-performance RO and nanofiltration (NF)
membranes [8]. A thin selective layer is deposited on top of a
porous substrate membrane by interfacial in situ polycondensa-
tion. There are a number of modifications of this method pri-
marily based on the choice of the monomers [13]. However,
for the matter of simplicity, the polycondensation procedure is
described by a pair of diamine and diacid chloride monomers.
A diamine solution in water and a diacid chloride solu-
tion in hexane are prepared. A porous substrate membrane is
then dipped into the aqueous solution of diamine. The pores
at the top of the porous substrate membrane are filled with
the aqueous solution in this process. The membrane is then
immersed in the diacid chloride solution in hexane. Since
water and hexane are not miscible, an interface is formed at
the boundary of the two phases. Polycondensation of diamine
and diacid chloride will take place at the interface, result-
ing in a very thin layer of PA. The preparation of compos-
ite membranes by the interfacial in situ polycondensation is
schematically presented in Figure 3.4.
 Reverse Osmosis Membrane 37

O O H
H O O H
C C N H
N C C N
N
m n
C O
CO2H
(a)

O H
O H H O
C N
C N N C
m
(b)
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O O H H O O H H
C C N N C C N N

m n
N H C O

C O N H

O H
C CO2H N NH2

(c)

O
O H O H O
C O
C N S N C
C N N
O m
n
(d)

FIGURE 3.3  Representative chemical structures of the conventional TFC of (a) Dow, (b) DuPont, (c) Toray, and (d) Toyobo membranes.

Aqueous phase Hydrocarbon phase
Porous
substrate
(a) (b) (c)
FIGURE 3.4  Schematic of in situ IFP.
There are a number of combinations for the choice of
diamine and acid chloride monomers. For example, if TMC,
which has three –COCl groups in an aromatic ring, is mixed
with phthaloyl chloride, which has two –COCl groups, cross-
linking will form between two main chains. Unreacted –COCl
will become –COOH upon contact with water and the mem-
brane will become negatively charged. Monomers with reactive
groups other than amine and acid chloride can also be used.
3.2.2 Membrane Surface Modification
Since both the surface chemistry and morphology of the
membrane play a crucial role in determining the membrane
performance, its enhancement has been attempted through
modification of the membrane surface [14,15]. In fact, the
Composite
­latest researches on TFC membranes are mostly on the mem-
membrane
brane surface modification as summarized [16]. To the authors’
knowledge, most of them remain research attempts and yet to
be commercialized.
Soaking the freshly prepared TFC membranes in solu-
tions containing various organic species, including glyc-
erol, sodium lauryl sulfate (SLS), and salt of triethylamine
and camphorsulfonic acid (TEACSA), can increase the
(d) membrane flux in RO applications by 30%–70% [17]. The
physical properties of TFC (abrasion resistance) and flux sta-
bility can also be improved by applying an aqueous solution
composed of polyvinyl alcohol (PVA) and a buffer solution
as a posttreatment step during the preparation of the TFC
membranes [18]. On the other hand, using PVA-based amine
compounds having a side-chain amino group at the aqueous
phase monomer instead of MPD can produce high-flux TFC
membranes for low-pressure applications [19,20]. The addi-
tion of alcohols, ethers, sulfur-containing compounds, mono-
hydric aromatic compounds, and more specifically dimethyl
sulfoxide (DMSO), in the aqueous phase, can produce TFC
membranes with an excellent performance [21–24].
It was also found that the water flux of TFC-RO mem-
branes could be doubled without affecting the salt rejection
by incorporating zeolite nanoparticles in the thin layer of the
 38 Handbook of Membrane Separations: Chemical, Pharmaceutical, Food and Biotechnological Applications
TFC-RO membranes [25]. To prevent microbial fouling, a
new type of antifouling membrane was developed by intro-
ducing TiO2 nanoparticles to TFC membranes in order to
reduce the loss of RO permeability [26,27].
Water permeability of PA-TFC-RO membranes could be
increased using an oxygen plasma treatment by introducing
carboxylic groups, which increases the hydrophilicity of the
treated membrane. On the other hand, the chlorine resistance
of the TFC-RO membrane can be enhanced using an argon
plasma treatment that causes cross-linking to take place at
the nitrogen sites on the membrane surface [28].
Since hydrophilic surfaces are believed to attract more
water than organic contaminants of high hydrophobicity, many
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attempts have been made to increase membrane surface hydro-
philicity by surface modification techniques, each having its
own advantages and disadvantages. Hydrophilization by treat-
ing the membrane surface with water-soluble solvents (acids,
alcohols, and mixtures of acids, alcohols, and water) is one
of the surface modification techniques, as mentioned earlier.
This method increases the flux without changing the chemical
structure, but one of its disadvantages is that the  water flux
decreases with time because of the leaching of the hydrophi-
lizing agent by water permeation [29]. Using a mixture of acid
and alcohol in water for the surface treatment can improve the
surface properties since acid and alcohol in water cause partial
hydrolysis and skin modification, which produces a membrane
with a higher flux and a higher rejection. It was suggested that
the presence of hydrogen bonding on the membrane surface
encourages the acid and water to react on these sites producing
more charges [29,30]. Kulkarni et al. hydrophilized a TFC-RO
membrane by using ethanol, 2-propanol, hydrofluoric acid, and
hydrochloric acid [29]. They found that there was an increase
in hydrophilicity, which led to a remarkable increase in water
flux with no loss in ion rejection.
A hydrophilic, charged TFC could be produced by using
radical grafting of two monomers, methacrylic acid and
poly(ethylene glycol) (PEG) methacrylate, onto a commer-
cial PA-TFC-RO membrane [31]. It was found that the use of
amine containing ethylene glycol blocks enhanced the per-
formance of the membrane and highly improved membrane
water permeability by increasing hydrophilicity [32]. PEG
and its derivatives have been used for surface modification.
TFC membrane resistance to fouling could be improved by
grafting PEG chains onto the TFC-RO membranes [33,34].
Louie et al. coated the surface of commercial TFC-RO mem-
branes with a solution of polyether–PA (PEBAX 1657) to
produce antifouling membranes [35].
Another alternative and less common approach for the
membrane surface modification is the introduction of an
active additive. The basis of this technique is the idea that
those additives can move toward the top film surface dur-
ing membrane formation and alter membrane surface chem-
istry, while keeping bulk properties unchanged. According
to this method, only a very small quantity of the additives is
enough to change the surface chemistry of the membranes
[36]. Blending is a conventional technique used for mem-
brane surface modification, and recently, much attention
has been given to utilize this technique, in which hydro-
phobic surface-modifying macromolecules (SMMs) are
blended to a base polymer for membrane surface modifica-
tion [37]. Preparation of PA-TFC membranes for desalina-
tion using novel hydrophilic SMMs improved flux stability of
PA-TFC-RO m ­ embrane by using hydrophilic SMMs formed
simultaneously by in situ polymerization reaction when the
polycondensation reaction takes place within the organic sol-
vent of the TFC system [38,39].
3.2.3 Development of Membranes
for Boron Removal, Chlorine
Tolerance, and Antibiofouling
Boron occurs in seawater at an average concentration of
4–6  mg/L. Toxicological effects of exposure of the human
body to boron, primarily by consumption of desalinated sea-
water, were also reported [40]. A provisional guideline of the
WHO suggests a maximum boron concentration of 2.4 mg/L
in drinking water (see, e.g., [41]). The California Department
of Public Health (CDPH) set a notification level of 1.0 mg/L
for the drinking water. It has been found that the RO mem-
brane is not very effective in boron removal. According to the
study for the two-stage RO desalination of Atlantic Ocean
water under the conditions of feed pressure 802–966 psi, a
product recovery of 38%–42%, for the boron concentration
of 4.2–4.7 mg/L and with pH 7.0–8.2, was achieved. Boron
removal in the first stage was 80.0%–83.4%, while in the sec-
ond stage, it was 64.4%–66.0%. These low values of boron
rejection cannot satisfy the WHO standard for the drinking
water. The difficulty of boron removal arises from the fact
that boron exists in seawater either as boric acid (H3BO3)
or borate ion (H2BO3−) with their respective concentration
depending on pH. Based on the first dissociation constant,
pKa1 = 8.7, boron is primarily present as boric acid in neutral
seawater. It was found that the charged H2BO3− is rejected at
97.3%–99.6% by commercial spiral-wound modules, while
the rejection of H3BO3 is much lower (85.7%–96.7%) [42].
A recent paper published by Koseoglu et al. reported boron
rejection of 85%–90% from seawater of pH = 8.2 (average
seawater pH) and >98% at pH of 10.5 [43]. The experiments
were carried out at 700 psig at ambient temperature using
two commercial seawater reverse osmosis (SWRO) ­modules,
that is, Toray™ UTC-80-AB and Filmtec™ SW30HR (Dow
Chemical). SWRO membranes with better boron r­ ejection are
still being sought. Further improvements in boron removal
by RO membranes can be found in the literatures [44,45].
There are still drawbacks in the commercial integrally
skinned CA and PA-TFC-RO membranes. CA membranes
are susceptible to microbiological attack, undergo compac-
tion at high temperatures and pressures, and are workable
only within a narrow range of pH (3–7). PA membranes,
on the other hand, can tolerate a wider range of pH but suf-
fer from poor resistance to continual exposure to oxidizing
agents such as chlorine that is most widely used as an oxi-
dizing biocide in water treatment. Namely, performance of
 Reverse Osmosis Membrane 39

A B
n 1–n

Disulfonated poly (arylene ether sulfone) random copolymers

O –M+
O
S
O O
A= S O O
O O
S
+M–
O (M = H or Na)
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Hydrophilic part
(disulfonated polymer segment)
O
O O O For BPS–XXY series

S
B= or

O
P O O For BPO–XXY series

FIGURE 3.5  Reaction scheme of copolymerization. (From Park, H.B. et al., Angew. Chem., 120, 6108, 2008. With permission.)

PA membranes deteriorates at a continuous exposure to water
containing more than a few parts per billion (ppb) of chlorine.
A number of attempts have been made to change the macro-
molecular structure of PA, as already mentioned in surface
modification section, but the problem has not yet been solved
completely.
Recently, an attempt was made to synthesize a sulfo-
nated PS using a disulfonated monomer. Namely, a ran-
dom copolymer is synthesized by direct polymerization of
3,3′-disulfonato-4,4′-dichlorodiphenyl sulfone (SDCDPS),
4,4′-dichlorodiphenyl sulfone (DCDPS), and 4,4′-biphenol
(BP), or another copolymer is synthesized from SDCDPS,
BP, and 4,4′-difluorotriphenylphosphine oxide (DFIPPO)
[46]. The reaction scheme is presented in Figure 3.5 [46].
In contrast to sulfonation of PS, sulfonated PS of a given
ion exchange capacity (IEC) is obtained by this method in
a more controlled manner. Using these polymers, RO mem-
branes were prepared and their chlorine resistance was exam-
ined. One laboratory-made membrane (BPS-40H, based on
the second type of synthesized copolymer with 40% sulfonic
acid component in H form) was compared with SW30HR
SWRO membrane from Dow with a feed solution contain-
ing 2000 ppm NaCl and 500 ppm chlorine at pH = 9.5.
While the solute rejection of commercial RO membranes
decreased by 20% within 10,000 ppm-hours of chlorine
exposure, there was hardly any change in salt rejection in
the laboratory-made membrane. This chapter indicates that
there are still many things to be done in RO membrane mate-
rial ­development, a research topic that has been neglected for
many years.
3.2.4 Membrane Development with Low
Pressure and High Flux
Kurihara summarized the improvement in RO membrane
performance up to 1999 [47]. The membrane productivity
in terms of water flux normalized by operating pressure has
increased by an order of magnitude. This allowed the opera-
tion of RO for brackish water desalination and ultrapure-
water production at pressures lower than 1 MPa, resulting
in significant saving in energy cost. Kurihara attributed the
high productivity of the newly developed membrane to an
increase in surface roughness. Currently, there seems no
limit in sight in further improvement of membrane produc-
tivity. Table 3.1 also shows similar advancement made for the
Dow RO membranes [48].
3.2.5 Membrane Development for
High Operating Pressure
The present seawater desalination technology aims to
increase the pure water recovery by a membrane module
from the conventional 40% to 60%. Since the osmotic pres-
sure of the retentate will increase from 4.5 to 7.0 MPa when
 40 Handbook of Membrane Separations: Chemical, Pharmaceutical, Food and Biotechnological Applications

TABLE 3.1
Advances in Dow RO Membrane
Year Production Capacity (gpd) Salt Rejection (%)
Brackish water
1990 8,000 98
1998 10,000 99.2
2007 11,000 99.8
Seawater
1990 4,000 99.4
1998 5,500 99.5
2007 7,500–8,000 99.8
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Source: Micklos, M., The development of reverse osmosis and nanofiltration through
modern times, Plenary Lecture III, International Congress on Membranes
and Membrane Processes (ICOM), Honolulu, HI, July 12–18, 2008.

the water recovery increases from 40% to 60%, the develop-
ment of a high-pressure vessel, as well as the development
of a membrane that will show little compaction under a
high pressure, is necessary. Kawada reported the develop-
ment of an RO membrane that was suitable for operation
at 9 MPa [49]. The compaction of membrane usually takes
place at the porous sublayer rather than at the skin layer. An
attempt was therefore made to reduce the compaction by
making a large number of uniform pores of small sizes at the
surface of the porous sublayer on which an aromatic PA skin
layer was coated by in situ IFP. The stability of the membrane
module productivity increased significantly as compared to
the conventional seawater desalination membrane.
3.3  REVERSE OSMOSIS TRANSPORT
3.3.1  Single Component System
Currently, the mainstream of RO membrane transport ­theory
is the solution–diffusion model [50]. According to the model,
mass transfer occurs in three steps: absorption to the membrane,
diffusion through the membrane, and desorption from the mem-
brane. The chemical potential gradient from the feed side of the
membrane to the permeate side of the membrane is the driv-
ing force for the mass transfer. When the difference in hydro-
static pressure is greater than the difference in osmotic pressure
between the upstream and downstream sides of the membrane,
a chemical potential difference of water across the membrane
drives water against the natural direction of water flow.
Thus, the water transport through the membrane can be
described by
N A = L (Δp − Δπ) (3.1)
where
NA is the water flux through the membrane (subscript A
denotes water)
L is the water permeability coefficient
Δp is the transmembrane pressure difference
Δπ is the difference in osmotic pressure between the
upstream and downstream sides of the membrane
The osmotic pressure can be given by an equation similar to
the van’t Hoff equation:
π = iϕCRT (3.2)
where
i is the dissociation parameter, which is the number of
ions produced by the dissociation of the salt
ϕ represents a correction factor
C is the salt concentration
R is the universal gas constant
T is the absolute temperature
The permeability coefficient can be given by
DSV
L= (3.3)
RTl
where
D is the diffusivity of water in the membrane
S is the water solubility in the membrane
V is the partial molar volume of water
l is the thickness of the skin layer of the membrane
The osmotic pressure of seawater is typically 2300–2600 kPa
and can be as high as 3500 kPa [51]. Osmotic pressures of
brackish water are much smaller than those of seawater.
Corresponding to the concentration range of 2000–5000 mg/L,
the osmotic pressure ranges from 100 to 300 kPa [51]. To
overcome these osmotic pressures, the pressures applied to
RO seawater desalination are typically 6000–8000 kPa, and
for the desalination of brackish water, they are 600–3000 kPa.
The recovery of product water is an important parameter
of RO operation. It is defined as
Qp
Rw = (3.4)
Qf
where Qp and Q f are the volumetric flow rates of the per-
meate and feed streams, respectively. Typically, the recovery
 Reverse Osmosis Membrane 41

of RO seawater desalination is 40%. When the recovery

is increased, the salt concentration on the upstream side CA2
increases and more pressure should be applied to overcome
the osmotic pressure. A special design of both membrane and CA3
membrane module is required to apply such high operating
pressures. The problem of salt precipitation will arise as well.

Boundary layer
Main body of feed solution
On the other hand, the recovery of RO brackish water desali-
nation can reach as high as 85%.
Assuming the passages of water and salt through the
membrane are independent from each other, the salt trans-
port through the membrane occurs by the concentration

Permeate solution
difference between the upstream and the downstream sides
of the membrane as the driving force. The salt transport
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through the membrane can be given by

CA1
N B = B(C fs − C p ) (3.5)

y

where
NB is the salt flux (subscript B denotes salt)
B is the salt transport parameter
δbℓ
Cfs and Cp are the salt concentrations at the membrane sur-
face on the feed side and in the permeate, respectively

B is further given by Feed flow

DB K B FIGURE 3.6  Schematic illustration of concentration polariza-

B= (3.6)
l tion. (From Matsuura, T., Synthetic Membranes and Membrane
Separation Processes, CRC Press, Boca Raton, FL, 1994.)

where By solving simple transport equations in the boundary

DB is the diffusivity of salt through the membrane layer at the membrane surface, the preceding two concentra-
KB is the partition coefficient of salt between the solution tions can be related to each other by the following equation:
and the membrane
C fs − C p ⎛N ⎞
A more important parameter to express the salt passage = exp ⎜ A ⎟ (3.8)
C fb − C p ⎝ c Ak ⎠
through the membrane is salt rejection given by

where
C fb − C p
R= ×100% (3.7) cA is the molar concentration of water
C fb k is the mass transfer coefficient of the salt

where To minimize the concentration polarization, that is, to make

Cfb is the salt concentration in the bulk of the solution on
the feed side
R = 100% means perfect salt rejection and R = 0 means no
salt rejection by the membrane
It should be noted that Cfs is the salt concentration at the
membrane surface on the feed side that was used to cal-
culate NB, while Cfb is the salt concentration in the bulk
of the solution on the feed side of the membrane. Cfs and
Cfb may become different due to a phenomenon called con-
centration polarization. This occurs due to the rejection of
the salt and its accumulation at the membrane surface. The
concentration polarization is schematically illustrated in
Figure 3.6.
Cfs as close to Cfb as possible, k should be increased, which is
enabled by increasing the turbulence of the feed solution. All
the RO modules include devices to achieve this goal.
3.3.2 Multicomponent System
Seawater is a complicated mixture of many components.
Hence, it is difficult to predict the membrane performance
under different operating conditions based on transport theo-
ries. Most of the theories treating the separation of multicom-
ponent electrolytic systems are based on the Debye–Hückel
theory, Donnan effect, and Nernst–Planck equation [52,53].
Although they are applicable to the mixture of any number of
ions involved in the feed, there are only few works in which
 42 Handbook of Membrane Separations: Chemical, Pharmaceutical, Food and Biotechnological Applications
agreement between experimental results and theoretical pre-
dictions was tested for mixtures of more than four ions. One
of the noted exceptions is the work of Rangarajan et al. [54].
These authors have expanded the transport theory to treat
a multicomponent system involving nine ions of primary
importance present in seawater. The separations of individ-
ual ions were predicted theoretically and the prediction was
examined by experiments.
3.4  COMMERCIAL MODULES
The commercial RO modules that have appeared in the lit-
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erature since 1977 are summarized in Table 3.2 together with
the typical operating conditions and performance. Some of
them might no longer exist in the market. From the table, it is
clear that the majority of high-salt-rejection RO membranes
are spiral-wound aromatic PA-TFC membranes with a noted
exception of Toyobo that is based on CTA hollow fiber. The
reason might be easier cleaning of the spiral-wound module,
on one hand, and chlorine resistance of CA, on the other.
3.5 RECENT OPERATIONAL EXAMPLES
OF LARGE-SCALE RO MODULES
Table 3.3 summarizes recent operational examples of large-
scale RO modules.
The brief outline of each paper in Table 3.3 is as follows:
This study deals with the optimization of membrane fil-
tration performance in the treatment of acid mine drainage
(AMD) using two NF membranes (NF99 from Alfa Laval
and DK from GE Osmonics) and one RO membrane (RO
HR98PP from Alfa Laval) [55]. RO experiments were per-
formed with a laboratory-scale membrane area of 63.6 cm2,
and pressure, pH, temperature, and flow rate were changed.
In 2007, two of the world’s largest wastewater reclamation
plants using similar energy-saving RO membrane technology
were commissioned [57]. One plant, Orange County Water
District’s (OCWD) Groundwater Replenishment System
(GWRS) located in Southern California, was expanding
the plant to 265,000 m3/day (70 MGD), while the other, Ulu
Pandan located in Singapore, was producing 148,000 m3/day
(39 MGD). This paper discusses the evolution of the design
of these large-scale wastewater reclamation plants using
energy-saving RO membranes (PA-TFC membranes from
Koch, Dow, and Hydranautics). Lessons learned from years
of pilot, demonstration plants, and full-scale plant experience
at both OCWD and UP were presented.
A case study of a natural gas production site covering var-
ious technical issues related to selection of an appropriate RO
system is presented [59]. As part of the pretreatment selection,
two types of ultrafiltration (UF) membrane modules, namely,
spiral wound and hollow fiber, with molecular weight cutoff
(MWCO) of 8,000 and 50,000 Da, respectively, were tested
in parallel with NF membranes of the spiral-wound type with
MWCO 200 Da. The NF plant with 50% capacity gave a
recovery of 75%, and the RO plant gave a recovery of 60% in
comparison to the expected 92%–95%. The long-term tests
have indicated that the remainder of the membranes could
be installed to achieve full capacity of the plant. This study
also demonstrates the importance of the selection of a proper
pretreatment setup for the RO system design.
The following three case studies of wastewater desalina-
tion are described [60]. (1) Effluent from a poultry and meat
processing industry in southern Europe was treated by RO
(Filmtec PA-TFC membrane). Pretreatment by UF and/or con-
tinuous MF (CMF) was made before NF ­treatment followed
by RO. (2) Secondary municipal and agricultural effluent
was treated by Filmtec BW30-365FR2 with B ­ W30-330RO.
(3) High-salinity brackish well water was treated by (SWRO)
Filmtec SW30-8040. In each case, a cost estimation of the
product water was made.
The performance and characteristics of new RO mem-
branes operating at ultralow pressure (ULP) (7–10 bar)
are presented [61]. The total cost comparison based on a
4 km3/day plant revealed that TFC ULP provides about 10%
savings over the traditional TFC HR (traditional brackish
water RO membrane). Generally, the use of TFC ULP con-
tributes to energy saving, but the capital cost increases due to
the higher membrane cost.
The study focuses on the behavior of the ULP RO mem-
branes in the full-scale system [62]. The ULP membranes
have salt rejections comparable to conventional RO mem-
branes, but the hydraulic characteristics are significantly
different. Hence, modifications to conventional membrane
system design must be considered to optimize the use of the
ULP RO membrane. Several design options are evaluated for
function, effectiveness, and cost impact.
The growing success of membranes in municipal and
industrial wastewater is related to improved process designs
and improved membrane products [63]. Key factors that have
been determined to result from successful operation of large-
scale plants are discussed in this paper. Factors that play a
key role in the use of RO membranes include ultra- or micro-
filtration pretreatment, low fouling membranes, flux rate, and
recovery and control of fouling and scaling. In particular,
high flux rates can be used when UF or MF pretreatment
is used. These technologies remove most of the suspended
particles that would normally cause heavy fouling of lead
elements. It was demonstrated by a 2.5-year operation of the
10,000 m3/day Bedok, Singapore, demonstration plant.
The conventional hollow-fiber-type RO element is a single
open-ended (SOE) structure, in which the pressure drop of
the permeated water in the bore side of the hollow fibers pre-
vents the development of a large-sized (longer) RO element
[70]. In this work, a both open-ended (BOE) element was
devised to reduce the permeate pressure drop. Medium-sized
Toyobo RO module HJ9155 (CTA) was used for the test. It
has been confirmed that the permeate flow rate of BOE was
greater by about 30% than that of SOE.
Organic foulants obtained from UF (Kolon Membrane,
Gwacheon, Korea), and RO (4-stage spiral-wound PA-type
TFC-RO membrane system, Woongjin Chemical, Seoul,
Korea) membranes of a large-scale municipal water
 TABLE 3.2
Typical Commercial Module Performance at Various Operating Conditions
Test Conditions Performances
Surface Operating Salt Rejection
Manufacturer Membrane Code Module, Area (m2) Material Pressure (MPa) Temp. (°C) pH Feed Conc. (mg/L) PWP (m3/day) (%) References
Alfa Laval, HR98PP Thin-film- 16–40 bar 25 2–10 200 NaCl 39 L/m2 h at 20 >96 [55]
Sweden composite bar
(TFC) on
Reverse Osmosis Membrane

polypropylene
Dow Chemical XFS-4167.08 Hollow fiber, 85/8 Aromatic 56 atm 35 4–7.5 290–470 TDS 9.4 (2,500 gpd) 98.5 [56]
in. × 40 in. L, 335 polyamide (PA)
BW30-400FR 400 ft2 PA reverse 225 psi 6 2000 NaCl 39.7 m3/h (10,500 99.5 [57]
osmosis (RO) gpd)
XLE-440 440 ft2 PA RO 100 psi 6 500 NaCl 48.1 m3/h (12,700 99.0 [57]
gpd)
DuPont de Permasep B-10 Hollow fiber, 5 1/2 Aromatic PA 56 atm 35 5–9 290–470 TDS 5.5 (1,500 gpd) 98.5 [56]
Nemours in. OD × 4 5/8 in.
ID × 47 in. L, 139
Permasep B-10 Hollow fiber, 4 in. Aramid 800 psi 25 30,000 NaCl 1,500 gpd [58]
dia., 4 ft long
Permasep B-10 Hollow fiber, 8 in. Aramid 800 psi 25 30,000 NaCl 5,000 gpd [58]
dia, 5 ft long
Filmtec Corp. BW30-4040 Spiral wound TFC 18 bar 30 6.81 0.89 L/m2 h [59]
SW30-2540-2 Spiral wound TFC 60 bar 30 6.81 0.5 L/m2 h [59]
SW30-2540-2 Spiral wound TFC 62 bar 30 6.81 0.14 L/m2 h [59]
SW30-380 61.0 bar 19.9 33,030 TDS 5.8 m3/h (8,000 99.3 [60]
gpd)
Fluid systems TFC ULP PA 100–150 psi 4–11 1,300 TDS 105.8 m3/h 90.2 [61]
TFC HR PA 100–150 psi 4–11 1,300 TDS 103.3 m3/h 96.2 [61]
TFC 8822 HR 30.6 (330 ft2) PA-TFC 1.55 (225 psi) 2,000 NaCl 32.2 (8,500 gpd) 99.5 [62]
TFC 8821 ULP 30.6 (330 ft2) PA-TFC 1.05 (150 psi) 500 NaCl 32.2 (8,500 gpd) 99.0 [62]
Hydranautics 8040-LSY-CPA2 33.8 (365 ft2) PA-TFC 1.55 (225 psi) 1,500 NaCl 32.2 (8,500 gpd) 99.5 [62]
8040-UHY-ESPA 37.1 (400 ft2) PA-TFC 1.05 (1500 psi) 1,500 NaCl 32.2 (8,500 gpd) 99.0 [62]
LFC 37.2, 3-stage 28:14:8 PA 15.5 bar 25 6.8–7.0 1,500 NaCl (2,380 gpd) 98.7–99.5 [63]
array with 6
elements per vessel
Hydranautics LFC1 400 ft2 PA RO 225 psi 6 1,500 NaCl 41.6 m3/h 99.5 [57]
(11,000 gpd)
LFC3 400 ft2 PA RO 225 psi 6 1,500 NaCl 36.0 m3/h 99.7 [57]
(9,500 gpd)
ESPA2 400 ft2, 3-stage 6:4:2 PA RO 150 psi 30 6 1,500 NaCl 34.1 m3/h 99.6 [57]
array with 7 (9,000 gpd)
elements per vessel
(Continued)
43

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 44

TABLE 3.2 (Continued)

Typical Commercial Module Performance at Various Operating Conditions
Test Conditions Performances
Surface Operating Salt Rejection
Manufacturer Membrane Code Module, Area (m2) Material Pressure (MPa) Temp. (°C) pH Feed Conc. (mg/L) PWP (m3/day) (%) References
ESPA2+ 440 ft2 PA RO 150 psi 30 6 1,500 NaCl 3
45.4 m /h 99.6 [57]
(12,000 gpd)
LFC1-4040 37.2 per element PA RO 7.5–8.2 bar 30 633–987 TDSa 9.4 gfd 97.1–98.1 [64]
ESPA2-4040 37.2 per element PA RO 7.5–8.2 bar 30 633–987 TDS 11.3 gfd 97.1–98.1 [64]
LFC3-4040 37.2 per element PA RO 7.5–8.2 bar 30 1,500 NaCl 14.1 gfd 97.1–98.1 [64]
Koch Membrane TFC HR 400 ft2 PA RO 225 psi 6 2,000 NaCl 42.4 m3/h 99.5 [57]
(11,200 gpd)
Nitto Electric NRO-A (first stage) Tubular, 190 mmϕ × Cellulose 50 kg/cm2 25 5.5–6.0 35,000 NaCl 0.30 m3/day 89 [65]
Ind. Co./Kobo 2674 mm L, 1.75 diacetate, FPRa
Steel (tube) (12.5 mm ID (tube)
× 18 pcs)
NRO-B (second stage) Tubular, 190 mmϕ × Blend of cellulose 40 kg/cm2 25 5.5–6.0 5,000 NaCl 0.56 97.5 [65]
2674 mm L, 1.75 diacetate and
(tube) (12.5 mm ID CTA, FPR
× 18 pcs) (tube)
Nitto Electric NRO-A, NRO-B (first Tubular, 12:4 parallel Blend of 50 kg/cm2 35 3,800 TDS 2.75 [56]
Ind. Co. stage) 2–1 × 3 series cellulose
diacetate and
CTA
NRO-A, NRO-B Tubular, 3 numbers Blend of 40 kg/cm2 35 250 TDS 1.7 [56]
(second stage) cellulose
diacetate and
CTA
Toray Co. SC-5000A (first stage) Spiral wound, 12: CA 56 kg/cm2 35 3,000 TDS 12.5 [56]
X-mas tree series
6–4–2
SC-5000B (second Spiral wound, 4 CA 40 kg/cm2 35 200 TDS 10 [56]
stage) numbers
SC-5100A (first stage) Spiral wound, CA 56 kg/cm2 25 5.5–6.0 35,000 NaCl 2.0 95 [65]
100 mmϕ × 1.0 mL,
6.8
SC-5100B (second Spiral wound, CA 30 kg/cm2 25 5.5–6.0 2,000 NaCl 3.2 98 [65]
stage) 100 mmϕ × 1.0 mL,
6.8
PEC-1000 Spiral wound 53.4–59.5 kg/ 11.8–23.8 6.4–6.9 18,400–19,800 Cl− 706–812 99 [66]
cm2
(Continued)
Handbook of Membrane Separations: Chemical, Pharmaceutical, Food and Biotechnological Applications

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 TABLE 3.2 (Continued)
Typical Commercial Module Performance at Various Operating Conditions
Test Conditions Performances
Surface Operating Salt Rejection
Manufacturer Membrane Code Module, Area (m2) Material Pressure (MPa) Temp. (°C) pH Feed Conc. (mg/L) PWP (m3/day) (%) References
SU-720 Spiral wound, low PA composite 1.5 25 1,500 NaCl 26.0 99.4 [67]
pressure
SUL-G20 Spiral wound, ULP PA composite 0.75 25 1,500 NaCl 26.0 99.4 [67]
Reverse Osmosis Membrane

SUL-H20 Spiral wound, super PA composite 0.5 25 1,500 NaCl 26.0 99.4 [67]
ULP
Toyobo Co. HR-5350 (first stage) Hollow fiber, 5 CA 38 kg/cm2 35 2,000 TDS 14 [56]
parallel
HR-5350S (second Hollow fiber, 1 CA 70 kg/cm2 35 200 TDS 10 [56]
stage) number
Hollosep Hollow fiber, CA 55 kg/cm2 25 5.5–6.0 35,000 NaCl 2.5 94 [65]
HR 5350 (first stage) 125 mmϕ ×
1.1 mL, 80
Hollosep Hollow fiber, CA 22 kg/cm2 25 5.5–6.0 2,000 NaCl 10 97 [65]
HR 5350S (second 125 mmϕ ×
stage) 1.1 mL, 80
Hollosep Hollow fiber, CTA 55 kg/cm2 G 25 3–8 35,000 NaCl >10 99.7 [68]
HR 8350 305 mmϕ ×
1330 mm L
Hollosep high pressure Hollow fiber, CA 75 kg/cm2 G 40 4,200 NaCl 67.5 L/m2 day 99.8 [69]
temp. (HPT)
JM-12 Hollow fiber, 5 CA 70 kg/cm2 G 25 3,500 NaCl 167–132.5 99.1–99.4 [69]
elements
(HR1235ON-5)
Hollosep Hollow fiber, 8 in. 54.8– 11.7–28.1 6.15– 47,550–51,000 μs/cm 366–439 99 [66]
module 58.3 kg/cm2 6.94
Hollosep Hollow fiber, 12 in. 53.2– 11.7–28.1 6.15– 47,550–51,000 μs/cm 340–440 99 [66]
module 57.4 kg/cm2 6.94
HJ9155 Hollow fiber, 870 CTA 5.5 25 3,500 NaCl 34 99.6 [70]
Universal Oil ROGA-2B-TFC Spiral wound, 8 in. CTA TFC 60 atm 35 4–7.5 290–470 TDS 120 L/day (32 98.5 [56]
Products ϕ × 10 3/4 in., 0.36 gpd)
Vontron HOR21-8040 33.9 (365 ft2) Aromatic PA 4.14 25 7.5 2,000 NaCl 34.1 (9,000 99.2 [67]
Membrane gpd)
Tech., Beijing
HOR21-4040 7.9 (85 ft2) Aromatic PA 4.14 25 7.5 2,000 NaCl 8.3 (2,200 gpd) 99.2 [67]
HOR-2012 0.46 (5.0 ft2) Aromatic PA 2.07 25 7.5 250 NaCl 0.19 (50 gpd) 97.5 [67]
Woongjin RE8040-FL Spiral wound, 37.2 PA-TFC 10–11.5 kgf/cm2 7.5 3.85 mg/L TSSa 0.5–0.8 m3/m2 Not detected [71]
Chemical, Seoul day

a TDS, total dissolved solid; TSS, total suspended solid; FRP, fiber-reinforced plastic.
45

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 46 Handbook of Membrane Separations: Chemical, Pharmaceutical, Food and Biotechnological Applications

TABLE 3.3
Examples of Large-Scale RO Applications
Membrane and Planta (Elementb)
Module Capacity Water Type Location Other Remarks References
Pretreatment and fouling
PA-TFC membrane 30 m3/day Wastewater generated from Thailand Selection of pretreatment [59]
natural gas production (pretreatment)
PA-TFC a2, 1.05, and Meat processing effluent, Southern Europe, Pretreatment study and cost [60]
14 km3/day municipal and agricultural South America, evaluation (pretreatment)
effluent, agricultural runoff Southern Spain
PA-TFC membrane a10 m3/h Municipal wastewater Bedok and Kranji, MF and UF pretreatment [63]
Singapore (pretreatment)
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PA-TFC 37.2 m2 Municipal water Gwangju, Korea Characterization of organic [71]

foulant (fouling)
PA spiral wound a36 m3/h RO River water Steel industry Bremen, UF pretreatment of RO [72]
Germany feedwater (pretreatment)
Filmtec BW 30 LE 440 a1.56 km3/day Surface water Geleen (NL) Pretreatment by UF [73]
(pretreatment)
Not specified Various Various Various Review, pretreatment [74]
(pretreatment)
New membranes and modules
PA spiral wound a24,000 m3/day Brackish water Hypothetical ULP (100–150 psi) (membrane) [61]
Fluid Systems TFC and a1.9 km3/day TDS 1000 and 5000 mg/L Collier County, FA System design for ULP RO [62]
Hydranautics TFC membrane (membrane)
CTA hollow fiber b34 m3/day Seawater Arabian Gulf Open-ended hollow fiber [70]
(membrane)
16 and 8 in. spiral- a180 mgd Colorado river water Metropolitan Water Cost evaluation of 16 and 8 in. [75]
wound element (Koch District of California RO element (cost)
membrane)
Energy
PA-TFC membrane a265 and 148 km3/ Groundwater and Orange County Use of energy-saving RO [57]
(Koch, Dow, and day wastewater District, CA, and Ulu membranes (energy)
Hydranautics) Pandan, Singapore
PA-TFC membrane b0.18 L/min Brackish water Aqaba Gulf, deep well Photovoltaic powered (energy) [76]
(maximum)
Not specified Various Various Various Review, solar-powered RO [77]
(energy)
Cost evaluation
PA-TFC and zeolite a50 m3/day Wastewater produced from San Juan Basin Cost evaluation (cost) [78]
membranes various sources
Not specified Not specified Not specified Not specified NF/RO/MD hybrid system cost [79]
evaluation (hybrid)
Miscellaneous
PA-TFC membrane Small lab scale AMD — Synthetic AMD (miscellaneous) [55]
(Alfa Laval)
— a120 k + 30 km3/ Seawater Gaza Strip Model development based on [80]
day BBNs (miscellaneous)
PA composite, Dow 1 km3/day 2000 ppm NaCl solution, — Removal of the top skin layer [81]
BW30FR fouled by BSA solution for reuse (miscellaneous)

reclamation plant were rigorously characterized using
conventional and advanced characterization analyses
(e.g., pyrolysis and mass spectrometry) in order to iden-
tify major constituents of the organic foulants and inves-
tigate fouling characteristics in a large-scale application
of the UF and RO membranes [71]. Hydrophobic fractions
comprising carboxylic acids and aldehydes strongly con-
tributed to the fouling formation of the UF membrane,
whereas the RO membrane foulants mainly consisted of
hydrophilic fractions comprising amides and alcohols,
indicating that the membrane characteristics could play
an important role.
 Reverse Osmosis Membrane
UF was used as a single-stage process to pretreat
s­urface water as an alternative to conventional multistage
treatment processes (e.g., ozonization–precipitation–
floculation–coagulation–chlorination–gravel filtration), in
which the use of different chemicals necessitates special
safety measures and careful harmonization and control
of water chemistry in view of the requirements of down-
stream RO [72]. By contrast, processes based on membrane
technology enable a simply designed plant to be used with
several advantages. The pretreated water was supplied to
the final stage of RO treatment to produce drinking water.
Two UF modules MOLPURE FW50 technology, a four-end
module produced by Daicen (cross-flow), and type S-225-X
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PVCUFC M5 from X-Flow (dead end) were used for compari-
son. The total operating costs were 0.25–0.35 EURO/m3 and
lower than 0.5 EURO/m3 of the conventional pretreatment.
The water demineralization plant in Geleen (NL) for
the production of boiler feedwater from surface water with
a capacity of 1560 m3/h uses RO and UF for the pretreat-
ment [73]. In this study, a series of pilot scale study was
made using different UF membranes and a suitable UF mem-
brane was selected. As for the RO membrane, Filmtec BW
30 LE 440 was chosen primarily due to its high-flux and
high-salt-rejection capacity.
This paper reviews the recent representative research that
is related to SWRO antifouling strategies and answers the
most crucial questions about the design and operating param-
eters of SWRO and its pretreatment processes [74]. Also the
economic evaluation of the SWRO system in regard to anti-
fouling strategies is discussed. The pretreatment technologies
to prevent membrane fouling and to extend the lifetime of the
RO membrane are commonly grouped into two categories:
conventional and nonconventional (membrane). After dem-
onstrating many case studies, the authors concluded that the
conventional pretreatment system applied in various SWRO
plants in various parts of the world proved to be able to pro-
vide the feedwater quality required for the RO lines. However,
the system was very difficult to control. On the other hand,
membrane pretreatment provides a more stable and reliable
system that can tolerate feedwater quality variations.
Three 16 in. diameter and 60 in. long RO-ULP elements
from Koch Membrane Systems were evaluated parallel with
two commercially available 8 in. diameter elements [75]. The
overall specific flux for 16 in. was comparable to that of 8 in.
element. Slightly higher fouling was observed for the former
element. Cost evaluation revealed that for a 185 million gpd
plant, 16 in. element can save as much as 12.4% in total cost.
The capital cost saving alone is 27%.
An experimental study was conducted to investigate the
potential of the development of water desalination using a
photovoltaic powered system in Jordan [76]. A testing rig was
built, where an RO (PA-TFC) desalination system is driven
by photovoltaic power by directly coupling the photovoltaic
powered system to a DC motor, which was coupled to a pump
that was capable of providing sufficient torque to run the RO
system. Analysis of results shows that a gain of 25% and 15%
of electrical power and pure water flow, respectively, could
47
be achieved using the east–west one-axis tracking system
compared with fixed flat plate.
The paper aims to provide a comprehensive review of all
the indirect solar desalination technologies along with plant-
specific technical details [77]. Solar desalination plants are
summarized since the year 1978 when solar RO desalination
started. The factors affecting PV-RO water cost are capital
cost of PV array and battery, inclusion of energy recovery
device, type of feedwater, and type of RO unit. A water cost
of around $7 m−3 for a 44 m3/day is estimated, which is very
high. For large-scale plants having a capacity of >1000 m3/
day, however, the specific plant cost is in the range of $4500–
$6200 m3/day with an estimated water cost of <$2 m−3 owing
to the reduction of high-efficiency PV module cost.
RO membranes including polymeric (PA-TFC membrane)
and molecular sieve zeolite membranes were investigated for
ion removal from the water produced at oil field and coal bed
methane sites by a cross-flow RO process [78]. Pretreatments
including NF and adsorption by active carbon were imple-
mented. The study revealed that (1) most of permeation tests
lasted only 3 months due to severe fouling, (2) multistage pre-
treatment is crucial to extend membrane life, and (3) only NF
treatment could extend the membrane life to 6 months.
In a comparative study of an integrated hybrid membrane-
based system with an earlier locally designed RO unit, such
system comprises NF, RO, and membrane distillation (MD)
subsystems [79]. The comparison is essentially based on
using the NF technique in pretreatment section, while the
MD was contributed to concentrate the two brine streams
from both NF and RO. Thus, high recovery rate of product
water is aimed for. The proposed system was economically
evaluated and compared with the RO unit. It was concluded
that 76.2% water recovery was possible with a water produc-
tion cost of $0.92 m−3.
Characterization of uncertainties in the operation and econ-
omies of the proposed seawater desalination plant in the Gaza
Strip was made by using a Bayesian belief network (BBN)
approach [80]. In particular, the model was used to (1) charac-
terize the different uncertainties involved in the RO process,
(2) optimize the RO process reliability and cost, and (3) study
how uncertainty in unit capital cost, unit operation and main-
tenance (O&M) cost, and permeate quality was related to dif-
ferent input variables. The minimum specific capital cost was
found to be 0.224 ± 0.064 US$/m3, and the minimum O&M
cost was found to be 0.59 ± 0.11 US$/m3. This unit cost was
for a production capacity of 140,000 m3/day.
This study aimed to assess the technical feasibility of
removing the dense PA active layer of RO membranes, with
the intent to reuse degraded RO into porous low-pressure
membranes [81]. The study assessed the ability of three
degrading solutions (NaOH, KMnO4, and NaOCl) to remove
the active layer. The most promising results were found using
NaOCl. Membranes treated with at least 300,000 ppm of
NaOCl presented an increased permeability to 175 ± 4 L/
m2/h/bar with <4% salt rejection. The fouling behavior of the
degraded RO membranes was also compared to commercially
available UF membranes, to which they displayed similar
 48 Handbook of Membrane Separations: Chemical, Pharmaceutical, Food and Biotechnological Applications
fouling characteristics, and by using LC-OCD, the MWCO of
the reused membranes was estimated to be 5–10 kDa.
From this review, it is quite obvious that the most seri-
ous concern over the large-scale plant operation is pretreat-
ment and fouling prevention. The membrane pretreatment
seems more effective and economical than the conventional
pretreatment. The recent membrane module development is
focused on ULP RO membranes and the construction of a
16 in. diameter module, both generating economic benefits.
But care must be taken for the large-diameter module opera-
tion. As energy cost keeps increasing, search for alternative
energies is continued. In the arid regions of the Middle East,
use of solar power has been attempted for quite some time
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to construct medium-sized desalination plants. However, the
production of water seems quite costly due to the high cost
of photovoltaic power. But the price may go down as the size
of the plant increases. Last but not least important, almost
all of the articles deal with the cost of water production.
3.6 FUTURE DIRECTIONS OF THE
RESEARCH AGENDA
Improvement of membrane performance to achieve higher
flux, higher salt rejection, and low energy consumption
simultaneously is still the subject of greatest interest. As is
obvious from this review, enhancement of membrane flux,
while maintaining high salt rejection, has been achieved
primarily by the major industrial RO membrane manufac-
turers by decreasing the skin layer of the PA-TFC mem-
brane. On the other hand, many attempts have been made,
mostly in the academia, to increase the flux by incorporating
nanoscale hydrophilic particles. Another interesting attempt
is to replace the conventional support membrane for in situ
polymerization with a highly porous material such as nano-
fibrous membrane [82]. In all of these attempts, the approach
is based on the improvement of the PA-TFC membrane due
to the latter membrane’s enormous commercial success. But
there may be polymeric materials other than PA to form the
thin surface layer in situ. Moreover, membranes of over-
whelmingly high fluxes may come from totally different
approaches, such as the use of recently developed aquaporin
or carbon nanotubes [83].
Fouling continues to be of great concern for the practical
application of RO membranes, and the development of intrin-
sically fouling-free membranes is the goal of many research-
ers [16]. Surface modification is the most popular approach
to reduce fouling. In this regard, one of the unconventional
approaches of blending SMMs to the host polymer matrix
should be further explored [36–39]. Despite the simplicity of
its process, that is, the requirement of only a small amount
of SMM in one step to modify the membrane surface, the
method has not yet fully taken off, since amphiphilic macro-
molecules of rather exotic structures have so far been used.
The SMMs should be found among the bulk chemicals that
are easily accessible to many laboratories with low cost.
As the modern characterization method advances, the
details of the membrane morphology are being revealed.
The size and size distribution of the water channels can be
measured precisely by the modern instrument, which makes
the water and solute transport theories based on the black
box approach look more obsolete. A new transport model
that matches the advancement of the modern characteriza-
tion method is called for. As well, the precise control of the
water channel size and its distribution, as well as the surface
roughness, is required for the future membrane design.
Regarding the module development, the module size con-
tinues to become larger along with the increase of the plant
size, and currently, there seems no limit for this trend. As the
module size increases, so also do the sizes of pumps, pipes,
etc., and more precise system control will be required.
Hybrid processes are also being considered more seriously
than ever [84]. There are hybrid processes, such as pretreatment
by UF and NF to provide RO feedwater and RO treatment of
boiler water for the distillation process, and those are already
in practice. Combining RO with the emerging membrane sep-
aration processes such as MD and forward osmosis (FO) will
become more important to decrease the amount of effluent
from the RO desalination plant. As drinking water production
by the desalination of seawater and brackish water increases,
increase in the quantity of salty RO effluent will become more
of environmental concern. The RO hybrid process with MD
and FO may become the answer to solve the problem.
3.7 CONCLUSIONS
Many new polymers have been synthesized and tested for
their permeation properties, specifically fouling resistance,
chlorine resistance, thermal and mechanical stabilities, etc.,
aiming at improvement in membrane performance for RO
applications. These efforts seem to continue with insight-
ful vision and a strong commitment for the future. However,
only a handful of polymers are currently being used as mate-
rials for commercial applications, and they are not necessar-
ily the polymers with the best performance properties. This
is mainly due to the cost factor that governs the present mem-
brane market. The RO performance of membranes, on the
other hand, is known to be primarily ruled by the membrane’s
active surface. The surface modification and surface coating
will be focused on the new membrane development tech-
niques in future, as only small amount of polymer is required
for the surface coating. The knowledge of the effects of these
factors on the RO performance will allow for full utilization
of the potential of polymers for membrane materials, which
will open up new promising avenues for further research and
development of the areas.
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