Journal of Cleaner Production 197 (2018) 1435e1446

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Journal of Cleaner Production

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

Review

Application of zeolite in removing salinity/sodicity from wastewater:

A review of mechanisms, challenges and opportunities
Jia Wen a, b, *, Haoran Dong a, b, Guangming Zeng a, b
a
College of Environmental Science and Engineering, Hunan University, Changsha 410082, PR China
b
Key Laboratory of Environmental Biology and Pollution Control (Hunan University), Ministry of Education, Changsha 410082, PR China

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

Article history: Elevated salinity levels in wastewater usually have negative consequences to soil quality and crop growth
Received 5 April 2018 if used directly in irrigation without proper treatment. Though many techniques have been developed to
Received in revised form solve the problem, high capital costs or energy consumption have hindered their application in wider
22 June 2018
regions. One economical solution of reusing the wastewater of high salinity is applying natural or syn-
Accepted 25 June 2018
Available online 27 June 2018
thetic zeolites as ion exchanger and adsorbent. Chemically modified natural zeolites or synthetic zeolites
have been utilized to reduce Naþ in various kinds of saline/sodic waters. In this paper, we reviewed the
recent technical improvements of using natural or modified zeolites in the field of water salinity
Keywords:
Zeolite
reduction. The mechanisms governing the salt removal process by zeolites are mainly ion exchange,
Wastewater adsorption, and salt storage. Factors such as zeolite's geochemical properties, pH, co-existing anions,
Salinity concentration, valency, surface charge, and experimental conditions all influence the ion exchange
Sodicity process. Adsorption isotherm of Naþ ions on zeolites, mostly reported to follow either Langmuir or
Cation exchange Freundlich isotherm, has a composition-dependent behaviour. The adsorption kinetics of Naþ on zeolites
Ion adsorption is mostly a pseudo-second-order type with an exothermic nature. Sodium removal by zeolites appears to
be an effective water treatment technology for maximizing the beneficial use of poor-quality saline/sodic
wastewater. However, challenges still remain and further work is required in areas of lowering opera-
tional cost and improving zeolite's regenerability. To overcome these challenges, researchers could make
more efforts in technical improvements, including alterable surface properties and the incorporation of
other approaches to achieve better salt removal outcome.
© 2018 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1436
2. Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1436
2.1. Literature screening . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1436
2.2. Selection of literature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1436
2.3. Categorization of literature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1436
3. Uses of zeolite in water industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1436
4. Ion exchange on zeolite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1437
4.1. Geochemical factors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1438
4.2. pH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1439
4.3. Anions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1439
4.4. Concentration-valency effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1439
4.5. Point of zero charge . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1439
4.6. Experimental conditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1439
5. Adsorption isotherms, kinetics and thermodynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1439

* Corresponding author. College of Environmental Science and Engineering,

Hunan University, Changsha 410082, PR China.
E-mail address: jwen@hnu.edu.cn (J. Wen).

https://doi.org/10.1016/j.jclepro.2018.06.270
0959-6526/© 2018 Elsevier Ltd. All rights reserved.
1436 J. Wen et al. / Journal of Cleaner Production 197 (2018) 1435e1446

6. Salt storage vs. salt exchange . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1441

7. Assessment of zeolite application in wastewater industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1442
7.1. Challenges: economic considerations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1442
7.1.1. Commercial synthesis of zeolite and likely cost . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1442
7.1.2. Regeneration ability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1442
7.2. Opportunities: technical improvement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1443
7.2.1. Pretreatment/modification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1443
7.2.2. Dual adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1443
7.2.3. Zeolite-based membrane and composite materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1443
8. Conclusion and future outlooks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1444
Acknowledgement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1445
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1445

1. Introduction salt removal by zeolite and factors influencing these processes.

Regenerability and cost of synthesis are also crucial subjects to
Wastewater generated from wastewater treatment plant (WTP) determine the feasibility and life-span of such material used in
is usually saline compared to fresh water because of dissolved salts. wastewater industry. To the best of our knowledge, there has not
The associated elevated salinity levels in wastewater could have been a review article addressing these aspects. Therefore, this re-
negative consequences to soil quality and crop growth if used view hopes to provide a detailed illustration of using zeolites for
directly in irrigation without proper treatment. To make the saline water salinity reduction, and to make reasonable suggestions on
wastewater reusable, many techniques have been introduced into future paths for technical development.
the water industry, including the use of medium filtration and
membrane filtration, cation exchange, electro dialysis, sorption, 2. Methods
and electrochemical treatments (Lyu et al., 2016; Norton-Branda ~o
et al., 2013; Teow and Mohammad, 2017). Some of these tech- 2.1. Literature screening
niques requiring high capital investment or energy consumption
may be limited for application in regions of low economic income. The Web of Science database was used to support the literature
The treated wastewater is then further utilized in agriculture to search for this review. During this stage, several keywords were
meet the growing demands of world population and alleviate the used to identify relevant literature. The authors first used the
serious situation of water shortage (Lyu et al., 2016). keyword “zeolite”, the results came out with 102,797 references
Zeolites have been widely used in water industry as ion ex- published from 1963 to 2018. The authors then narrowed down the
changers and adsorbents (O'Brien et al., 2008; Smi ciklas et al., search results by adding more restrictive keywords “sodium/water/
2007). Zeolite is a crystalline, hydrated aluminosilicate of alkali ion exchange/adsorption” within the domain of “Science Technol-
and alkaline earth cations having an infinite, open, three- ogy”, the results finally turned out with 311 references.
dimensional structure (Mumpton, 1999). The empirical formula of
a zeolite is of the type M(2/n)OAl2O3xSiO2yH2O, where M is any 2.2. Selection of literature
alkali or alkaline earth atom, n is the charge on that atom, x is a
number from 2 to 10, and y is a number from 2 to 7 (Pabalan and The abstracts of all references found in the literature screening
Bertetti, 1999). The pores of the molecular size are between 0.5 process were further assessed to see if they were related to the use
and 1.2 nm. The porous zeolite is a host to water molecules and ions of zeolite for reduction of water salinity. In this stage, the references
of singly- and doubly-charged atoms. Nevertheless, only those of were assessed to include all terms used in the screening process.
appropriate molecular size that can fit into the pores are admitted, The terms appeared either in the title, abstract or keywords of the
thus creating the “sieving” property. Substitution of some silicon references. Moreover, only high-quality studies identified by a
(Si) with aluminium (Al) (or other metals) in the silicate frame- detailed methodology, complete list of parameters, and a compre-
works leads to a negative charge on the framework, resulting in its hensive discussion of the results were selected for further review.
ability to attract cations (principally sodium (Naþ), potassium (Kþ),
and calcium (Ca2þ), less frequently lithium (Liþ), magnesium 2.3. Categorization of literature
(Mg2þ), strontium (Sr2þ) and barium (Ba2þ)) within the pore
structure (Pabalan and Bertetti, 1999). The weakly bound extra- The selected references were then categorized into three sec-
framework cations can be removed or exchanged readily by tions for further analysis. The first section is a collection of studies
washing with a strong solution of another cation. This characteristic relating to principles and theories of ion exchange and adsorption.
makes zeolites excellent materials to be used in cation exchange These studies also point out the underlying mechanisms governing
applications. Other important properties include a high degree of the salt removal process. The second section includes studies
hydration/dehydration, low density, and good crystal stability involving directly with water desalination technology using zeolite,
when dehydrated (Taulis, 2007). which functions as the foundation of this review paper. Lastly,
Nowadays, many researchers have brought great attention on studies related to the topic “zeolite” or “desalination” were selected
using the natural and low-cost zeolites for water salinity reduction to support the assessment of opportunities and challenges of the
(Ganjegunte et al., 2011; Gibb et al., 2017; Paul et al., 2017; Taulis, technique.
2007; Wang et al., 2012; Wibowo et al., 2017a), which may enor-
mously benefit areas of water shortage. To facilitate the manufac- 3. Uses of zeolite in water industry
ture of zeolites that suits the special demand of treating saline/
sodic wastewater, it is important to understand the mechanism of Zeolites have been made in the use of wastewater treatment due
 J. Wen et al. / Journal of Cleaner Production 197 (2018) 1435e1446 1437

to their unique physical and chemical properties (crystallinity,
thermal stability, well-defined cage structure of molecular size, and
ion-exchange, etc.). To date, zeolites have been used in removal of
heavy metal contaminants from wastewater (Choi et al., 2016;
Dimirkou and Doula, 2008; Mondale et al., 1995; Song et al.,
2015; Tran et al., 2018; Wingenfelder et al., 2005), removal of ra-
dioisotopes (e.g., 137Cs and 90Sr) form radioactive waste streams
(Dyer et al., 2006; Olguín and Deng, 2016; Vipin et al., 2016),
reduction of excess ammonium (NHþ 4 ) from municipal wastewater
(Du et al., 2005; Huang et al., 2015; Rodríguez-Iznaga et al., 2018;
Xu et al., 2002; Zhang et al., 2016), removal of organic contami-
nants (e.g., aniline, cationic surfactants, phenol, and sulfonamide
antibiotics) (Amin et al., 2010; Braschi et al., 2010; Li et al., 2008;
O'Brien et al., 2008; Peng et al., 2015), and reduction of salinity
and sodicity in various water (Paul et al., 2017; Wibowo et al.,
2017a,b; Zhao et al., 2008, 2009), etc.
An important application of zeolites as ion exchanger is as water
softeners in laundry detergents (Ates and Akgül, 2016). In this
process, monovalent ions, mainly Naþ, in zeolites exchange with
Ca2þ and Mg2þ in hard water. Therefore, more synthetic Na-type
zeolites are produced than other zeolites. In countries with low
wastewater treatment standards, synthetic zeolites are largely
consumed by the detergent industry because they are more envi-
ronmental friendly than polyphosphate as a raw material used for
manufacturing detergents (Suboti c and Broni c, 2003).
Salinity and sodicity are the principal water quality concerns in
arid and semi-arid regions using water of poor quality for irrigation.
Many international and national environmental organisations and
authorities have set up guideline limits to regulate the safe use of
treated wastewater for irrigation, which include limits of salinity
and sodicity (Table 1). High concentrations of Naþ are undesirable
in water because Naþ adsorbed onto soil cation exchange sites will
cause soil aggregates to disperse and reduce its permeability. So-
dium concentration is therefore an important salinity parameter
when evaluating the suitability of wastewater for irrigation. The
sodicity level is measured as sodium adsorption ratio (SAR), which
is the mille-equivalent ratio of Naþ to the combination of Ca2þ and
Mg2þ.
A SAR value > 4 indicates the quality of water is sodic and un-
suitable for agricultural irrigation (Gibb et al., 2017).
Saline and sodic water can be produced naturally owing to the
ion exchange process. An example to this would be the ion ex-
change process taking place between clay minerals and CSG water,
where Ca2þ and Mg2þ are held more tightly than Naþ in clays when
groundwater encounters clays or shales as it flows through the coal
seam (Taulis and Milke, 2007), leaving the CSG water saline and
sodic. Therefore, the use of zeolite in Naþ reduction process is
opposite to that in the water softening process, as other cations
such as Ca2þ or NHþ þ
4 in zeolites replace Na in the saline and sodic
water. For most zeolites that are naturally abundant in Naþ, zeolites
used for this particular purpose should therefore be modified or
synthesized to have low Naþ occupation.
To make the salt removal process a success by using zeolites, the
mechanism governing it should be well understood before tech-
nical improvement is pursued. The removal of salt from wastewater
greatly depends on tree closely-correlated processes: ion exchange,
adsorption, and salt storage.
4. Ion exchange on zeolite
Ion exchange is the trading of one singly-charged exchangeable
atom in the zeolite for another singly-charged atom from solution

Table 1
Guideline limits of water used for irrigation.

Guideline FAO (1992) US EPA (2012) ANZECC (2000) SEPA PRC (2005)

Type of guideline Wastewater Quality Guidelines for Water Reuse National Guidelines for Standards for Irrigation
Parameter Symbol Unit Guidelines for Agricultural Water Quality Water Quality
Use
Salinity
Electrical ECw dS/m 0.7; 0.7e3.0; 3.0a 0.7; 0.7e3.0; 3.0a <0.65; 0.65e1.3; 2.9e5.2b e
conductivity
Total dissolved TDS mg/L 450; 450e2000; 2000a 450; 450e2000; 2000a e <1000 (non-salinity area),
solids <2000 (salinity area)
Sodium adsorption SAR Dimensionless 3; 3e9; 9a e 5e10 e
ratio
Cations and anions
Magnesium Mg2þ mg/L e 0.2; 10c 0.2; 10c e
þ d
Sodium Na mg/L e <69; >69 115e230 e
Total Mercury Hgtot mg/L e e e 0.001
Cadmium Cd2þ mg/L 0.01 0.01 0.01; 0.05c 0.01
Lead Pb2þ mg/L 5.0 <5.0 2; 5c 0.2
Sulfide S2- mg/L 1
Chromium (VI) Cr(VI) mg/L 0.1 0.1; 1c 0.1; 1c 0.1
Total Arsenic Astot mg/L 0.1 0.1 0.1; 2b 0.05; 0.1d
Bicarbonate HCO 3 mg/L 1.5; 1.5e8.5; 8.5a e e e
Chloride Cl meq/L 4; 4e10; 10a <1; 1e10; 10a e 350
Fluoride F mg/L 1.0 1.0 e 2
Miscellaneous
Boron B mg/L 0.7; 0.7e3; 3a <0.75 e 1; 2;3a
Hydrogen ion pH unit 6.5e8 6.5e8.4 e 5.5e8.5
activity
e
E. coli CFU/100 mL 200; 1000 e e 4000
a
Non-restriction, moderate-severe restriction and severe restriction, respectively.
b
Sensitive, moderately sensitive and tolerant crops, respectively.
c
Long- and short-term application respectively.
d
None-restriction and slight to moderate-restriction respectively.
e
Irrigation for public lawns; and irrigation of crops likely to be eaten uncooked, sports fields, public parks.
1438 J. Wen et al. / Journal of Cleaner Production 197 (2018) 1435e1446

or trading of two singly-charged exchangeable atoms in the zeolite Box 1

by one doubly-charged atom from the solution. The exchanging
species occupy the exchangeable process and form outer-sphere
complexes as Eq. [1]:



≡S  Ο nþ
C3n þ M 2þ 4 ≡S  Ο M2þ þ ð3  nÞC nþ
2… 2…
[1]
where M2þ is exchanging species, C is the counterbalanced ion with
charge n (n ¼ þ1 or þ2), and S corresponds to the surface central
metal (i.e., Si, Al, Fe) (Dimirkou and Doula, 2008).
Cation exchange capacity (CEC) is commonly measured in terms
of moles or equivalents of exchangeable cation per gram of zeolite.
Expressing CEC in terms of equivalents eliminates the need for
stating the nature of the exchanging cations. The normal CEC of
natural zeolite minerals are listed in Table 2. The CEC of a zeolite is
basically a function of the amount of Al that substitutes for Si in the
framework tetrahedra. Sherry (2003) has well presented the rules
of ion exchange on zeolites (Box 1).
The CEC of zeolites can be determined by standard American
Society of Agronomy method, following the same procedure as soil
CEC testing (Hulbert, 1987). However, the soil method may un-
derestimate the CEC of zeolites due to the internal pores and
channels existing in the zeolite structure. Ammonium acetate
saturation method (AMAS) was then proposed by Kitsopoulos
(1999) to measure zeolite CEC. In this method, the NHþ 4 -saturated
samples of zeolites are washed with 10% NaCl, and the amount of
the NHþ 4 ions in solution is equivalent to the CEC of zeolite. How-
ever, some researchers pointed out that the AMAS method should
be modified because washing with 10% NaCl does not facilitate
release of all NHþ 4 ions within the zeolite structure. Instead, they
used CsCl to replace native cations on clinoptilolite zeolitic ex-
change sites (Latifah et al., 2011; Ming and Dixon, 1986), as cli-
noptilolite has a specificity for Cs according to the ion exchanging
rules (Sherry, 2003).
There are a number of factors regulating the change of CEC in
zeolites, which further determine the trend and potential for salt
removal using zeolites for wastewater treatment. Because the fac-
tors influencing CEC also have a consequence in ion adsorption, we
have summarized factors most important for the two processes as
follows:
4.1. Geochemical factors
There are two main geochemical factors involved in cation ex-
Rules of ion exchange on zeolite (Sherry, 2003)
1. All zeolites prefer Naþ to Liþ;
2. All zeolites prefer NHþ þ
4 to Na ;
3. The most aluminous zeolites have the highest selec-
tivity for Ca2þ and other alkaline earth cations. This
selectivity decreases with increasing Si:Al ratio, and
should be even more marked for trivalent cations;
4. The most siliceous zeolites have the highest selectivity
for Csþ, Rbþ, NHþ þ
4 , and K . This selectivity decreases
with decreasing Si:Al ratio;
5. Selectivity will decrease with increasing salt concen-
tration if the ingoing cation has a higher charge than the
outgoing cation;
6. In zeolites with very high Si:Al ratio, complete ion ex-
change of divalent ions for monovalent ions becomes
very difficult. Selectivity and degree of exchange in-
creases with increasing size of the divalent ion and
decreasing Si:Al ratio. Exchange of trivalent cations
should be even more difficult;
7. All zeolites are highly selective for polarisable ions such
as Agþ, Tlþ, Pb2þ, and Cd2þ. The lower the Si:Al ratio the
higher the selectivity;
8. Partial ion exchange may take place where ions are
located in large and small cages, and ingoing hydrated
ions or bare ions are too large to diffuse into small
cages;
9. Redistribution of cations that are initially present in a
zeolite may take place if the ingoing cation is very large.
Therefore, incomplete exchange is not necessarily an
indication of ion sieving, yet may be a result of ion
crowding;
10. Zeolites with a Si:Al ratio of 10 or higher can undergo
reversible hydronium ion exchange using strong acids.
for cation of specific sizes to travel through them (Mumpton, 1999).
In general, the greater the charge (the bigger the size) on the cation,
the more likely it is prevented from entering the seat of inner
framework of zeolites. For example, cation selectivity of clinopti-
lolite (CEC z 2.25 meq/g) was reported to be
Cs > Rb > K > NH4>Ba > Sr > Na > Ca > Fe > Mg > Li (Mumpton,
1999). Similarly, the order of selectivity of NHþ4 ions for other cat-

change in zeolites, including: (1) the size and configuration of ions on the zeolites was reported to follow Naþ[Kþ>Ca2þ>Mg2þ
cavities (cages and channels). Different sized channel have diverse (Watanabe et al., 2003). Exchange capacity is not sensitive to crystal
configurations throughout the zeolite crystal structure and allow size, but the rate of exchange process considerably depends on the

Table 2
Cation-exchange capacity (CEC) of zeolite minerals based on the number of equivalents of exchangeable cations (adapted from Gottardi and Galli (1985) and
Perego et al. (2013)).

Zeolite Typical Unit-Cell Formula Major cation CEC (meq/g)

Analcime Na16(Al16Si32O96)$16H2O Na 3.6e5.3

Chabazite Ca2(Al4Si8O24)$12H2O Na, K, Ca 2.5e4.7
Clinoptilolite (Na,K)6(Al6Si30O72)$20H2O Na, K, Ca 2.0e2.6
Erionite NaK2MgCa1.5(Al8Si28O72)$28H2O Na, K, Ca 2.7e3.4
Faujasite Na20Ca12Mg8(Al60Si132O384)$235H2O Na, K, Mg 3.0e3.4
Ferrierite (Na,K)Mg2Ca0.5(Al6Si30O72)$20H2O Ca 2.1e2.3
Heulandite (Na,K)Ca4(Al9Si27O72)$24H2O Ca 3.2
Laumontite Ca4(Al8Si16O48)$16H2O Na, K, Mg 3.8e4.3
Mordenite Na3KCa2(Al8Si40O96)$28H2O Na, K, Ca 2.0e2.4
Natrolite Na16(Al16Si24O80)$16H2O Na 5.3
Phillipsite K2(Ca0.5,Na)4(Al6Si10O32)$12H2O Na, K, Ca 4.5
Wairakite Ca8(Al16Si32O96)$16H2O Ca 4.6
 J. Wen et al. / Journal of Cleaner Production 197 (2018) 1435e1446
crystal size. The diminishing crystal size of zeolite is favorable for
improvement of exchange efficiency in water softening process
(Subotic and Bronic, 2003) and desalination process (Belbase et al.,
2013; Zhao et al., 2008); (2) Si:Al ratio. The smaller the Si:Al ratio
the larger the ion exchange capacity of the zeolite (Wenk and
Bulakh, 2006). The factor is due to that every replacement of Si4þ
by Al3þ results in a greater charge imbalance.
4.2. pH
Solution pH influences the adsorption of cations on zeolites in
two ways: one is an effect on metal solubility and speciation of
metal ions in solutions, and another is an effect on the overall
charge of the sorbent (Ji et al., 2007). Therefore, the quantity of
metal species adsorbed is a function of pH and composition of so-
lution. Carland and Aplan (1988) and Inglezakis et al. (2003) found
that the uptake of metal ions in wastewater by zeolites was limited
at low pH. This is also supported by Wingenfelder et al. (2005) who
found a reduced zinc (Zn) and cadmium (Cd) uptake by zeolite from
pH 5.5 to pH 2.0. The reduced metal uptake can be attributed to
increased competition for sorption sites with protons. However, it
does not indicate the high pH would lead to a constant increase of
cation exchange and adsorption. As found by Han et al. (2007), the
adsorption of UO2þ
2 diminished as pH rose from 6.0 to 11.0. They
deduced that it might be due to increases of dissolved carbonate
and biocarbonate ions which could also compete for adsorption
sites.
Solution pH affects zeolite framework also because aluminosil-
icates are not resistant to strong acids and alkalis, hence dissolution
is likely to occur. Aluminium is preferentially dissolved under
strong acidic conditions, while Si is more likely to dissolve under
strong alkaline conditions. Interestingly, dissolution of Al and Si is
at the minimum under neutral pH conditions, so that the effect of
dissolution on ion-exchange equilibrium can be neglected (Pabalan
and Bertetti, 1999). Ji et al. (2007) obtained the highest adsorption
capacity of CaY and NaY in an NH3 removal process at pH ¼ 6. The
optimum pH condition for the highest cation exchange capacity
could therefore be the neutral to slight acidic pHs.
4.3. Anions
Anions in certain modified zeolites can also be exchanged in
pores and cavities in zeolites. In all-Si zeolites, F ions can replace
OH in the framework, except that F are located at the centre of a
different unit (Liu et al., 2011). When zeolites are surface-modified
by altering its surface charge using appropriate charge reversing
chemical species such as surfactants, thus they are also suitable for
removing anionic contaminant from water (Barczyk et al., 2014;
Onyango et al., 2010, 2004; Tran et al., 2018). In saline waters, the
presence of dominant anions (e.g., Cl) greatly affects the adsorp-
tion of Naþ by zeolites. For instance, the adsorption of Naþ from a
dechlorinated seawater was more than double of that from the
same untreated seawater (Wibowo et al., 2017a). The occupation of
pores and cavities by anions likely accounted for the reduced
number of exchanging sites open for cation exchange.
Solution pH can also affect the anion adsorption process in the
surface-modified zeolites. An increase in pH could cause a slight
decrease in anion (e.g., NO 
3 , F ) adsorption due to interaction
during passive transport in pores and competition between OH
and those anions for active sites (Onyango et al., 2010).
4.4. Concentration-valency effect
The total concentration of an aqueous solution does not have a
1439
large effect on the selectivity of zeolite for a particular ion for ex-
change if the exchanging ions have equal charges (e.g., Naþ and Kþ).
However, the ion-exchange behaviour strongly depends on the
solution concentration if the exchanging ions have different
charges (e.g., Naþ and Ca2þ). With increasing dilution (decreasing
concentration), the selectivity of zeolite for ions of higher valency
becomes progressively greater. The effect of concentration on ion
exchange is called 'concentration-valency' effect (Pabalan and
Bertetti, 2001). Therefore, cation valence plays an important role
in zeolite retention for metal ions. Olguín et al. (1999) found the
exchange efficiency of U4þ on zeolite X in equilibrium was more
evident than UO2þ 2 , with the maximum uptake value of 1.86 meq/g
of zeolite X for UO2þ 4þ
2 and of 2.86 for U . The difference was likely
controlled by the effective charge of each ion.
4.5. Point of zero charge
The point of zero charge (PZC) is usually used to define the
surface state of a dispersed solid phase at the solid-electrolyte so-
lution. The PZC of a specific minerals is the pH value (pHpzc) at
which the surface concentrations of negative ([MO]) and positive
([MOHþ 2 ]) ions are equal, i.e., z ¼ 0. Therefore, the surface charge is
negative at pH > pHpzc, and positive at pH < pHpzc. The PZC can be
changed by altering surface properties. It was reported that the
zeolite F-9 was negatively charged over a pH range of 3e11. When it
was Al-modified (Al3þ ions were exchanged for Naþ ions in the
zeolite), the zeolite particles were charge reversed and the pHpzc
was found to be 8.15; when it was lanthanum-modified (La3þ ions
were exchanged for Naþ) to form La-zeolite F-9, the zeolite had a
lower pHpzc of 5.25 (Onyango et al., 2004).
4.6. Experimental conditions
To improve the cation exchange capacity of zeolites, soft
chemistry based process (i.e., chemistry at low temperatures and
pressures, from molecular or colloidal precursors) offers innovative
strategies to obtain tailored nanostructured materials. The mild
conditions of sol-gel chemistry provide reacting systems mostly
under kinetic control. Therefore, slight changes of experimental
parameters (i.e., pH, concentrations, temperatures, nature of the
solvent, and counterions) can lead to substantial modifications of
the physical or chemical properties of the resulting materials. Ze-
olites can be synthesized to have distinct characteristics by modi-
fying experimental parameters, such as Si:Al ratio, Na2O/SiO2 mole
ratio, H2O/SiO2 mole ratio, crystallisation temperature and time,
etc. For example, by changing the Si:Al ratio on zeolite A from 1 to 2,
Cd uptake in zeolite increased from 17.8% to 94% (Ismail et al., 2010).
Wibowo et al. (2017b) also found an increased temperature from
100  C to 225  C led to disposal of organic substances that clog the
channels and increased dealumination, consequently it helped to
reduce the salinity in seawater, whereas a further temperature in-
crease from 225  C to 600  C resulted in decreased efficiency
possibly due to zeolite solidification.
5. Adsorption isotherms, kinetics and thermodynamics
As an important factor controlling the salt removal process,
adsorption reaction takes place to ensure the salt ions are held by
the zeolites. The adsorption characteristics of zeolites are deter-
mined from aspects of adsorption isotherm, thermodynamics and
kinetics. Information as such could entail whether the adsorption is
spontaneous or not; the type of adsorption process is physical or
chemical; the adsorption is endothermic or exothermic; and the
maximum adsorbent capacity, etc. Through understanding the
intrinsic nature of salt adsorption on zeolites, it enables researchers
1440 J. Wen et al. / Journal of Cleaner Production 197 (2018) 1435e1446

to better improve the adsorption capacities of zeolites through 2008).

altering synthetic routes or modifying zeolite's surface properties.
The adsorption isotherm models most frequently used for
interpreting the salt adsorption mechanism include Langmuir,
Freundlich, Temkin and Dubinin-Radushkevich models. Details of
the determining factors in each model are illustrated in Table 3. By
comparing the fitted research result with each isotherm model, one
would be able to identify whether the adsorption of Naþ ions onto
zeolite happens on homogeneous or heterogeneous surface. It has
been reported that the adsorption of Naþ on the clinoptilolites
originating from two locations in USA followed better with the
Langmuir model (Zhao et al., 2008). Similarly, the adsorption of Naþ
on a thermally activated zeolite followed the Langmuir type, sug-
gesting a monolayer adsorption (Wibowo et al., 2017a). Interest-
ingly, Gibb et al. (2017) found that Freundlich model provided a
good fit (R2 > 0.98) for Naþ adsorption on zeolites using a normal,
Cl containing wastewater; whereas the Langmuir model fitted
better for that using the same but dechlorinated wastewater. In a
study done by Ganjegunte et al. (2011), it is also clear from the data
that Freundlich model described best for the adsorption of Naþ
from CBNG water featuring in high concentrations of CO2 3 and
HCO þ
3 on Ca-rich natural zeolites. It implies that Na adsorption on
zeolites has a composition-dependent behaviour. If wastewater is
not pretreated to eliminate the effect of co-existing anions (e.g., Cl,
 þ
CO2
3 , HCO3 ), the adsorption of Na on zeolite normally followed a
multilayer adsorption on heterogeneous surface; by pretreating
wastewater (e.g., dechlorinating) prior to zeolite adsorption, the
uptake of Naþ on zeolite conformed to a monolayer adsorption on
homogeneous surface. The maximum adsorption capacities, SAR
reduction and adsorption pattern of Naþ adsorption on zeolites in
various studies were listed in Table 4.
Differences in adsorption by various zeolites can be attributed to
variations in the chemical and physical properties of zeolite (i.e.,
composition, pore size, surface area, surface charge, and sodium
affinity) (Zhao et al., 2008). A zeolite high in Ca2þ level does not
always lead to a high Naþ exchange and adsorption. For example,
the St. Cloud (ST)-zeolite with naturally higher Ca2þ concentrations
than that of Bear River (BR)-zeolite adsorbed less Naþ than the
counterpart, owing to the stronger occupation of Ca2þ in the ST-
zeolite. In comparison, a higher Kþ concentration in the BR-
zeolite suggested the preference for Kþ on the stronger adsorp-
tion sites, leaving Ca2þ bound to relatively weak adsorption sites
that facilitated the replacement by Naþ in CBNG water (Zhao et al.,
Regeneration of the spent zeolite material and recuperation of
adsorbed ions is essential for the sustainable use of zeolite in
wastewater salinity/sodicity reduction. If the adsorbed Naþ ions are
required to be easily eluted, the adsorption force between Naþ and
zeolites is thereby preferably not be too strong, in which case a
physical adsorption of Naþ on zeolites would be ideal. However, it
has been more frequently reported that the adsorption of salt ions
on zeolite followed the pseudo-second-order kinetic which nor-
mally agrees well with chemisorption as the rate controlling step,
including the adsorption of sea salts on clinoptilolite (Wibowo
et al., 2017a), adsorption of Mg2þ and Ca2þ on LTA zeolites (Xue
et al., 2014), and adsorption of Naþ from CBNG water on a Ca-
type clinoptilolite (Ganjegunte et al., 2011; Santiago et al., 2016;
Zhao et al., 2008). However, these researchers did not undergo
deeper analysis on the nature of chemisorption, i.e., coordination
interactions, acid-base reactions, or chemical bonding, etc. In
addition, the pseudo-second-order does not always guarantee a
chemical sorption. Wibowo et al. (2017a) showed that the
adsorption of sea salts on clinoptilolite was a physical adsorption
(with E < 8 kJ/mol) while following the pseudo-second-order ki-
netic model. They explained the adsorption of salt ions onto zeolite
surface by using electrical double layer (EDL) theory (Fig. 1). In this
theory, when zeolite particles are dispersed in salt solution, an
electrical double layer exists around each particle zeolite. The first
layer is occupied by strongly bound ions (stern layer), where zeo-
lites surface attracts positive ions through van der Waals force
(attraction potential, VA) and rejects negative ions through elec-
trostatic repulsion (repulsion potential, VR). If the electric charge of
zeolites is still strong enough to attract free ions, then the second
layer (diffuse layer) is formed with a weaker electric potential than
the first layer. Some positive ions can still be attracted to the second
layer even though the electric charge is diminished, because the
overall electric charge has not yet been balanced by the first layer
and is still negative. Outside the diffuse layer, the salt ions behave as
free ions while the ions and zeolite particles inside the diffuse layer
form a stable entity. Generally, the greater the total electrical charge
(VT¼VA þ VR, negative) of zeolite, the wider the diffuse layer that
will adsorb more salt ions. Once the total electric potential is
reduced to zero (i.e. zeta potential), the binding process is vanished
and adsorption process will be disappeared.
Thermodynamics is used to evaluate whether a process will
happen spontaneously by considering both energy and enthalpy

Table 3
Determining factors of adsorption isotherms.

Adsorption model* Description Determining factor Condition

Langmuir isotherm Based on assumption that the adsorption occurs on a homogeneous Separation factor RL: RL > 1, unfavorable adsorption;
qe ¼ kL Ce qmax= surface which each molecule own constant enthalpies and sorption 1 RL ¼ 1, linear adsorption;
1 þ kL Ce RL ¼
activation energy without interaction between adsorbed molecules; 1 þ k L Ci RL ¼ 0, irreversible adsorption;
monolayer adsorption. 0<RL < 1, favorable adsorption.
Freundlich isotherm Based on assumption that the adsorption occurs on a heterogeneous n n ¼ 1, linear adsorption;
1=n
qe ¼ Kf Ce surface with interaction between adsorbed molecules. n < 1, favorable adsorption;
n > 1, unfavorable adsorption.
The smaller of 1/n, the greater of
expected heterogeneity.
Temkin isotherm Based on assumption that the decrease in the heat of adsorption of all BT BT < 8 kJ/mol, physical adsorption
qe ¼ BT lnðAT Ce Þ molecules in the surface layer is linear; uniform distribution of binding
energies.
Dubinin-Radushkevich isotherm Based on Gaussian energy distribution onto a heterogeneous surface. Energy E: E < 8 kJ/mol, physical adsorption;
qe ¼ qs expð  bε2 Þ 1 8 < E < 16 kJ/mol, chemical
E ¼ pffiffiffiffiffiffi
2b adsorption.
*
where qe (mg/g) refers to the adsorption capacity at equilibrium; kL refers to equilibrium constant of Langmuir model; qmax (mg/g) refers to the maximum adsorption
capacity; Kf (mg/g) refers to Freundlich isotherm constant which is an approximation indicator of adsorption capacity; n refers to adsorption intensity; AT is an equilibrium
binding constant; BT refers to a Temkin isotherm constant; T (K) is the absolute temperature; R is the gas constant (8.314  10-3 kJ/K mol); qs refers to theoretical isotherm
saturation capacity; b refers to Duinin-Radushkevich isotherm constant; and ε refers to the Polanyi potential (J/mol).
 J. Wen et al. / Journal of Cleaner Production 197 (2018) 1435e1446 1441

Table 4
Comparison of Naþ adsorption parameters on zeolites.

Zeolite type Treated object Adsorption characteristics Adsorption capacity SAR Reference
qmax (mg/g) reduction

Clinoptilolite Seawater Physical, non-monolayer 51.43 e Wibowo et al.,

2017a
Acid-activated CSG water e 1.27 73.7%
Wang et al., 2012
clinoptilolite
Natural Ca-rich CBNG water Chemisorption 4.76e8.39 70.6%
Ganjegunte et al.,
clinoptilolite
2011
Clinoptilolite CBNG water Chemisorption 9.6e12.3 66.7%
Zhao et al., 2008
Acid-treated Brine-impacted water e 1.77 88.5%
Paul et al., 2017
clinoptilolite
Acid-treated Dechlorinated brine- Monolayer adsorption on homogeneous surfaces 24.4 70.7%
Gibb et al., 2017
clinoptilolite impacted water
Brine-impacted water Multilayer adsorption on heterogeneous surfaces e e
(chlorinated)
Natural zeolite CSG water Film, pore, and intra-particle diffusion 3.72 10.4%
Santiago et al., 2016
Ca2þ-modified zeolite 3.57 9.86%
Hþ-modified zeolite 4.69 12.46%
Kþ-modified zeolite 7.98 17.4%
NHþ4 -modified zeolite 8.43 22.3%
Bear River zeolite NaHCO3 solution Monolayer adsorption 21 e Belbase et al., 2013
NaCl solution 18 e
Bear River zeolite (1.3 Simulated CBNG water e 86%
e1.5 mm)
Zeolite X Seawater Favorable adsorption e ~40%
Kwakye-Awuah
et al., 2016
Australian natural Simulated CSG water Intra-particle diffusion and others control rate; 10.3 e Millar et al., 2016
zeolite (NaHCO3) monolayer adsorption
Simulated CSG water (NaCl) 6.4 e
Actual CSG water 2.1 e

entropy (DS ) (kJ/mol$K). The negative value of DG indicates a

spontaneous nature of adsorption; the negative value of DH in-
dicates the adsorption process is exothermic, inversely it is endo-
thermic, and the absolute value of DH lies in the range of
2.1e20.9 kJ/mol for physical adsorption and 80e200 kJ/mol for
chemical adsorption; the negative value of DS indicates the
configuration of the adsorbate on zeolite surfaces is less random.
The adsorption of various adsorbates on zeolites has been
repeatedly reported with a negative DG value, indicating the
adsorption process is spontaneous in nature (Runtti et al., 2017;
Wibowo et al., 2017a). The adsorption of various adsorbates on
zeolites were reported to be either exothermic (Günay et al., 2007;
Wibowo et al., 2017a) or endothermic (Runtti et al., 2017), but the
thermodynamic property during the adsorption of Naþ on zeolite
has scarcely been reported. In a study done by Wibowo et al.
(2017a) using a clinoptilolite for the reduction of seawater
salinity, a negative DH value (i.e., 16.71 kg/mol) indicated the
adsorption of Naþ on the zeolite was of exothermic nature, and a
negative DS value (i.e., 0.0116 kg/mol$K) indicated the configu-
ration of sea salts on the zeolite surface was less random due to
physical sorption.

6. Salt storage vs. salt exchange

Zeolites can actually store salt in their porous structure because

Fig. 1. Illustration of the adsorption mechanism of salt ions onto zeolite surface
(Reprinted with permission from reference Wibowo et al. (2017a). Copyright 2017.
Desalination).
factors. The thermodynamic parameters used to determine the
adsorption processes include the changes in standard free energy
(DG ) (kJ/mol), standard enthalpy (DH ) (kJ/mol) and standard
of the crystalline characteristics. This is attributed to the salt
accumulation happening on zeolite's surface and cavities. Sherry
(2003) has well explained the phenomenon of salt storage in zeo-
lites: the concentration of Naþ ions in the large cavities of a zeolite
NaA is extremely high, much higher than can be achieved in an
aqueous solution of NaCl. When the zeolite NaA is immersed in a
NaCl solution there is a thermodynamic driving force for Naþ ions
1442 J. Wen et al. / Journal of Cleaner Production 197 (2018) 1435e1446
to diffuse into the aqueous solution because of the concentration
gradient between the zeolite and solution phase. Likewise there is
also a thermodynamic driving force for Cl to diffuse into zeolite.
The diffusion of cations (i.e., Naþ) into the solution and anions (i.e.,
Cl) into the zeolite results in the accumulation of negative charge
in zeolite and positive charge in the solution. The first few diffusing
ions cause an electric potential difference, called Donnan potential,
to exist in between the two phases where no semipermeable
membrane was actually present, which was also found in the study
of Bhandari (1998) where the establishment of Donnan potential
was between a base resin and an acid solution due to the ion ex-
change process. Donnan potential pulls the cations into the zeolite
and anions back into the solution, hence the inhibition of the
ingress of anions into zeolite channels would result in accumula-
tion of them in solution (Millar et al., 2016). Although both salt
storage and salt exchange are controlled by salt concentration, the
influences are distinctly different. Zeolite does not exhibit strong
cation selectivity in salt storage, and salt storage increases with
increasing salt concentration because the concentration gradient
will eventually overwhelm the Donnan potential (Sherry, 2003). It
is distinctively different from the ion exchange in which the
selectivity increases with decreasing salt concentration if the
ingoing cation has a higher charge than the outgoing cation (Sherry,
2003).
7. Assessment of zeolite application in wastewater industry
7.1. Challenges: economic considerations
7.1.1. Commercial synthesis of zeolite and likely cost
Synthetic zeolites offer greater exchange capacities and wider
range of properties than their counterparts (i.e., natural zeolites)
(Mondale et al., 1995). Due to the huge demands in water industry,
synthetic zeolites have taken a great role in the water treatment
market. Every year, more than 100 zeolites are manufactured across
the globe (Deshmukh, 2014). Zeolite can be synthesized with SiO2
higher or lower than in nature for the same framework type. Higher
SiO2 generally gives greater hydrothermal stability, stronger-acid
catalytic activity, and greater hydrophobicity as adsorbents
(Sherman, 1999). Lower SiO2 gives greater cation exchange capacity
and higher absorbance for polar molecules (Sherman, 1999).
Therefore, synthetic zeolites having lower SiO2 content are used in
wastewater treatment where cation exchange plays the major role.
Synthetic zeolites can also be composited with other materials to
overcome its shortage as being too small for application in WTP. By
synthesizing clinoptilolite upon an expanded lamella matrix
(vermiculite), the resulted composites showed comparable hy-
draulic conductivity and grain size (2e5 mm) to the natural zeo-
lites, yet the rate of adsorption and maximum coverage were
improved by 4 times (Johnson and Worrall, 2007).
As discussed above, if zeolites were to be used for reducing
sodicity in wastewater treatment, the zeolite bed should be loaded
with more Ca2þ, Mg2þ or NHþ þ
4 rather than Na . Zeolite of this kind
could be either synthesized or modified from its Na form. The
preparation of Ca-type zeolites involves a few steps of ion exchange
reactions. For example, Ji et al. (2007) described the process of
preparing CaY zeolite: at first the natural clinoptilolite was treated
with saturated NaCl solution at boiling point for 2 h, and then the
resultant NaY was changed to NH4Y by washing it with NH4Cl at
room temperature, and finally the CaY zeolite was prepared by
washing the NH4Y with Ca(OH)2 at boiling point for 2e3 h. When
the Ca-type zeolite is used in the wastewater treatment, the ex-
change capacity would still be affected by the Ca loading level. In a
NaeCa competitive experiment, it was shown that Fort LaClede
clinoptilolite preferentially took up Ca2þ over Naþ at low to
moderate loadings of Ca2þ (<80% Ca), and the preference for Ca2þ
was greater at a higher temperature (63  C). However, the prefer-
ence was reversed above this loading (>80% Ca) and at lower
temperature (30  C) (Hulbert, 1987). This indicates that the syn-
thesis or modification of Ca-type zeolites should be performed at a
relatively high temperature with low to moderate loadings of Ca2þ.
Synthetic zeolites have a huge market due to their multiple uses.
Bear River Zeolite, Luoyang Jianlong Chemical Industry Co. Ltd.,
Anten Chemical Co. Ltd., and WR Grace among others are the main
producers of synthetic zeolites (Deshmukh, 2014). By 2008, the
world production of synthetic zeolites was already estimated to be
about 1.4 million metric tons per year. The likely cost of synthetic
zeolites varies according to their purposes of application, which can
range up to US$100 per pound or US$2,000,000 per metric ton
(Bearriverzeolite, 2017). This is much dearer than natural zeolites
which have average prices ranging from US$40 to US$900 per
metric ton, according to the US Geological Survey. In addition, the
energy consumption, waste treatment and disposal all add up the
overall cost of application of synthetic zeolites, thereby hindering
its wider application than natural zeolites in global market. How-
ever, if the spent zeolites used in other applications (such as the
zeolites used after water softness) are explored and employed
locally, regionally or nationally, it would significantly reduce the
treatment cost.
7.1.2. Regeneration ability
Regeneration ability of zeolite is considered an important aspect
to determine the lifespan and overall cost of its use in wastewater
treatment. Simply, the regeneration process is another ion ex-
change reaction, generally with a high concentration of desorption
solution at high temperatures.
For sustainable operation of the process, zeolite's exchange ca-
pacity should not be compromised during the regeneration process.
The electrochemical regeneration of zeolites with the objective of
removing ammonia (NH3) from water was investigated by Lei et al.
(2009). They pointed out that the synthetic zeolites could be
completely regenerated even after the regeneration solution was
used for five times, and 96% of the by-product NH3 was converted
into N2 (Lei et al., 2009). An even higher regenerability was
observed in the study of Huang et al. (2015) where no obvious
deterioration tendency was observed for NHþ 4 removal perfor-
mance of zeolite even after 20 operational cycles. Though zeolites
used in water desalination was reported to be easily regenerated by
washing with alkaline solution (e.g., CaCl2) (Taulis and Milke, 2009;
Zhao et al., 2008), the regenerability of zeolites was rarely exam-
ined in many other studies.
Traditional regeneration method using Ca(OH)2 or CaCl2 solu-
tions at high pH may be time and energy consuming, and the waste
products could result in secondary pollution that needs further
treatment. Therefore, some researchers proposed biological
regeneration to be an alternative approach to restore zeolite's
adsorption and exchange ability (Lahav and Green, 1998; Wen et al.,
2006). Biological regeneration refers to the growth of nitrifying
biofilm on the surface of zeolite, and the so-called bio-zeolite acts
as the ion-exchanger and growth media for microorganisms. The
mechanism was identified to be NHþ 4 release by ion exchange fol-
lowed by nitrification of the liberated NHþ 4 (Semmens, 1979). Ac-
cording to this, biological regeneration seems to be only effective
and applicable in treating NHþ 4 -loaded zeolites. For zeolites
exhausted in sodic wastewater treatment which are saturated with
excess Naþ, bio-regeneration is currently unable to be established
because Naþ cannot be transformed to others through microbial-
assisted biochemical reaction. Therefore, there is a difficulty of
developing a biological regeneration technique for zeolites
exhausted in water desalination process, which hinders the
 J. Wen et al. / Journal of Cleaner Production 197 (2018) 1435e1446
application of such in a green and sustainable manner.
The salt-saturated zeolites can alternatively be used directly
(without regeneration) in another application. For example, a so-
lution high in Kþ ions should also exchange the Naþ ions from the
zeolite, but then the zeolite might not be useful for further filtration
of NH3 and Naþ ions as the Kþ would likely be retained within the
zeolite structure (Guo et al., 2013). The zeolite could be used as soil
amendment to act as a K fertiliser. Moreover, zeolite has been used
to exchange NHþ þ
4 and K from urine collected by urine separating
toilets that are popular in Scandinavian countries (Beal et al., 2007)
and Australia (Ganrot et al., 2007a, b). If zeolite is flushed with
urine, it is theoretically possible that NHþ þ
4 and K in the urine
would exchange with Naþ in the zeolite. This would produce a
zeolite soil amendment high in nitrogen (N) and K and a liquid
trade-waste with a significant Naþ concentration (Beler-Baykal
et al., 2011). These means of reusing discarded zeolites from
wastewater industry should be greatly encouraged in regions and
areas where soil fertility is depleted and cost-effective approaches
are required.
7.2. Opportunities: technical improvement
It has long been discussed that the cation adsorption capacity
and selectivity by zeolites are influenced by factors such as cation
valence, hydration degree, ion concentration, number of adsorption
sites, mineral purity, initial composition, and degree of accessibility
(Zhao et al., 2008). Here we focus on those operational factors
aiming to improve salt adsorption on zeolites, which at the same
time may alter one or more of the above-mentioned classic factors.
The existing and on-going developed techniques significantly
impact the future trend of using zeolites in wastewater industry.
Meanwhile, problems occurring in the techniques provide chal-
lenges and opportunities for future research.
7.2.1. Pretreatment/modification
Because natural zeolites normally have limited adsorption ca-
pacity, they are usually subject to various pretreatment/modifica-
tion procedures to improve their adsorption capacity and purity.
For instance, a natural clinoptilolite was modified either chemically
(changing time duration of NaOH treatment) or mechanically (ball
to powder mass ratio in wet ball milling) to increase its NHþ 4 and side-products in the process. Though dual adsorption is
retention capacity (Jha and Hayashi, 2009). Through the surface
modification by NaOH, zeolites were mostly the Na-type which
favours the exchange for NHþ 4 in the wastewater (Jha and Hayashi,
2009). For zeolites used to treat salinity in various water systems,
acid treatment (e.g., HCl, H2SO4) is perhaps the most widely
adopted method due to its multi-function in zeolite modification.
Firstly, the acid treatment causes the partial breakage of AleOeAl
and SieOeAl linkages through dealumination (as shown by an
increased Si/Al molar ratio), then the dealuminated AleOe and
SieOe links become possible sites for Naþ/Hþ ion exchanges; sec-
ondly, acid treatment and associated modification procedure that
involves mixing and thermal treatments may cause increases in the
surface area and particle porosity by washing out of impurities as
well as opening blocked pores and cracks (Paul et al., 2017; Wen
et al., 2016); thirdly, some native exchangeable cations will be
replaced by protons, resulting in the transition of the zeolite to its
near-homoionic H-form (Gibb et al., 2017). Through pretreatment
with 0.1 M acetic acid or chloric acid, the modified zeolites reduced
the SAR of CSG water from 70.3 to below 15 (Wang et al., 2012).
Some researchers proposed the use of salts opposite to acids to pre-
condition zeolite (Santiago et al., 2016). They found that by treating
the natural zeolite with a series of acids and salts, such as CaCl2, KCl,
HCl, or NH4C2H3O2, the Naþ adsorption capability was in accord
with the order of NHþ þ þ 2þ
4 >K >H >Ca . Recently, Ates and Akgül
1443
(2016) found that high concentrations of NaOH led to structural
deformation and serious desilication and dealumination of cli-
noptilolite, which further gave rise to increased adsorption capacity
of manganese. Though alkali pretreatment has not been attempted
for Naþ removal by zeolites, this could be an area worth exploring
in future studies.
Owing to the Naþ/Hþ exchanges, the effluent treated with ze-
olites would have decreased pHs. In order to reduce the effluent
acidity after treatment, zeolites are often subject to post-
conditioning using alkaline solutions such as Ca(OH)2. The
Ca(OH)2 post-conditioning may produce potential functional sites
for pH neutralization in the zeolite (e.g., >AleOeCaeOH and
>SieOeCaeOH). A schematic diagram showing the processes of
Naþ removal and neutral-water generation is shown in Fig. 2. In this
way, the generated wastewater effluent would normally be slight
acidic to slight alkaline, thus being more acceptable to environ-
mental endpoints.
7.2.2. Dual adsorption
If Naþ is removed from wastewater stream through cationic
exchange, its accompanying anions such as Cl, NO 2
3 , SO4 and
3
PO4 would still remain in the system. Therefore, some scientists
proposed using anionic adsorbents in combination with cationic
adsorbents to remove the salts completely from the system. This
dual adsorbent system, initially developed by Pless et al. (2006),
comprised an anion-exchange material (i.e., hydrotalcite) and a
cationic-exchange material (i.e., amorphous aluminosilicate per-
mutite). These ion exchangers eventually desalinate a brackish
water which was further used directly in rangeland or industrial
applications. Gibb et al. (2017) used a dual adsorbent containing
calcined and reconstructed layered double hydroxide (CLDH)
minerals and acid-treated zeolite (H2SO4, HCl, HNO3, 1 M) to
desalinate a brine-impacted groundwater dominated by Naþ, Kþ,
and Cl. The CLDH consists of positively charged brucite-like sheets
with anions occupying the interlayers and can be used to remove
anions and divalent ions. Through employing the dual adsorbents
in the treatment, the concentrations of Naþ, Kþ, and Cl were
reduced by 87, 97, and 87%, respectively (Gibb et al., 2017). Dual
adsorbents used in these desalination processes are thereby
considered a cost- and energy-efficient method for the lack of salt
implemented in practical terms, Naþ and accompanying anions are
removed in separate steps, which may lengthen the operation
process and exhaust more energy. Modifying zeolites to simulta-
neously remove cations and anions is perhaps the next target of
technical improvement, which will augment the material's effi-
ciency while minimizing operational cost.
7.2.3. Zeolite-based membrane and composite materials
Zeolites can be composited with other functional materials so
that they are tailored for special demands. For example, zeolites
have been incorporated with zero-valent iron (Kim et al., 2013;
Kong et al., 2016) or chitosan (Wan Ngah et al., 2013) for the
removal of heavy metals from water, incorporated with TiO2 for
abatement of organic pollutants, such as formaldehyde, phenol,
methyl orange and rhodamine B (Zhang et al., 2018), incorporated
with geopolymer for CO2 capture (Minelli et al., 2018), and so on.
Zeolites incorporated with other materials have not been exten-
sively studied for their potential in salinity/sodicity reduction.
Novel adsorbents with exceptionally high surface area and
adsorption capacities (e.g., metal organic frameworks, nano mate-
rials, etc.) are thus worthy exploring for the potential of cooperating
with zeolites in water desalination.
To facilitate the use of zeolite for desalination in a wider range,
zeolites have also been incorporated with membrane technique to
1444 J. Wen et al. / Journal of Cleaner Production 197 (2018) 1435e1446
Fig. 2. Conceptual diagram for the acid treatment, Ca(OH)2 post-treatment, and adsorption-pH neutralization (Reprinted with permission from reference Paul et al. (2017).
Copyright 2017. Desalination).
treat water of high salinity (An et al., 2014; Swenson et al., 2012;
Cay-Durgun et al., 2017; Zhu et al., 2013, 2015). Natural zeolites
machined into thin membranes efficiently rejected 99.99% Mg2þ,
98.52% Ca2þ, and over 97.5% Naþ and Kþ in synthetic seawater
(Swenson et al., 2012). An et al. (2014) further improved water flux
through the zeolite membrane by incorporating it with phosphate
and achieved over 95% removal of Naþ. Nevertheless, the challenge
remaining in the zeolite-embedded membrane technique is that
water molecules and ions can penetrate zeolite's intercrystal defect,
thus making it difficult to determine the role that zeolite have in
water transport and salt rejection, and lower the salt rejection ef-
ficiency (Humplik et al., 2011). To overcome the difficulty, Humplik
et al. (2017) developed the zeolite-membrane by inclusion of hy-
drophobic sub-nanometer pores. However, it is still unclear
whichever transport resistances (e.g., surface barriers, pore
collapse or blockage due to contamination) limited the rejection
performance as compared to molecular simulation. Methods that
can help direct and limit the transport of salt ions to the intrinsic
zeolite pores are thereby the potential research focus of the tech-
nology. In addition, evaluation of the membrane performance un-
der extreme conditions (e.g., temperature, pH, chemicals, etc.) is
needed in future research.
8. Conclusion and future outlooks
With an increasing demand of water usage yet degrading water
quantity and quality worldwide, it has never been less urgent to
develop wastewater recycling strategies for a sustainable environ-
ment. However, the high dissolved solids concentration causes
most wastewater to have salinity and sodicity levels. Over the years,
efforts have been made to reduce salt levels down to acceptable
ranges. Nevertheless, some of the techniques are not economically
viable due to high cost. This review summarizes the application of a
cleaner, effective and cost-friendly sorbent e zeolite in various
saline/sodic wastewater treatments over the last 50 years. Results
show that natural or modified zeolites effectively reduce water
salinity through ion exchange, adsorption, and salt storage. Results
also indicate that although modified and synthetic zeolites take a
big share in market due to their optimized exchanging capacity and
adjustable properties, manufacturing cost is still a hindering factor
for large-scale application. Application of zeolite in wastewater
industry also faces a difficulty of increasing reusability (or regen-
erability) while maintaining a low operational cost. Nevertheless,
continuing technical improvements would provide strong support
for sustainable development of the technique, including upgrade in
modification/synthesis procedure and incorporation of cutting-
edge technologies. Future outlooks for the use of zeolite in waste-
water treatment include, but not limited to, the following aspects:
1. Use of natural zeolites for removal of Naþ in CSG water and
seawater has been successful, yet large scale application of
natural or modified zeolites for Naþ removal from domestic
wastewater has scarcely been reported. Laboratory and field
trials using domestic wastewater are thereby needed to evaluate
zeolite's salt removal performance;
2. Future research may focus on modification methods to produce
zeolites highly selective for salinity/sodicity removal. Though
dual adsorption is implemented in practical terms, Naþ and its
accompanied anionic species are removed in separate steps.
Modifying zeolites to simultaneously remove cations and anions
will largely increase the efficiency of the material and reduce the
operation cost;
3. Combination of zeolites (mesoporous) and state-of-art nano-
technology (microporous) to improve material's adsorption ca-
pacity and reusability is an area worth exploring in future
studies;
4. Challenges still remain in the zeolite-incorporated membrane
technique as the exclusion of salt ions by intrinsic zeolite pores
is interfered by inter-crystal defect, surface barrier, pore
contamination, etc. To overcome the obstacle, a deep analysis of
ion transport mechanism through zeolite membrane and
improvement of membrane performance to maximize water
permeability and salt rejection is needed;
 J. Wen et al. / Journal of Cleaner Production 197 (2018) 1435e1446
5. Capital cost of using modified or synthetic zeolites in waste-
water industry is of paramount importance to determine its
applicability in real situation. Synthetic zeolite being too small
and more costly than its natural counterpart is not a preferential
option in desalination process, while modifying natural zeolites
using expensive chemicals also increases the operational time,
energy and cost. Further efforts should be made to consider
these aspects while optimizing the regenerability of zeolites,
thus maintaining its effectiveness and longevity in water
treatment.
Acknowledgement
This work was supported by the National Natural Science
Foundation of China (No. 51409099).
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