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Separation and Purification Technology 116 (2013) 253–264

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Separation and Purification Technology


journal homepage: www.elsevier.com/locate/seppur

Review

Hybrid ion exchange – Pressure driven membrane processes in water


treatment: A review
Hasan Al Abdulgader a, Victor Kochkodan a, Nidal Hilal a,b,⇑
a
Centre for Water Advanced Technologies and Environmental Research (CWATER), College of Engineering, Swansea University, Swansea SA2 8PP, United Kingdom
b
Masdar Institute of Science and Technology, Abu Dhabi, United Arab Emirates

a r t i c l e i n f o a b s t r a c t

Article history: Over the last decades, the tightening of water quality regulations and the increased attention given to
Received 7 December 2012 trace contaminants in water has been favouring the emergence of novel treatment technologies in order
Received in revised form 29 May 2013 to upgrade or improve conventional water treatment processes. This review surveys recent studies on
Accepted 30 May 2013
using combined ion exchange (IX) and pressure driven membrane processes (microfiltration (MF), ultra-
Available online 6 June 2013
filtration (UF), nanofiltration (NF) and reverse osmosis (RO)) in water treatment. It was shown that inter-
est on these hybrid processes has increased substantially in the last years from both industry and
Keywords:
academia due to need for higher efficiency, optimization and cost reduction of water treatment processes.
Hybrid processes
Water treatment
The studies on using of hybrid IX-pressure driven membrane processes for prevention of membrane foul-
Ion exchange ing, selective removal of targeted pollutants, treatment of waste waters and desalination of brackish/sea
Reverse osmosis water have been critically analysed. It was shown that in some cases the combination of ion exchange
Nanofiltration resins (IXR) with MF, UF, NF and RO has a pronounced synergetic effect in creation of efficient and
Ultrafiltration cost-effective technologies for water treatment. For example, RO-IXR treatment may be regarded as a
standard technology for boron removal from RO permeate during seawater desalination. Hybrid IX-mem-
brane processes also seem as promising solutions for prevention of membrane scaling/fouling, reduction
of desalination costs, treatment of new types of waste waters such as produced waters from unconven-
tional gas resources. However, further research including long-term operability, feed-specific and eco-
nomical life-cycle analysis should be conducted to evaluate the feasibility of these hybrid processes for
various potential applications in water treatment.
Ó 2013 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 254
2. Hybrid IX-pressure driven membrane processes in water treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 254
2.1. Prevention of membrane fouling with NOM and other organic pollutants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 254
2.2. Use of hybrid IX-membrane processes for selective removal of water pollutants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 257
2.2.1. Selective removal of boron . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 257
2.2.2. Selective removal of heavy metals and oxyanions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 259
2.3. Using of hybrid IX-membrane processes for waste waters treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 259
2.4. Using of hybrid IX-RO/NF processes for desalination of brackish/sea water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 260
3. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 263
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 263
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 263

Abbreviations: AXR, anion exchange resin; BDC, brine disposal cost; BSR, boron selective resins; COD, chemical oxygen demand; CSF, coagulation, sedimentation and rapid
sand filtration; CXR, cation exchange resin; DOC, dissolved organic carbon; DOM, dissolved organic matters; ECSF, enhanced flash mix coagulation, sedimentation and rapid
sand filtration; FNU, formazin nephelometric units; IX, ion exchange; IXR, ion exchange resins; MIEX, magnetic ion exchange resin; MF, microfiltration; NF, nanofiltration;
NOM, natural organic matter; PRO, primary reverse osmosis stage; PSf, polysulfone; RO, reverse osmosis; SRO, secondary reverse osmosis stage; TDS, total dissolved solids;
TRO, tertiary reverse osmosis stage; TSS, total suspended solids; UF, ultrafiltration.
⇑ Corresponding author.
E-mail address: n.hilal@swansea.ac.uk (N. Hilal).

1383-5866/$ - see front matter Ó 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.seppur.2013.05.052
254 H.A. Abdulgader et al. / Separation and Purification Technology 116 (2013) 253–264

1. Introduction (NOM) removal and fouling [18,19]. Mozia [20] thoroughly re-
viewed research on hybrid photocatalytic membrane reactors in
The world population is over seven billions and estimated to water and waste water treatment, while work on combined coag-
reach ten billions in 2040 [1]. This increase in the population has ulation and UF/MF may be found in studies [21,22]. It should be
been met with an even more dramatic rise in water consumption, noted that, in certain processes, IXR features such as a possibility
mostly from developing countries [2,3]. Although over 70% of of selective removal of some targeted pollutants from water, pre-
earth’s surface is covered with water, less than 0.3% is available vention of inorganic membrane scaling and possible regeneration
as fresh water (e.g. rivers and lakes). Around 90% of Earth’s water offer an advantage over sorption–membrane technologies based
is in the form of salty water [4]. In order to avoid possible global on using of activated carbon or other sorbents.
crises due to depleting available resources of clean and potable The first studies on hybrid IX-RO processes to soften feed water
water, the need is inevitable to maximise the treatment of waste- prior to RO membranes and then to use the RO retentate to regen-
water, minimise the discharge from water treatment plants, and erate an IXR column were published in the 1970s and 1980s
tap into the virtually unlimited available salty water in the oceans. [23–25], however they were not widely adopted at that time. As
Humans, thousands of years ago, tried and succeeded in improving seen from the literature, nowadays, interest on hybrid IX-pressure
the quality of potable water through technologies such as strain- driven membrane processes of water treatment is greatly renewed
ing, boiling, filtering through charcoal and use of chemical alum both from industry and academia [26–36]. The main factors
to separate suspended solids from water [5]. During the last cen- responsible for that include: (i) the current very strict regulations
tury various water treatment technologies including adsorption, of water quality, (ii) the problems of membrane brine disposal
coagulation, flotation, ozonation, ion exchange (IX), and pressure [37], (iii) the increased attention given to so called ‘‘emerging pol-
driven membrane processes such as microfiltration (MF), ultrafil- lutants’’, which have been identified in surface water and in drink-
tration (UF), nanofiltration (NF) and reverse osmosis (RO) have ing water and are poorly removed by conventional methods of
been thoroughly investigated for surface water and waste water water treatment [38], (iv) the introduction of new efficient IXR
treatment [6–8]. [39], and (v) new ecological challenges coupled with a huge
Over the last decades, the tightening of water quality regula- amount of new waste waters such as produced water from uncon-
tions and the increased attention given to trace contaminants in ventional gas resources. This review for the first time surveys the
surface water and drinking water has been favouring the emer- studies on using combined IX and pressure driven membrane pro-
gence of alternative treatment technologies in order to upgrade cesses in water treatment, including purification of surface water
or improve conventional water treatment processes. and waste water, and desalination of sea and brackish water.
In this paper we are focusing on the combined use of ion ex-
change resins (IXR) and pressure driven membrane processes in
water treatment. IX is based on the phenomenon of exchanging 2. Hybrid IX-pressure driven membrane processes in water
same charge ions between a medium and an electrolyte solution. treatment
The medium can be a resin which is usually made of a complex
crosslinked polymer matrix [6,7]. IXR have been widely used for The interest on hybrid processes in water treatment are mainly
water softening and production of ultrapure water [9,10]. Advanta- stimulated by the need for higher quality of purified water, overall
ges of IXR include simplicity of operation and the fact that there is optimization of the treatment process and cost reduction (Fig. 1).
no energy need for the exchange phenomenon to occur, while the According to literature, studies on hybrid IX-pressure driven mem-
limitations of IXR are restricted resin exchange capacity and con- brane processes are focused mainly on prevention of membrane
sumption of chemicals for regeneration [11,12]. Currently MF, UF, fouling during water treatment, selective removal of targeted pol-
NF and RO are widely used for treatment of surface and waste lutants, treatment of waste waters and desalination of brackish
water, including desalination of brackish and sea water [13]. How- and sea water.
ever, one of the main problems arising upon the operation of
membrane units is membrane fouling, which seriously hinders 2.1. Prevention of membrane fouling with NOM and other organic
the application of this technology [14]. Moreover, RO, which is re- pollutants
garded as one of the most attractive methods for water desalina-
tion, is hampered by a high energy consumption [15]. Therefore The majority of studies on hybrid IX-MF/UF processes for water
a search for new approaches to overcome or at least minimise treatment have been focused on prevention of membrane fouling
these drawbacks is of a special interest. Among these approaches by NOM and other organic substances [31–35,40–44]. Fouling of
are, so called hybrid membrane processes. In the mid-90s, hybrid membranes by organic compounds is a significant issue affecting
membrane processes were described as processes where ‘‘one or the efficiency of membrane filtration in both potable and waste
more membrane process is coupled with another unit process such water treatment systems. General approaches to reduce fouling in-
as adsorption, ion exchange, coagulation, bioconversion, and catal- clude careful membrane material selection and appropriate feed
ysis’’ [16]. In the last years, the interest on hybrid processes has in- pretreatment. The most common pretreatment targeting NOM is
creased substantially and is derived by the need for overall process coagulation/flocculation followed by either traditional rapid sand
optimization and/or cost reduction. Often a combination of various filtration or direct filtration, where flocculated water is flowed di-
water treatment technologies is required to provide high level of rectly onto the membrane, forming a porous, low density cake on
water treatment and purification. the surface that is easily removed by scouring or backwashing
The recent scientific literature mostly focuses on the combina- [45,46]. Coagulation/flocculation preferentially removes high
tion of low pressure membrane processes such as MF and UF with molecular weight NOM [47] but in many cases, conventional
adsorption, coagulation and photocatalysis. For example a compre- clarification is not sufficient to achieve dissolved organic matter
hensive review on hybrid membrane processes using activated (DOM) values lower than 2 mgC/L, which is the reference guideline
carbon for drinking water treatment was published recently by in the EU [48]. Among the possible alternatives to coagulation/floc-
Stoquart et al. [17]. Another interesting hybrid adsorption–mem- culation for NOM removal several studies at the end of the 1970s
brane process, led by Benjamin and others, includes the deposition highlighted the strong potential of anion exchange resins (AXR)
of metal oxide particles on membrane surface to enhance the and found that AXR outperformed activated carbon [49] and non-
membrane’s performance in terms of natural organic matter ionic resins [50]. The high efficiency of IXR for the reduction of
H.A. Abdulgader et al. / Separation and Purification Technology 116 (2013) 253–264 255

Ion exchange resins

(IXR)

• Enhance filtration performance


Potential outcomes • Consistent water quality
include • Reduction in discharge amount
• Cost reduction of produced water

Pressure driven
membrane processes

Fig. 1. Potential benefits of hybrid IX-pressure driven membrane processes in water treatment.

DOM have been also reported recently in many studies [39,47,51] be removed with higher efficiency by AXR treatment than by
and is used in hybrid IX-MF/UF processes for the reduction of clarification.
membrane fouling. It should be noted that combinations of powder It should be mentioned that the high DOC reductions performed
activated carbon with UF or MF might be also used for reducing by AXR treatment allow a significant reduction of the coagulant
membrane fouling with NOM [52]. However, the possible regener- doses (by a factor of 6) with no significant impact on the quality
ation of AXR offers an advantage compared to activated carbon. of the produced water in terms of NOM removal and membrane
A recent technology developed specifically for the removal of fouling properties (Fig. 2).
NOM is the patented magnetic IXR (MIEX) process [53,54]. This Recently, Humbert et al. [48] used a combined AXR/UF process
process utilises a strong base AXR, incorporating magnetic iron for the polishing treatment of a high DOC content (from 7.5 to
oxide particles within its core, which is applied to raw water utilis- 9.7 mgC/L) surface water from the Cébron drinking water treat-
ing a stirred contactor. The small resin beads facilitate rapid reac- ment plant in France. The experiments were conducted with
tion whilst the magnetic component allows separation and fractions of a strong base styrenic AXR of different particle size
recycling of the resin in a continuous process. This differs from (50–500 lm). It was shown that both resin dose and bead size
other more traditional applications where IXR is applied as the fi- had a significant impact on the kinetic removal of DOC for short
nal polishing step within a filter [55]. The first MIEX plant was
commissioned at Mt Pleasant in South Australia in August 2001
[34]. This plant has been divided into two streams of 1.25 ML/d
capacity, each incorporating the MIEX process but the plant also
enables comparison of two separate subsequent processes for the
removal of suspended matter by the conventional treatment (com-
prising coagulation, flocculation, sedimentation, and filtration) and
submerged MF. The operation of this plant over a 2 year period
showed that using of MIEX resin as a pretreatment to MF or con-
ventional coagulation treatment produced water with lower dis-
solved organic carbon (DOC) concentration and lower specific UV
absorbance over the entire period of study. The processes incorpo-
rating MIEX also produced more consistent water quality and were
less affected by changes in the concentration and character of the
raw water DOC. This would make treatment plants that utilise
MIEX easier to operate and maintain good quality water even when
subjected to large variations in the raw water DOC concentration
and character [34].
Humbert et al. [40] used Amberlites IRA958 and MIEX, both are
AXR, prior to UF membranes (regenerated cellulose with molecular
weight cut off of 100 kDa) for the removal of DOM from surface
water [40]. MIEX was chosen due to its high capabilities in remov-
ing negatively charged NOM, particularly humic acids and fulvic
acids [56]. The obtained results showed that both resins were able
to remove up to 80% of DOC from Villejean raw water in less than
an hour of operation. Although AXR treatment was shown to be
very effective in reducing DOC content, both MIEX and IRA958 res-
ins had no impact on the reduction of reversible membrane foul-
ing. It was assumed that high molecular weight compounds of
microbial origin (polysaccharides, amino sugars and proteins) con-
tribute, to a large extent, to UF membrane fouling (reversible foul-
ing) whereas these foulants only contributed 10% of the total DOC
content in the raw water. These organic compounds were largely
removed by clarification but are mainly refractory to AXR treat-
ment probably because of their size (exclusion from the resin Fig. 2. (a) DOC content and ultraviolet adsorption at 254 nm (UV254) of the raw
pores) and their neutral and/or hydrophilic character. On the con- water and waters treated by coagulation/flocculation and IXR (MIEXs or IRA958s)
used either alone or combined. (b) DOC content of MIEX-treated water clarified
trary, the low molecular weight fraction of NOM, which is mainly with coagulant doses ranging from a dose d (the one applied at the water treatment
responsible for the irreversible membrane fouling, were found to plant) to d/6 [40].
256 H.A. Abdulgader et al. / Separation and Purification Technology 116 (2013) 253–264

contact times (<15 min). For resin doses higher than 700 mg/L and Remarkably, the proposed hybrid process essentially reduces
median bead sizes below 250 lm DOC removal remained constant the produced waste. Regenerating the resin after it only adsorbed
for a 30 min of contact time with about 80% and 40% removal a small fraction of its total capacity leads to lower salt concentra-
yields on DOC for raw and clarified (after coagulation–floculation) tions for the regeneration fluid. This fluid is then treated by biolog-
water. These removal values with the hybrid AXR-UF process are ical denitrification and NF to re-use about 80% of the sodium
much higher than that of UF alone (3% DOC removal). It should chloride. The NF retentate, which is 20% of the regeneration fluid
be noted that some increase of reversible membrane fouling was volume, is treated with dynamic vapour recompression to lower
observed in the presence of AXR because of the attrition of the re- this volume down to 1% or less. Based on SIX™-Ceramac™ process
sin by the use of centrifugal pump in the external loop. However a new treatment facility with a capacity of 5000 m3/h, for direct
due to efficient DOC removal by the hybrid process, the irreversible production of drinking water from IJsset Lake (The Netherlands)
membrane fouling was reduced by 15–20% compared to UF alone. will put into operation in 2013 [57].
Cornelissen et al. [41] used two fluidised columns containing Kim and Dempsey [42] studied the effect of using AXR to pre-
cation exchange resins CXR and AXR, prior to UF membrane, for treat wastewater effluent (tertiary-treated wastewater effluent
the reduction of hardness and NOM content in surface water that from an aeration tank) and reduce organic matter fouling in both
was taken from Amsterdam-Rhine Canal in the Netherlands. Fluid- MF and UF. They tested a non-ionic macroporous resin DAX-8
ised Purolite A860L, a strong base macroporous type I AXR, was (Supelco), and three types of AXRs: a strong base macroporous
able to continuously remove 60% of NOM in surface water for IRA-958 (Rohm and Haas), a pre-swollen weak base gel resin DEAE
1 month of operation and without the need of regeneration. In (Whatman International), and a strong base MIEX resin (Orica
the first 5 days a high NOM removal was observed of 80–90%. After Watercare). The authors claimed that DEAE and MIEX resins man-
this, the NOM removal decreased and stabilised at 60%. Fluidised aged successfully to remove organic foulants from the wastewater
Purolite C104E FL, which is a weak acid polyacrylic CXR, managed effluent and prevent almost all fouling in both MF polyvinylidene
to remove 80% of calcium and 40% of magnesium from feed for fluoride and UF polyethersulfone membranes (Fig. 4). DAX-8 and
3 days operation. It was shown that IXR pretreatment lowered IRA-958 resins, however, were only able to partially remove organ-
the level of irreversible fouling in the subsequent UF unit. This ic compounds from the feed and therefore only partially reduced
was due to, as suggested by the authors, the decreasing feed con- the membrane fouling. The IRA-958s partial removal of organic
tent of calcium and magnesium ions, which caused a change in acids was attributed to competition between organic and inorganic
NOM structure from compact coiled to open linear structure. As anions of the resin’s exchange sites.
a result, a fouling layer formed by linear NOM macromolecules Controversial results were reported by Hofs et al. [44], who
was easier to remove from membrane surface by backwashing. studied the effect of AXR pretreatment on fouling of Al2O3 tubular
Recently a new hybrid SIX™-Ceramac™ process based on IXR MF membranes with NOM. The feed surface water was taken from
and MF with ceramic membranes have been developed and suc- Noardburgum Lake in the Netherlands and contained 15.1 mg/L
cessfully commercialised for direct treatment of surface water, DOC and a turbidity of 9.7 FNU. The AXR (Lewatit VPOC 1071)
containing high amount of suspended matter, dissolved organic
carbon and nitrate [57]. In this process, resin is dosed from a dosing
tank into the raw water leading to a low concentration of 4–
15 mL resin/L depending on the raw water quality, desired water
quality and resin type. This mixture is then led to vertically cylin-
drical contactors. After the contactors, the resin is separated and
treated water is sent to a MF stage.
As can be seen in Fig. 3, SIX™-Ceramac™ process provide a
much higher efficiency in DOC and nitrate removal comparing with
both conventional coagulation, sedimentation and rapid sand fil-
tration (CSF) and enhanced flash mix coagulation, sedimentation
and rapid sand filtration (ECSF) during treatment of surface water.
Lanxess Lewatitt VPOC 1071, an acrylic gel anion resin designed for
NOM and colour removal was used for this treatment. The new
water treatment process leads to a superior water quality, reduced
energy consumption, less waste and a smaller carbon footprint.

Fig. 3. Average DOC and nitrate concentration in feed water after different Fig. 4. Fouling resistance of UF (a) and MF membranes (b) during filtration of
treatment [57]. wastewaters after pretreatment with various IXR [42].
H.A. Abdulgader et al. / Separation and Purification Technology 116 (2013) 253–264 257

pretreatment reduced greatly the DOC content, water turbidity and


reversible membrane fouling. However, the remaining foulants,
mostly uncharged high molecular weight NOM, were able to form
a more compact and robust fouling layer on the MF membrane.
This led to an increase in irreversible fouling and as a result an in-
crease in the transmembrane pressure. The data obtained in this
paper also suggest that feed characteristics could greatly affect
the performance of IXR pretreatment.
An interesting approach to minimise membrane fouling using
IXR was proposed by Ochoa et al. [58]. They prepared hybrid UF
polysulfone (PSf) membranes with resins’ particles deposited in
the membranes’ porous structure (Fig. 5) to enhance the mem-
brane fouling resistance and improve the membrane overall per-
formance during treatment of oily water. The hybrid membranes
were prepared through three steps. The first step involved dissolv-
ing PSf and polyvinylpyrrolidone in N,N-dimethylformamide.
DOWEXÒ 50WX8 strongly acidic resin was then added to the poly-
Fig. 6. Normalised flux versus filtration time for PSf membranes prepared at
meric solution. Finally, the solution was cast onto a non-woven
various IXR dosage in casting solutions, %: 0 (PSf); 1 – (PSfC1); 10 – (PSfC10) and 20
support using a film extensor. The experimental results indicated (PSfC20) [58].
a shift in pore size distribution to larger pore sizes as the resin dos-
age in the casting solution increases. This was attributed to the
void spaces created in the polymeric solution due to low adhesion
of seawater [62]. However boron removal with RO membranes are
between resin particles and the polymer matrix during the phase
often insufficient under common RO conditions [63]. In seawater,
inversion process. It was also shown that increasing the resin load-
boron is usually present as boric acid H3BO3. The rejection of
ing in the UF membrane yielded an increase in the membrane foul-
non-ionised boric acid by RO is low due to its smaller size and lack
ing resistance during oily water treatment (Fig. 6). At 20% resin
of electric charge [62]. The membranes available presently for sea-
content, fouling, both reversible and irreversible, was nearly elim-
water desalination remove only 60–90% of the boron in the first
inated due to an increase in electrostatic exclusion between the
pass [64]. Taking into account that seawater contains an average
membrane and foulant particles [59].
of 5 mg/L of boron, the first pass RO permeate would contain be-
tween 1–2 mg/L of boron. This concentration is unacceptable for
2.2. Use of hybrid IX-membrane processes for selective removal of both human consumption and irrigation purposes. The problem
water pollutants of high boron concentration in RO permeate was observed first
after commissioning a SWRO plant in the Middle East in 1997.
During the recent years, increased attention has been given to Farmers using post treated product water for irrigation noticed
trace pollutants found in water which are poorly removed by con- poisoning of crops and partly discoloured leaves. Later, boron
ventional water treatment methods [38]. Therefore, there is a was identified as the toxic element responsible for these effects
strong need to develop novel treatment technologies in order to [65].
upgrade or improve the conventional treatment processes. Post treatment with boron-selective chelating resins (BSR) was
suggested to selectively remove boron from RO permeate
2.2.1. Selective removal of boron [26,62,64,66–68]. This approach is based on the fact that polymers
One of the most promising combined IX-membrane processes is supported iminodipropylene glycol groups are very efficient for
dealing with removal boron from water [29,30,60]. The existence chelation with boric acid and can be used for removal of boric acid
of boron in water, if present at concentration less than 0.3 mg/L, even at trace level [66,69]. Commercial BSR are primary classified
is beneficial for both humans’ consumption and irrigation. How- as macroporous crosslinked polysteric resin, functionalised with
ever, at higher concentration (i.e. above 0.3 mg/L) it can be hazard- N-methyl-D-glucamine groups [70]. These groups capture boron
ous to humans and plant [61]. through a covalent attachment and formation of an internal coor-
In the Middle East and North Africa region a large amount of dination complex as shown in Fig. 7. The borate ion is complexed
drinking water and irrigation water is produced by RO desalination by two hydroxyls and the role of the tertiary amine in the

Fig. 5. SEM cross sections of PSf membrane prepared without (a) and with addition of 20% IXR content (b) in casting solution [58].
258 H.A. Abdulgader et al. / Separation and Purification Technology 116 (2013) 253–264

Table 1
Performance comparison between the double pass RO and the hybrid RO-IXR systems
for boron removal from seawater [64].

Double pass RO Hybrid RO-IXR


RO 1st pass size (m3/d) 121,800 111,900
RO 2nd pass size (m3/d) 48,250 NA
IXR size (m3/d) NA 37,270
Total waste (m3/d) 67,000 61,340
TDS of final product (mg/L) 79 480
Boron content of final product (mg/) 0.48 0.47
By-pass (%) 12 26
Fig. 7. Complexation of BSR with boric acid [70].

functional N-methyl-D-glucamine group is to neutralise the proton aqueous solutions. Later this hybrid BSR-MF process was used for
brought by the formation of tetraborate complex to prevent the de- treatment of geothermal waters containing high level of boron
crease of pH that may results in boron liberating hydrolysis [70]. (8–9 mg/l) [30]. A submerged MF system with polypropylene cap-
Because BSR are highly selective, they remove only boric acid illary membranes with a pore diameter of 0.4 lm was used to sep-
from feed and have no significant effect on the concentration of arate Diaion CRB02 and Dowex XUS-43594.00 resins from the
other ions. Jacob [64] claimed that introduction of BSR for boron solution. It was shown that as the resin size decreased from 45–
removal from RO permeate reduces the overall capital and operat- 125 lm to 0–20 lm, boron removal efficiency improved essen-
ing cost compared to a conventional RO system. Usually to reduce tially due to increased surface area of resin. Fig. 10 represents
boron concentration in RO permeate to an acceptable level, a sec- the effect of suspension concentration on boron removal from geo-
ond RO pass is needed with corresponding increase of energy con- thermal water by Dowex (XUS 43594.00) for a longer period. At a
sumption. Additionally, the second RO pass would operate at high resin concentration of 2 g/L, the boron concentration in treated
pH 10–11 to provide high rejection of ionised boric acid. This in water was less than 0.3 mg B/L which is permissible level of boron
turn requires the use of caustic soda and an antiscalant. As a final in drinking water.
result, the size of RO system becomes very big and the salinity of The sorption kinetic data of boron selective resins showed that
the produced water is lower than necessary. Therefore, Jacob sug- IX-MF hybrid process could be an alternative method to commonly
gested using an IX stage instead of a second pass RO when the used fixed bed column mode operation. BSR remove boron very
salinity of the first pass RO permeate meets the final specification. quickly from the geothermal water due to their large available sur-
This approach shown in Fig. 8 reduces the size of the first RO pass, face areas and high efficiency of the water deboronation process.
and is more flexible in case the boron passage if the RO is higher The hybrid BSR-MF method was also used for polishing boron
than expected, e.g. when membranes are ageing. removal from RO permeate [65,71]. Checking the process parame-
The benefits of the hybrid RO-IX system for sea/brackish water ters, the effect of resin particle size, slurry rate delivery, resin con-
treatment compared to double RO pass include savings of the centration in suspension, and volume of permeate flux was
membrane area in the first RO stage, reduction in total waste and evaluated. Significant reduction of boron concentration in perme-
increase in by-pass volume (Table 1). Currently hybrid RO-IXR ate was observed in the first 15 min of the process. It was con-
treatment may be regarded as a standard technology for boron re- cluded that sorbent particle size largely affected the economics
moval from RO permeate during seawater desalination and a num- of the hybrid BSR-MF membrane system for water treatment.
ber of desalination plants have already installed this process. The However, to optimise the process, a detailed cost analysis should
world’s first desalination plant using a combination of RO and be performed.
IXR for drinking water production was built in 2006 in the Middle There were studies to find out the effect of each experimental
East, and fed with brackish water. The water is used for human parameter on the performance of hybrid BSR-membrane process.
consumption as well as irrigation [64]. Bryjak et al. [71] developed mathematical modelling and investi-
Kabay et al. [60] suggested a hybrid sorption-MF concept using gated the effects of several parameters such as, feed flow rate,
BSR for the removal of boron from water. As is shown in Fig. 9, the BSR suspension concentration, and rate of suspension replacement
process includes following stages: (i) boron sorption by BSR; (ii) on the process efficiency. The simplified equation derived from the
separation of saturated BSR from water on an appropriate semi- boron balance of the system is:
permeable membrane; (iii) splitting (desorption) of the boron
complex with BSR onto free BSR and boron; and (iv) membrane Js
separation of BSR and boron to enable BSR regeneration and recov-
C p ðBÞ ¼ C f ðBÞ  XðoutÞqðoutÞ
Jf
ery. Two commercially available BSR with N-methyl-D-glucamine
ligands namely Diaion CRB02 and Dowex XUS-43594 were used
where Cp(B) is the boron concentration in permeate, Cf(B) is the ini-
for boron binding while MF Teflone Fluropore membrane with a
tial boron concentration, Js is the flux of suspension replacement, Jf
pore diameter of 0.2 lm were used for separation of BSR from
is the feed flux, X(out) is the concentration of solid in the suspension
replaced, and q(out) is the mass of boron in the suspension replaced.
It was found that the developed model acceptably described the
process performance. High boron removal is achieved when feed
flux (Jf) is low, and both the flux of suspension replacement (Js)
and the concentration of BSR (X(out)) are high to achieve high bor-
on removal. It was found that the use of a more concentrated resin
suspension is more effective than increasing the rate of suspension
replacement.
Although the proposed hybrid IXR-MF process seems promising
and managed to remove up to 97–99% of boron in seawater and
Fig. 8. Combination of single pass RO with IX treatment for boron removal from geothermal water, it still lacks a thorough investigation to deter-
seawater [64]. mine whether the treatment can substitute the adopted system
H.A. Abdulgader et al. / Separation and Purification Technology 116 (2013) 253–264 259

Fig. 9. Flow sheet of the hybrid sorption-MF system based on BSR [62].

expensive than nitrate selective resins but cannot effectively re-


move nitrate in the presence of other ions, such as sulphate, that
are more affine to the resin than nitrate. At the first stage, the feed
water was sent to NF membrane for sulphate and NOM removal.
The membrane was able to remove 95% of sulphate. NF permeate,
almost free from sulphate ions, was sent to a conventional AXR for
nitrate removal. The overall hybrid process performed well with up
to 97% nitrate removal and 90% water recovery.

2.3. Using of hybrid IX-membrane processes for waste waters


treatment

The rapid expansion of shale gas production over the world has
raised serious environmental concerns about the large amount of
‘‘flowback water’’ during shale gas drilling. During hydraulic frac-
turing, about 2–5 million gallons of hydrofracture water, a mixture
of water and chemical additives, is pumped into the gas bearing
formation. After hydraulic fracturing, about 10–40% of the hydro-
Fig. 10. Effect of suspension concentration on boron removal versus time using fracture water will return to the surface as ‘‘flowback water’’,
hybrid BSR-MF system [30]. depending on the geology and geomechanics of the formation
[73,74]. Flowback water from shale gas well drilling has a high
TDS (total dissolved solids) content, ranging from 5000 ppm to
in practice. Essential but unexplored areas of interest include resin
261,000 ppm, along with a TSS (total suspended solids) content
regeneration mechanism and cost evaluation of the new process.
of 300–3000 mg/L [74]. Therefore, on-site treatment of flowback
water is becoming a paramount ecological problem to meet strict
2.2.2. Selective removal of heavy metals and oxyanions regulatory standards prior to release this water into the
Ritchie and Bhattacharyya [72] used a hybrid NF-IXR system to environment.
effectively remove heavy metals and oxyanions from ground water Very recently Jiang et al. [75] suggested a hybrid process based
in the presence of interfering non-toxic ions, such as calcium, mag- on ceramic membranes filtration and IXR for the treatment of the
nesium, and sulphate. Possible treatments for this type of water in- flowback water from Marcellus Formation, the largest shale gas
clude IXR, RO and NF, but all these processes have their own formation in the world. The process combined filtration with cera-
limitations. IXR cannot effectively remove all toxic ions due to mic membranes, 1.4 lm and 0.2 lm of pore size respectively, and
exchange competition from other ions present in water, particu- mixed bed IXR stage. Both membrane and IXR stages are suitable
larly when the concentrations of theses ions are much higher than for on-site treatment due to their small footprint. DOWEX G-26
that of the toxic ones. RO membranes can reject almost all ions in resin (DOW, USA) with a mean diameter of 0.6 mm and Marathon
water. However they cannot selectively remove toxic ions and sep- A resin (DOW, USA) with a mean diameter of 0.5 mm were employed
arate them from other desired ionic species. NF membranes, on the as CXR and AXR respectively. The ceramic membrane contained a
other hand, allow some selective separation and they consume less ZrO2 separating layer deposited on a porous a-Al2O3 support.
energy than RO membranes. However, they are not able to reject After the membrane treatment to remove TSS and turbidity, the
all toxic species to appropriate levels. The authors [72] examined flowback water was pumped through the IXR mixed bed column at
the benefit of combining various separation technologies to a flow rate of 20 mL/min to reduce TDS and conductivity of the
achieve enhanced, selective and efficient removal of toxic species. treated water.
One case they studied was the removal of nitrate from sulphate As seen in Table 2 all TSS and >99% of TDS were successfully
rich waters using a hybrid NF-IX process. The utilisation of NF for removed from the flowback water to meet the criteria for surface
divalent ions removal permitted the use of conventional IXR in- discharge. In particular, the conductivity of the treated water was
stead of a nitrate selective one. Conventional IXRs are less 54 ls/cm, less than 1% of the raw flowback water. The Na+ and
260 H.A. Abdulgader et al. / Separation and Purification Technology 116 (2013) 253–264

Cl contents were reduced to 3.7 mg/L and 7.5 mg/L, respectively. oil. So, the payback period of the system was about 1 year which is
Other ionic species, such as Ba2+, Mg2+ were lowered to ppm level. very attractive.
TOC of the treated water was 82 mg/L, indicating that about 90% Hybrid IX-pressure driven membrane processes did not always
TOC was removed by the hybrid treatment. result in a more efficient treatment of waste waters. According to
The estimated total cost for flowback water treatment based on Singh et al. [78], landfill leachate pretreatment using IXR/coagula-
hybrid MF-IXR system is approximately $18.4/m3, which is about tion did not improve the permeate flux of subsequent RO and NF
10–25 times higher than the cost of seawater desalination treat- membranes, compared to no pretreatment. They attributed this re-
ment, but it is 40–70% lower than the cost estimate of the Depart- sult to changes in the RO/NF feed characteristics and membrane
ment of Environmental Protection in Pennsylvania, USA to treat surface properties due to continuous pH increase in the pretreated
flowback water from the natural gas industry. leachate. At high pH the precipitation of carbonate on membrane
However, it was shown that hybrid process is not well suited for surface could have caused greater permeate flux decline than with-
treating highly concentrated flowback water due to sharp increase out IXR pretreatment.
of the costs. When treating the flowback water with a TDS of
186,000 mg/L, the process cost increases to 64$/m3, four times as 2.4. Using of hybrid IX-RO/NF processes for desalination of brackish/
much as the process cost of treating the flowback water with a sea water
TDS of 48,000 mg/l mainly due to an increase of required resin
quantity and resin regeneration costs. The main motivation of hybrid IXR-RO/NF processes for treating
Murray-Gulde et al. [76] recommended a hybrid IX-RO system both brackish and sea water is prevention of membrane scaling
to treat produced water from oil production for irrigation or dis- and the reduction of the overall desalination costs [79]. Currently
charge purposes. Produced water refers to the water found in desalination of seawater and brackish water by RO has gained
underground oil reservoir. The water, after being separated from great significance particularly for potable water production. Unfor-
oil, was first passed through a series of conventional filtration med- tunately membrane scaling constrains the operation of RO units at
ia to remove suspended particles. Then, a CXR was introduced prior high water recovery. Scale formation at the membrane surface re-
to RO for water softening and hence prevent scaling on the surface sults from the increased concentration of one or more inorganic
of the RO membranes. The conductivity of the product was low- salts beyond their solubility limits and their ultimate precipitation
ered by 95% and the TDS by 94%. on the membranes [80]. Scaling usually refers to the formation of
Lin and Lan [77] employed a hybrid UF-IXR process to treat deposits of inverse-solubility salts such as CaCO3, CaSO4xH2O
waste oil/water emulsion used in the cable and wire industry. At and Ca3(PO4)2. The species with the greatest scaling potential in
the first stage of the process, UF Amicon YM30, Amicon YM100 RO and NF membranes are CaCO3 and CaSO42H2O, while other po-
and Amicon PM30 membranes were used for partial removal of tential scaling compounds include BaSO4, SrSO4, Ca3(PO4)2 and
copper and reduction of COD content in the feed. The UF stage Fe(OH)3 [81]. Membrane scaling causes permeate flux decline
was followed by a cationic exchange stage with H-type Ambersep and loss of product quality. To avoid scaling, one can operate the
132 CXR to reduce the UF permeate conductivity and a following RO process at low recovery (below the solubility limit of salts).
AXR treatment with OH-type Ambersep 900 resin for further However, operating at higher recovery is more beneficial as less
reduction of COD in the UF permeate. The IX process was tested feedwater is required, and less brine needs to be disposed. Minimi-
in two different modes, mixed and in sequence. The mixed mode zation of brine is essential nowadays due to more strict environ-
consisted of mixing cationic and anionic resins in a tank filled with mental legislations, especially for many inland locations that do
permeate from the UF unit. The second mode entailed two separate not have access to low cost environmentally acceptable disposal
CXR and AXR columns used in sequence to treat the UF permeate. methods [82]. The problem of scaling can be alleviated by pretreat-
The experimental results showed both modes, with total resin to ing the water with antiscalants before it is sent to RO membranes.
permeate ratio of 1:20 or less, provide good consistent water qual- However, even with the use of antiscalants, the problem of scaling
ity which permit direct discharge or reuse. The investigators sug- is not mitigated completely. Rahardianto et al. [82] have demon-
gested that if the sequence mode is used, the CXR needs to strated that RO desalination of Colorado River water at high recov-
precede the AXR for better overall performance. Preliminary cost ery levels of 96% resulted in 40% flux decline over a 24-h period,
assessment showed the cost of the proposed hybrid process was even with the use of antiscalants. There is still a need for robust
approximately equals to the annual disposal cost of waste drawing pretreatment techniques which would handle the problem of min-
eral scaling in RO desalination of brackish waters and allow the RO
process to operate at high recovery.
Table 2 In the 1970s–1980s Vermeulen and coworkers [23,25] have
Composition of raw flowback water and water after hybrid MF-IX treatment [75]. shown that pretreatment with an IX unit that was regenerated
Constituent Raw flowback water After IX treatment with concentrated brine from the RO unit would alleviate mem-
TOC (mg/L) 720 82
brane scaling. After undergoing filtration to remove suspended sol-
TSS (mg/L) 881 0 ids, chlorination for disinfection, precipitation with polyvalent
pH 6.85 6.91 metal hydroxides to remove silica and dechlorination with sodium
Conductivity (ls/cm) 67,000 54 bisulfite (NaHSO3) for membrane protection, brackish water was
Na (mg/L) 12,200 3.7
fed to the IXR column. The total ionic concentration of the brackish
K (mg/L) 363 <0.5
Mg (mg/L) 104 <0.05 feed is typically in the range of 0.1 eq/L–0.4 eq/L. At these concen-
Ca (mg/L) 2935 <0.1 trations, the equilibrium isotherm is favourable for the transfer of
Ba (mg/L) 697 <0.05 Ca2+ and Mg2+ from the solution to a Na+ form resin [7]. The eluent
Sr (mg/L) 591 <0.05 from IXR was pressurised and sent to RO to produce pure water
Al (mg/L) 105 <0.05
Fe (mg/L) <1 <1
and high pressure concentrated brine (retentate). Replacement of
Mn (mg/L) <2 <0.05 Ca2+ and Mg2+ ions with Na+ ions in feed water reduces membrane
Cl (mg/L) 28,500 7.5 scaling at high recoveries. The brine, which is concentrated in Na+,
Br (mg/L) 19 <0.01 was used to regenerate the IXR column and to displace the Ca2+
F (mg/L) <1 <0.01
and Mg2+ present on the resin. However, because of insufficient
SO4 (mg/L) 12.9 <0.05
membrane rejection, retentate had to be supplemented with
H.A. Abdulgader et al. / Separation and Purification Technology 116 (2013) 253–264 261

of brine corresponding to one softening step can regenerate the


ion exchange bed sufficiently to make the process self-sustaining.
No additional chemicals are required to regenerate the IXR; thus,
eliminating a major operating cost of any IXR unit. They also dem-
onstrated that brine disposal cost is an important factor which
influence optimum RO configuration. As seen in Fig. 11, without
pretreatment RO cannot be operated at recoveries >35% for Ca2+
rich feed, while IXR pretreatment allows operation at recoveries
as high as 90%. At high recoveries much less brine is produced,
and the brine disposal cost has little impact on the product water
cost. If the costs associated with feed water are included then oper-
ation of the system at higher recoveries will be even more
advantageous.
Based on these results, a high water recovery hybrid IXR-RO
process (without antiscalants) was designed and simulated for
Fig. 11. Product water cost for high Ca2+ feed 12,000 ppm, BDC:brine disposal cost desalination of Colorado River water (TDS = 941 mg/L) at the
[90]. capacity of 96 Mgpd [83]. Fig. 12 illustrates a schematic drawing
of the process. The feed with TDS of 941 mg/L was sent to a pri-
mary reverse osmosis (PRO) stage at 75% recovery and without
purchased salt to achieve sufficient regeneration of the IXR column precipitation of Mg2+, Ca2+ or SiO2. The reject from PRO membranes
[24] and the process was not widely adopted at that time. was fed to a CXR column in Na+ form for softening. Scale causing
Recently Venkatesan and Wankat [36] re-examined this pro- substances like Ca2+, Mg2+ and Ba2+ were removed at this stage.
cess. They have simulated the IXR pretreatment for Ca2+ rich and The breakthrough curves for these substances are shown in
Ca2+ poor brackish water of TDS 5000–15,000 ppm and have done Fig. 13. Due to differences in the ions affinities to the resin, the
a detailed cost analysis where brine disposal cost and equipment breakthrough point of Mg2+ occurred earlier than that of Ca2+.
installation cost were taken into account. They showed that when The breakthrough curve for barium is more complex. The initial in-
membranes with high rejection coefficients are used, the amount cline in barium concentration, noticed in Fig. 13b, is attributed to

Fig. 12. Diagram of a hybrid IX-RO process for desalination of Colorado River water [83].

Fig. 13. The IX breakthrough curves of CXR in Na+ form for Ca2+ and Mg2+ (a) and for Ba2+ (b) ions. The feed contained Ca2+, Mg2+ and Ba2+ with concentration of 95, 34.5 and
0.1 mg/L, respectively [83].
262 H.A. Abdulgader et al. / Separation and Purification Technology 116 (2013) 253–264

high energy consumption [84]. Typically energy inputs can account


for around 44% of the total water costs of a RO plant [85]. Therefore
the development of a technology capable of producing fresh water
by desalting brackish and/or seawater at the lowest possible cost is
of crucial importance. In this connection, Sarkar and SenGupta [86]
suggested the use of a hybrid IXR-NF process as a potential tech-
nology for seawater desalination. The concept is based on the pre-
mise that the pressure-driven membrane desalination process can
be carried out by replacing the more energy-consuming RO mem-
branes with more energy-efficient NF membranes coupled with an
IX unit. Through IX, monovalent chloride ions of salt water are con-
verted into divalent sulphate ions, which are efficiently rejected by
NF membranes. To remove chloride ions from model feed, con-
tained 560 meq/L of Cl, water was passed through a column filled
with Purolite A-850 AXR in a sulphate form. Breakthrough curves
of sulphate and chloride ions are shown in Fig. 14. The authors
Fig. 14. Breakthrough curves of chloride and sulphate ions with g Purolite A-850 attributed the sharpness of the curves to the insignificant resis-
resin with a feed water containing 560 meq/L Cl (corresponds to approximately tances from liquid phase film and intra-particle diffusion. The salt
32 g/L NaCl). [86]. in the AXR permeate was predominantly in the form of Na2SO4.
This water was fed to an NF membrane where the Na2SO4 salt
desorption of some barium ions affected by high concentrations of can sufficiently be retained. The authors also suggested the use
Ca2+ and Mg2+ ions. The fall of barium concentration after its peak of the NF concentrate to regenerate the AXR when it became satu-
was credited to its high selectivity to the resin compared to both rated with chloride ions. Schematic diagram of the proposed pro-
calcium and magnesium. IXR column managed to remove 99.9% cess is illustrated in Fig. 15. The process consists of three main
of barium and calcium and 97% of magnesium. The softened water steps: (1) Chloride removal by AXR in sulphate form, (2) sulphate
from the IXR column was then pressurised and sent to a secondary removal by NF membrane and (3) regeneration of the resin using
reverse osmosis (SRO) stage. The SRO system was run slightly be- NF retentate. This approach seems very attractive because an
low its recovery limit, 63%, at which precipitation of silica occurs. incorporation of an IX stage in an IXR-NF desalination process
To prevent the problem of silica scaling, pH adjustment and heat- might create a synergy that allows membrane desalination at sig-
ing of the concentrate from SRO was done before it is sent to an op- nificantly lower transmembrane pressure compared with RO and
tional Tertiary RO (TRO). The IX treatment helped to remove the thus will sharply reduce the required energy for water
scale causing precursors like Ba2+, Ca2+ and Mg2+ while pH adjust- desalination.
ment and heating partially alleviated the problem of silica scaling IX post-treatment can also be used to completely demineralise
allowing a maximum recovery of 96.4% with the PRO-IXR-SRO- the RO permeate [87–89]. Fendri et al. [89] tested several conven-
Heat-TRO sequence. Use of TRO concentrate for IXR regeneration tional and nonconventional demineralisation technologies includ-
eliminates need for regeneration chemicals. ing a combined double stage RO and mixed bed IXR treatment. In
Optimal process schemes were identified for different brine dis- their system, two Filmtech membranes, namely BW30LE-440 and
posal costs. Reductions in product water cost of 75% and 50% were BW30-400, were used in the first and second stage, respectively.
attained at high and low brine disposal costs, respectively; how- The concentrate from the second stage was recycled and mixed
ever a detailed economic analysis is essentially needed to confirm with the first stage feed (Black Sea water). The second stage perme-
feasibility of this hybrid process. ate, with a TDS of 9 mg/dm3, was fed to a mixed bed IXR. The
Despite the fact that RO is currently regarded as one of the most mixed bed contained a strong CXR (Dowex Monoshpere 650C)
attractive methods for water desalination, it is still hampered by and a strong AXR (Dowex Monosphere 550A). TDS of the product

Fig. 15. Schematic diagram of a hybrid IX-NF process for water desalination [86].
H.A. Abdulgader et al. / Separation and Purification Technology 116 (2013) 253–264 263

after IXR treatment did not exceed 0.019 mg/dm3. The final prod- resin and cost of regenerant used. So, it is of major interest to find
uct was intended to be used in a power production industry. The ways to reduce the frequency of regeneration and most impor-
authors noted that the use of this hybrid system would lower the tantly reduce or eliminate the cost of the regenerant. The latter
operation costs by up to 28% compared with a conventional high can possibly be achieved, in certain applications, though utilisation
density RO membrane system. of the membrane brine to regenerate the IXR.
Finally, it may be concluded that despite the fact that many ef-
forts are still needed to provide a future progress in hybrid IXR-
3. Conclusion pressure driven membrane processes, nevertheless, the potential
of these processes in tackling current challenges in water treat-
The use of hybrid IX-pressure driven membrane processes for ment will undoubtedly facilitate the development of modern
water treatment has been the topic of many investigations. More highly effective water treatment technologies.
than 60 publications were found on the subject in the scientific lit-
erature over the last few decades. The potential advantages of
these hybrid processes are enhanced produced water quality, bet- Acknowledgements
ter performance of water treatment processes, and/or reduced pro-
duction cost. In some cases the combination of IXR with MF, UF, NF The authors would like to thank the College of Engineering at
and RO has a pronounced synergetic effect in creation of efficient King Faisal University (KFU) in Al-Ahsa, Saudi Arabia for funding
and cost-effective water treatment technologies. For example, hy- the work of Mr. Hasan Al Abdulgader.
brid RO-IXR treatment may be regarded as standard technology for
boron removal from RO permeate during seawater desalination
and a number of desalination plants have already been installed References
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