Contents lists available at ScienceDirect

Colloids and Surfaces A: Physicochemical and

Engineering Aspects
Aspects 444 (2014) 338–344

Review

Removal technology of boron dissolved in aqueous solutions – A

review
∗
Boyang Wang, Xianghai Guo, Peng Bai
School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China

h i g h l i g h t s g r a p h i c a l a b s t r a c t

• Introduce importance and relevant

problem of boron.
• Update study on removal of boron
dissolved in water.
• Present solutions for boron
pollution.

a b s t r a c t
a r t i c l e i n fo

Article history: Boron is an essential micronutrient for plants, humans and animals, which is also an important
Received 17 August 2013
component used in various industries. Along with the wide spread of boron application, more and
Accepted 25 December 2013
more boron waste pollutes the drinking water sources, and leads to a series of environment and health
Available online 8 January
2014 problems. This paper reviews the reported boron removal technology from aqueous solutions,
including adsorption process, membrane process, hybrid process and other methods, presenting
available choices to solve the problem of boron pollution.
Keywords:
Boron removal © 2014 Elsevier B.V. All rights reserved.
Adsorption
Membrane
Hybrid process
Aqueous solution

Contents

1. Introduction............................................................................................................................................................................................................................ 339
1.1. Importance of boron..............................................................................................................................................................................................................339
1.2. Uses of boron and related problems..................................................................................................................................................................................339
1.3. Chemistry of boron in aqueous solutions..........................................................................................................................................................................339
2. Adsorption process for boron removal..........................................................................................................................................................................................339
2.1. Chelating resin mechanism...................................................................................................................................................................................... 339
2.2. Other absorbents........................................................................................................................................................................................................ 340
3. Membrane process for boron removal............................................................................................................................................................................................341
3.1. Ion-exchange membranes (IEM) method..........................................................................................................................................................................341
3.2. Reverse osmosis (RO) method.............................................................................................................................................................................................342
3.3. Electrocoagulation (EC) method.........................................................................................................................................................................................342
 ∗ Corresponding author. Tel.: +86 22 27406186; fax: +86 22 27403389.

E-mail address: chemeng114 tju@163.com (P. Bai).

0927-7757/$ – see front matter © 2014 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.colsurfa.2013.12.049
 B. Wang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 444 (2014) 338–344
3
4. Hybrid process for boron removal..................................................................................................................................................................................................342
4.1. Polymer enhanced ultrafiltration (PEUF) method...........................................................................................................................................................342
4.2. Adsorption membrane filtration (AMF) method.............................................................................................................................................................343
References............................................................................................................................................................................................................................... 343

1. Introduction Nowadays, the concentration of boron increases obviously in

ground water because of both natural and anthropogenic reasons.
Boron is a nonmetallic element, which is widely distributed in During the use of these boron products, boron waste becomes a
the world. Elemental boron is never found in nature, it is a ubiqui- serious problem. This element has high volatility, when it is dis-
tous element in surface and water in various forms of boric acid charged to the environment. It may volatilize and form acid rainfall
and borates. Its concentration in nature is very low. In the earth back to the ground, and be deposited in soil, and absorbed by
crust, the average concentration of boron is approximately 10 plants. Eventually, it pollutes the drinking water sources, and
mg/kg [1]. In soil, the average concentration is 30 mg/kg. In leads to a series of environment and health problems.
seawater, the con- tent of boron is about 4.5 ppm, while the The standard of boron is established throughout the word in
concentration in ground water range from 0.3 to 100 ppm [2]. drinking water, irrigation water, and waste water, but the level
of boron content is diverse in different regions. The
recommended content of WHO guideline in drinking water is
1.1. Importance of boron 0.5 ppm set in 1998, which is revised to 2.4 ppm in 2011.
However, only a few countries follow it. In fact, the value of 2.4
Boron is an essential micronutrient for plants, humans and ppm is below human tolerant level, but exceeds the required
ani- mals. For plants, it is a structural component of cell wall, concentration of several types of crops, which are sensitive to
plays an important role in the structural stability [3], and boron. Therefore, many countries still imple- ment their own
relates to cell wall formation and lignification. It also affects standard. The recommended content of boron is
pollen germina- tion, enzyme reaction, the metabolism of 1.0 mg/L in the European Union, UK, South Korea Singapore and
phenol and carbohydrate, nucleic acid synthesis, and membrane Japan. Instead of federal regulations in USA, the boron content
transportation [4–6]. If boron deficiency occurs in the plant level depends on the state in the range of 0.6 ppm to 1.0 ppm. In
growth, it will lead to thick leaf, excessive branch, and poor New Zealand and Israel, the concentration is 1.4 ppm and 1.5 ppm
germination [7]. For humans and ani- mals, it relates to the respectively. The maximum boron concentration in Canada and
organism of immune function [8], and affects hormone action Australia is higher than WHO guideline as 5 ppm and 4 ppm.
and bone metabolism [9]. Boron deficiency dis- arranges Saudi Arabia is the only country complying with the guidelines
embryo development for vertebrates [10], and impedes [2].
absorption of the element such as calcium magnesium and
phos- phorus [11]. 1.3. Chemistry of boron in aqueous solutions
Although boron is essential for organisms in many ways, it
changes to be toxic while its amount is slightly higher than
Boron dissolves in aqueous solutions as various species on
required. Excessive boron inhibits photosynthesis and root cell
the basis of concentration. In high boron concentration aqueous,
division, impedes deposition of lignin and chlorophyll [12], −
sev- eral boron species are found, such as B2O(OH) 62 , B3O3
causes yellowish spots on the leaves, less fruit, dwarf even − 2− −
rings including B3O3(OH)4 , B4O5(OH)4 , and B5O6(OH)4 [18].
death for plants [11]. In fact, the gap of boron amount between
As the
deficiency and excess is narrow. The required amount of boron
boron concentration is below 290 mg/L, these ions are negligi-
is different among dif- ferent plants, and boron excess is more
difficult to control than boron deficiency [13]. Tu et al. [14] ble. While the boron concentration is below 216 mg/L, B(OH)3
−
divided the crops into three groups by their boron toleration, and B(OH)4 are mainly found as boron species. Boron exists
they are sensitive, semi-sensitive and tolerant with below 1.0 domi- nantly in the form of B(OH)3 and B(OH)4 in nature. In sea
ppm, 1.0–2.0 ppm and above 2.0 ppm separately. water, they are the only boron species, as the concentration is
For humans and animals, the adverse effects of boron could not around 4.8 mg/L [19].
be ignored. Moderate boron is a beneficial nutrient, but a long- In acidic and neutral aqueous solutions, boric acid is the dom-
term chronic absorption of boron may cause a series of harmful inant specie of boron. Boric acid is a kind of solid, which could be
◦
impacts, such as growth retardation, the change of blood composi- solved in water with a solubility of 55 g/L at 25 C. As the pKa is
tion, nervous and reproductive system [15]. Boron is found in below 9.24 in aqueous solutions, boron acid is a weak Lewis acid,
fruits, vegetables, nuts and wine. Humans can absorb enough which accepts a hydroxide ion and releases a proton. In alkali aque-
boron from normal diet without any other special feed [16]. ous solutions, boric acid transform to monoborate anion. When the
pKa increases to above 9.24, the mainly boron specie is monoborate
anion [20].
1.2. Uses of boron and related problems

2. Adsorption process for boron removal

Boron has been used extensively in many industries, such as
glass, ceramics, porcelain, cosmetics, semiconductors, carpets
and fireproofing fabrics. Among them, the biggest user is the The most effective method to remove boron from aqueous solu-
glass industry, more than half of the boron compounds are tions is adsorption technique, because the process requirements
consumed in the glass industry. Beside, boron products are also are simple and can be used in aqueous media with low concen-
used in fertil- izer, welding, cleaning product, fuels, and tration of boron. Boron adsorption can be conducted on various
catalysts. Boron has two stable isotopes, the mass of which is 10 sorbents, e.g. chelating resins, polysaccharides, oxides, synthesized
and 11 respectively with a ratio of 20:80. The isotope boron-10 is clay and fly ash.
crucially used in the nuclear industry, which can control the
nuclear reaction rate in order to avoid explosion [17]. 2.1. Chelating resin mechanism

Chelating resins are the most important sorbents in boron

adsorption technique. Most of them have at least three hydroxyl

Scheme 1. Structure of borate complex.
Scheme 2. Structure of NMDG group.
groups or two adjacent phenolic hydroxyl groups as their
ligands. These hydroxyl structures are often located in the cis
position called “Vis-diols”, which has a high selectivity to
boron, and does not react with other elements. In this reaction,
tertiary amine group is critical for adsorption process, which
neutralizes the proton dur- ing complexation process [21]. The
principle of adsorption method is complexation reactions.
Hydroxyl groups could form various borate esters with boric
acid, which dissociates rapidly and release protons, and then the
acidifications react with diols and form borate complex,
achieving immobilization on the resin finally [19], which is
shown in Scheme 1.
Most synthesized resins have a macroporous polystyrene
matrix, which is attached to the N-methyl-d-glucamine (NMDG)
functional groups. The functional group is a polyol with five
hydroxyls and a tertiary amine end as is shown in Scheme 2,
which can offer more complexation sites, and form a stable
complex with boron. These materials have a promising
performance in boron removal process [22]. They are
available on the market from different manufacturers as
following, PWA10 and IRA743 (Amberlite), CRB01 and CRB02
(Diaion), BSR-1 (Dowex), S108 and S110 (Purolite) [2].
The traditional polystyrene resin is a kind of anion exchange
resin, the hydrophobic skeleton structure of which is not conducive
to the mass transfer process in aqueous solutions, which effects
boron removal from aqueous media. Beside, specific surface area of
support is also an important parameter, which can increase adsorp-
tion quality through raising the crosslink rate of functional groups.
Therefore, much research is done to find some hydrophilic
supports with big specific surface area like polyacrylic acid
resin, macro- porous solid material and so on. Some new
designed NMDG resin modified on different supports is shown in
Table 1.
Since the polystyrene resins with the functional groups of N-
methyl-d-glucamine function emerged in boron removal
process,
Table 1
some designed NMDG resins.
Polymer support (ab.)
Glycidyl methacrylate–methyl methacrylate–divinyl benzene (GMA–MMA–DVB)
Glycidyl methacrylate-co-trimethylolpropane trimethacrylate (GMA-co-TRIM)
Polyethylene styryl sulfonamide
Cellulose
Glucamine-modified MCM-41
Polyol-functionalized SBA-15
Tetraethoxysilane, (3-glycidoxypropyl) trimethoxysilane (TEOS-GPTMS)
Silica-polyallylamine composites (SPC)
Chitosan (CCTS)
6-Nylon fiber-GMA
Calyx 4 arene based magnetic sporopollenin
more chelating resins with different functional groups have been
developed.
Bicak et al. [33] synthesized a resin supported on polystyrene
with a sorbitol functional group, the boron removal capacity was
13.18 mg/g. Senkal et al. [34] developed a kind of boron che-
lating resin with iminopropylene glycols which was supported
on GMA–MMA–DVB, the boron loading capacity of the resin
was up to 32 mg/g, and the regeneration ability was also
reason- able in batch sorption test. Bicak et al. [35] used
terpolymer beads of GMA–MMA–EGDMA to react with diallyl
amine, then the diallylmino function yielded amino-bis(cis-
propane-2,3-diol) functions in presence of OsO4 as a catalyst,
finally prepared the polymer resin with amino-bis(cis-propane-
2,3-diol) functions, the adsorption capacity of which was 19.14
mg/g. Gazi et al. [36] synthesized a new boron chelating resin
with functional group of multi-hydroxyl iminobis (propylene
glycol) (IBPG), which was grafted on CCTS, the boron removal
ability of the resin was up to
29.19 mg/g, but the synthetic method of the resin was complex,
not suitable for mass production. Suzuki et al. [37] modified a
type of strong base anion exchange resin – Lewattitt MP 500WS
with chromotropic acid, obtained a chelating resin containing
two phe- nolic hydroxyl functional groups. The adsorption
capacity of the resin was 8.87 mg/g, and it was more dependent
on the solution pH compared with commercial resin. Yavuz et
al. [38] developed a polymeric sorbent with iminopropylene
glycol group supported on DHPVC using in boron adsorption
from wastewater, the desorption content of the sorbent was 21.62
mg/g. Ince et al. [39] developed a solid tethered imino-bis-
propanediol and quaternary amine func- tional copolymer,
which was able to remove trace boron from aqueous solutions
within less than a minute, the maximum capac- ity of the resin
in boron removal is 43.244 mg/g, the resin had a good
generation ability with unchanged boron loading capacity after
10 cycles test. Santander et al. [40] synthesized a novel che-
lating resin with poly(N-(4-vinylbenzyl)-N-methyl-d-glucamine)
(P(VbNMDG)) functional groups. The P(VbNMDG) resin had an
bet- ter performance and faster kinetics than the commercial
resin – Diaion CRB02 in boron removal from geothermal water.
However, including the widespread commercial resin, boron
chelating resins have many problems, such as limited surface
area, unordered pore structure, poor chemical and thermal
stability [41]. At the same time, resin regeneration requires a
large amount of acid and alkali, which increases the cost.
Therefore, research in find- ing new boron absorbents with low
cost, large surface area, good stability is essential.
2.2. Other absorbents
Orlando et al. [42] discovered some natural material like
polysaccharides with co-planar cis-diol groups or polyhydroxy
groups had boron chelating ability, presented to use natural
polymers in boron removal from aqueous solutions. Konjac glu-
comannan (KGM) is a neutral polysaccharide, which can form
Capacity (mg/g) Reference
23.24 [23]
14.9 [24]
25.57 [25]
11.90 [26]
8.65 [27]
6.81 [28]
12.4 [29]
16.76 [21]
35.13 [30]
12 [31]
12.32 [32]
 B. Wang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 444 (2014) 338–344
5
Table 2
Summary of ED system reported in boron removal.

Membrane type Initial boron salinity Initial boron pH Maximum Reference

content (ppm B) boron
removal
proportion (%)
MK-40, MA-40, MK-100 and MA-100 3.0–15.0 g/L NaCl 1.5–4.0 5.5 87 [56]
MK-40 and MA-40 0.2 mol/L HCl 162 3.6 33 [57]
MK-40 and MA-40 0.2 mol/L HCl 162 12.8 75 [57]
AMX–CMX and ACS–CMS 1.2–2.3 g/L TDS 62.5 and 76.5 3.2 and 8.3 12.4 [58]
AMX–CMX 0.6–2.3 g/L TDS 62.5 and 76.5 3.2 and 6.95 5.1 [59]
AMX–CMX 0.36 g/L TDS 59.6 9.25–10 97 [59]
AMX–CMX 0.4–0.6 g/L TDS 1.3 and 2.25 <9 85 [60]
AMX–CMX – 25–100 8.5 and 9.0 20 [61]
AMX–CMX – 100 9.0 20 [61]
AMX–CMX – 100 10.5 80 [61]
AMX–CMX 5 g/L NaCl 10 3–9 40 [62]
AMX–CMX 5 g/L NaCl 1.7 7 20 [62]
AMX–CMX 5 g/L NaCl 1.7 12 60 [62]
CMS–ACS 1.2 g/L TDS 63.5 8.31 12.4 [58]
CMS–ACS 1.2 g/L TDS 59 10.5 18 [58]
BPM 0–1.2 g/L NaCl 100 2.3–12 90 [53]

TDS – total dissolved solids.

a complex with boron. Unfortunately, KGM has good water
solubility, for which it cannot remove boron from aqueous solu-
tions. Oishi et al. [43] made KGM grafted on semi-gel as a boron
sorbent, solving the problem of solubility and avoiding the lost of
diol groups during gelation. Morisada et al. [44] obtained a tannin
gel (TG), and then modified it with ammonia, got amino modified
tannin gel (ATG), these two gels had poor performance in aqueous
solutions with pH less than 7, and the maximum boron adsorption
contents were 11.4 mg/g and 24.3 mg/g in alkaline solution.
Some materials with low cost as fly ash and tailing are also used
in boron removal process. Polowczyk et al. [45] used fly ash
agglom- erates generated from power plant to remove boron from
aqueous media, and the maximum boron loading capacity was
6.9 mg/g. Kıpc¸ ak et al. [46] took calcined magnesite tailing as
adsorbent, the Langmuir adsorption test showed the maximum
boron load-
◦ exchangers which is immobilized on membrane materials,
ing capacity of magnesite is 65.79 mg/g at 45 C, demonstrated
that
the magnesite was an effective adsorbent for boron removal
from aqueous solutions.
Layered double hydroxides (LDHs) are also a group of
adsor- bents for the uptake of various boron species. LDHs are a
group of clay minerals with a similar structure from both
waste prod- ucts and abundant deposits in nature. LDHs have
lots of divalent cations, these cations can be replaced by
trivalent cations causing a net positive charge, which can be
changed with anions in the layered structure [47]. Ferreira et al.
[48] used Mg/Al and Mg/Fe LDHs to remove boron from
wastewater, the maximum boron load capacity was 14.0 mg/g
according to the Langmuir model. Kentjono et al. [49] reported
the boron removal from optoelectronic waste- water with high
concentrations of boron using Mg/Al LDHs, and the maximum
boron removal capacity was 37.90 mg/g at pH 9.
Different from the materials discussed above, ionic liquids
(ILs) are taken as solvents in liquid–liquid extraction. They
consisted of various ions that are liquid at room temperature,
and these ionic liquids can remove boron successfully even in
high salinity aque- ous solutions [50]. Joshi et al. [51]
synthesized a new class of ionic liquids (ILs) from N-methyl-d-
glucamine, which have not only high selectivity toward boron
species but also the ability of phase sepa- ration rating from
water. The results of situ dispersive liquid–liquid extraction
were promising, and boron reduction is significant after
extraction process.
3. Membrane process for boron removal
Membrane methods are the most common used in
desalination of seawater and any other salt water. Although this
is the second
method to solve boron pollute problem, it has some limitation in
practical application. While the concentration of boron is below
permissive level, an additional process must be adopted in
order to solve the problem. The pH of the media used in this
method must be increased to the range of 10–11, and boric acid
will be trans- formed to borate and be separated finally. But this
way will lead to another problem. Although the separation
efficiency increased dra- matically to 98–99%, some hydroxides
like magnesium hydroxides precipitate on the surface of the
membrane. Therefore electrocoag- ulation or resin desorption
must be replied as a pretreatment step for membrane process.
3.1. Ion-exchange membranes (IEM) method
Ion-exchange membranes (IEM) are a group of synthetic ion
includ- ing cation-exchange membrane (CEM), anion-exchange
membrane (AEM), and bipolar membranes (BPMs). They are
usually used in boron removal process such as electrodialysis
(ED) and Donnan Dialysis (DD) systems.
In an ED system, electric potential gradient is the driving
force, CEMs and AEMs are set alternately and the space
between them is called dilate compartment. Cations and anions
will migrate across CEMs and AEMs respectively in the
opposite directions along the electric field lines, and
concentrate compartments are formed. Finally, the
desalination process finished and boron anions are removed
from feed solution [52]. But the mechanism in BPMs appli-
cation is a little different from above. BPM has two sides with
anion-exchanger and cation-exchanger respectively. So there are
only water molecules without ions in membrane pores, which
are dissociated into hydroxyl and hydrogen ions that are trans-
ported to anode and anode respectively in external electric field,
and the solution around the anion-exchanger of BPM turns alka-
line, resulting in borate enrichment. Borate is then migrated
across AEM and neutralized with hydrogen ions around cation-
exchanger, finally obtaining a concentrate solution with boric
acid and realizing the purpose of boron removal [53]. The
reports about ED system used in boron removal are
summarized in the Table 2.
Donnan dialysis (DD) is a kind of ion exchange process.
Unlike ED, there is no external electric field. When the solution
of boron compounds goes through an ion exchange membrane,
two compo- nents could be separated according to their
chemical differences [54]. Kir et al. [55] showed that, if AEMs
used in this method is modified with plasma, the separate
efficiency of boron would have
Table 3
Summary of RO membranes used in boron removal.

Membrane type pH Water condition Study medium Maximum Reference

boron removal
proportion (%)

UTC-80 8 4 ppm B Lab 90 [64]

UTC-80 8 32 g/L NaCl, 5 ppm B Lab 90 [65]
UTC80 8.19 1.30–3.96 ppm B Lab 67 [66]
UTC80A 8.19 1.30–3.96 Lab 71.7 [66]
UTC80S 8.19 1.30–3.96 Lab 61.4 [66]
SW30HR-380 8 32 g/L NaCl Field 90 [67]
SW30HR-320 8 32 g/L NaCl Field 90 [67]
SW-30 5.5 5.1 ppm B Pilot plant 55 [68]
SW30-380 8 32 g/L NaCl Field 88 [67]
SW-30-XHR-400i 8 32 g/L NaCl, 5 ppm B Manufacturing company 93 [69]
SW-30-HRLE-400i 8 32 g/L NaCl, 5 ppm B Manufacturing company 91 [69]
SW-30-XLE-400i 8 32 g/L NaCl, 5 ppm B Manufacturing company 88 [69]
SW-30-ULE-400i 8 32 g/L NaCl, 5 ppm B Manufacturing company 87 [69]
SW-30-2540 8–8.2 39 g/L NaCl RO plant 85 [70]
SW-30-XHR-2540 8–8.2 39 g/L NaCl RO plant 88 [70]
SW-30-HR-380 8 32 g/L NaCl, 5 ppm B Lab 90 [65]
SW30-2540 5.03–5.43 8.8–11.4 ppm B Pilot plant 84 [71]
XUS SW30XHR-2540 5.10–5.40 8.8–11.4 ppm B Pilot plant 88 [71]
BW30-400 8 32 g/L NaCl Field 65 [67]
BW30LE 8 32 g/L NaCl Field 55 [67]
BW-30 5.5 5.1 ppm Boron Pilot plant 75 [68]
GE-AG 5.5 5.1 ppm Boron Pilot plant 80 [68]
SU-820 8 32 g/L NaCl, 5 ppm B Lab 91 [65]
TM-820A-400 8 32 g/L NaCl, 5 ppm B Manufacturing company 93 [69]
TM-820C-400 8 32 g/L NaCl, 5 ppm B Manufacturing company 93 [69]
TM-820E-400 8 32 g/L NaCl, 5 ppm B Manufacturing company 91 [69]
TM-820-370 8 32 g/L NaCl, 5 ppm B Lab 91 [65]

a significant enhancement. But the limitation of this method is
that DD can only be used in the purification and concentration
of diluted solutions.
3.2. Reverse osmosis (RO) method
Reverse osmosis is a membrane technology which is widely
used in seawater desalination and water treatment. The
membrane used in RO is semi-permeable, only allow water
permeates while dis- solved species are rejected under external
pressure. In high pH solutions, boron is presented in the form
−
of boron ion, B(OH)4 , which can be separated easily by RO
technology. However, in sea- water and other low pH
solutions, the dominant form of boron is non-dissociated
uncharged boron acid, decreasing boron rejec- tion efficiency
across RO membranes. In recent years, many studies are
focusing on enhancing boron removal ability in RO technol-
ogy through new generation and system configuration
adjustment. Table 3 shows a summary of capable RO membrane
with higher boron rejection capacity [63].
In RO configurations adjustment aspect, a second-pass RO stage
added after the first-pass is developed. Before the second-pass, the
pH is adjusted after the first-pass in order to remove the rudimen-
tal boron [67]. Farhatet et al. [63] implemented a novel two-pass
system using new generation RO membranes without pH adjust-
ment, and boron rejection efficiency had a significant increase as
high as 96%. Bick et al. used the analytic hierarchy process (AHP)
model to select the optimal boron removal methods. According to
the analysis of Hasse diagram technique, the two stages of RO with
permeate split were preferred and the use of ion-exchange in series
could improve the performance of a single stage [72].
3.3. Electrocoagulation (EC) method
Electrocoagulation is often replied before membrane process.
It is an easy-to-operate method with simple equipment, which
can be used in most rigorous situations even when the boron
amount is negligible in the aqueous solutions. The solubility of
substance
would reduce to minimum, as it is in charge of neutralization. EC
has a cell with metal anode. At the beginning of the process,
pollutants form coagulant due to anode electrical oxidation, and
then emul- sion occurs, these destabilizing pollutants suspend in
the media and combine instable particles, form flocs and subside
finally [73,74]. The metal anode of EC is usually iron or aluminum,
but Vasudevan et al. [75] provided a zinc hydroxide anode, the
result showed that the optimum removal efficiency is 93.2% at pH
7.0.
4. Hybrid process for boron removal
Hybrid methods are the combinations of sorption system and
membrane filtration. In hybrid system, solutes like boron species
are absorbed by fine sorbents following a membrane filtration
pro- cess [76]. The fine sorbents used here has smaller particle
size but better performance in the reduction of sorbent cost
without a pressure drop compared with the conventional
sorption system. They are usually low molecular weight
materials like gluconates or mannitols. Sometimes other
surfactants, soluble polymers or solid particles are also used in
hybrid methods. Two typical hybrid methods – PEUF and AMF
are discussed as followed.
4.1. Polymer enhanced ultrafiltration (PEUF) method
The sorbents used in PEUF method are special water-soluble
polymers, with which the solutes form complexation that can be
separated from aqueous solutions by ultrafiltration based on the
mechanism of size-exclusion. PEUF can be operated under
lower pressure but higher flux with less energy cost compared
with NF, and the defect of mass-transfer may also be avoided in
a homoge- neous medium [77].
It is used to remove various pollutant ions especially cations
[78]. The aim of selective separation can be achieved by
applying target-specific polymers in the process. A lot of
chelating poly- mers are employed in PEUF method previously.
Smith et al. [79] investigated a kind of hyper-branched boron
chelating polymers, but in this study some drawbacks about
functional polymers
 B. Wang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 444 (2014) 338–344
7
were reported as well. Polymer gelation was found during the
process, and one-third of the polymers were lost after four
cycles of separation–regeneration experiment. In the study of
Zerze et al. [80], the problem of polymer precipitation was not
observed. They synthesized a copolymer, poly (vinyl amino-
r [22] Y. Xu, J.-Q. Jiang, Technologies for boron removal, Industrial & Engineering
N,N -bis-propane diol-co-DADMAC) (GPVA-co-DADMAC) in
three comonomer ratios (2%, 5% and 10%), 92% boron could be
rejected from the solution with initial boron concentration of 10
ppm at pH 9.0 via a contin- uous PEUF system. Zerze et al. [81]
reported an excellent chelating polymer-poly (vinyl amino-
N,N-bis-propane diol) (GPVA) for boron removal. The boron
removal efficiency is up to 96% at pH
9.0 without precipitation in total recycle PEUF system.
4.2. Adsorption membrane filtration (AMF) method
Microspherical sorbents and microfiltration membranes are
used in AMF process. This configuration does not need high
pressure and membranes can bear wild flux situation [76].
However, there are some requirements for the microspherical
sorbents. They must possess small diameters, uniform sizes, and
smooth edges to resist abrasion during the process without tear
the membranes. Wolska et al. [82] developed a kind of poly-
meric microspheres. They are monomer mixtures of vinylbenzyl
chloride-styrene-divinylbenzene (VBC/S/DVB) modified with N-
methyl-d-glucamine. The sorbents have a good performance at
boron removal from both acid and base solutions in AMF
process.
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