Journal of Water Process Engineering 33 (2020) 101104

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Journal of Water Process Engineering

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Facile and affordable synthetic route of nano powder zeolite and its T
application in fast softening of water hardness
Safaa El-Nahasa, Ahmed I. Osmanb,*, Abdulrahem S. Arafatc, Ala'a H. Al-Muhtasebd,*,
Hassan M. Salmana
a
Chemistry Department, Faculty of Science, South Valley University, Qena, 83523, Egypt
b
School of Chemistry and Chemical Engineering, Queen’s University Belfast, David Keir Building, Stranmillis Road, Belfast, BT9 5AG, Northern Ireland, United Kingdom
c
Red Sea Company for Drinking and Wastewater, Hurghada, Egypt
d
Department of Petroleum and Chemical Engineering, College of Engineering, Sultan Qaboos University, Muscat, Oman

A R T I C LE I N FO A B S T R A C T

Keywords: Herein, we proposed an affordable and facile way of treating the hardening of water from local groundwater and
Synthetic zeolite seawater sources. This was facilitated by synthesizing zeolitic materials via an effortless and affordable method
Hardness elimination from readily available disposed of waste materials. Firstly, by converting waste aluminium (scrap wire cables,
Ion exchange takeaway foil, cans, and spray aerosol bottles) along with disposed of silica gel into active zeolitic materials with
Seawater
the aid of a conventional domestic microwave. Small amounts of the produced zeolites (NaX and NaA) were
Groundwater
utilized in the removal of the hardness of water (10 g.L−1), showing elimination of Ca2+ and Mg2+ ions within
Regeneration
Aluminium waste 30 min, removing 90 % of the total hardness (> 1000 ppm). The spent zeolite samples can be further used for
Water hardness more than two consequent cycles, then the regeneration can be promoted by using NaCl solution at ambient
conditions. The total price for the synthesis of 1 kg of the zeolite produced herein is 14 $/kg. This is 70 % lower
than the price of commercial zeolites available in the market. Our proposed facile route in zeolite preparation
could potentially change the traditional costly softening treatment techniques. It also minimizes the use of extra
chemical materials, templates and multi-step procedures. The excellent hardness removal capacity in ground-
water and seawater using synthesized zeolite samples could open doors for various applications.

1. Introduction plants, especially for hardness removal. One of the main disadvantages
of this process is the generation of a large amount of discarded mate-
Nowadays, great focus has been drawn towards water pollution rials, as well as the necessity for re-carbonation of the used water [1,2].
globally as all living beings are in continuous need of water. In almost The most traditional methods for groundwater or wastewater
all developing countries, groundwater is the most used water supply for treatment include chemical precipitation, ion-exchange, chemical re-
safe drinking water. High level of minerals in water resources adversely duction, filtration, evaporation, flocculation, solvent extraction, ad-
affects human health. In addition to this, it can prevent water appli- sorption by activated carbon and other sorbents, electrodialysis, and
cations in many other disciplines. Two major cationic elements in the membrane separation methods. At present, desalination can be em-
form of calcium and magnesium are the primary reasons that lead to ployed as an accessible solution for managing the long-term needs for
water hardness. These ions can also cause clogging of a piping chassis drinking waters. Reverse osmosis (RO) and nanofiltration membranes
due to scale formation which, consequently, reduces the flow of water (NF) are the commonly known and preferred methods for desalination
inside the pipe causing serious operational issues. It is well known that and softening of water [3]. Currently, over than 80 % of countries
the foamy characteristic of soap and detergent is extremely reduced by worldwide utilize membrane technologies in operation for desalination
the hardness of the water. Furthermore, corrosion caused by hard water of seawater [4]. NF or RO membranes have high selectivity for the
lowers the lifespan of the internal surface network of equipment and removal of divalent ions and decreasing the high dissolved solids con-
heaters used in industry. Hard water containing more than 500 mg.L−1 tent of saline water [5]. Also, electrochemical methods are utilized in
is not suitable for consumption in most household applications. water softening, and, the final electro-precipitate structure highly de-
Quicklime and washing soda are used profusely in water purification pends on the initial water composition [6,7].

⁎
Corresponding authors.
E-mail addresses: [email protected] (A.I. Osman), [email protected] (A.H. Al-Muhtaseb).

https://doi.org/10.1016/j.jwpe.2019.101104
Received 11 September 2019; Received in revised form 17 November 2019; Accepted 7 December 2019
Available online 14 December 2019
2214-7144/ © 2019 Elsevier Ltd. All rights reserved.
S. El-Nahas, et al. Journal of Water Process Engineering 33 (2020) 101104

Ion exchange treatment is considered one of the most frequently low temperature has been used. Thus, no additional energy-intensive
utilized methods for solving the water hardening issue and is very ac- process in the form of temperature is needed to valorize the raw waste
tive in the elimination of several elements. Also, some low-cost and eco- materials. Consequently, the synthesized zeolites were utilized to re-
friendly ion exchanging materials are used such as modified pinecone, move the hardness of water in groundwater well. This can affect human
sugarcane bagasse or coffee husk. They usually are utilized at a low health and fulfil specific Sustainable Development Goals (SDGs) such as
concentration level of total hardness as in the work of Werkneh et al. the human health (goal no. 3), clean water (goal no. 6) and responsible
with a calcium concentration of 120 mg.L−1, while in Altundoğan et al. consumption and production (goal no. 12). This helps industry and is-
work it was 230 mg.L−1 [8,9]. The main advantages of ion exchange sues in general, as the water hardness can produce scaling and scale
materials are their selectivity, efficiency, less residual from sludge build-up in pipes which causes clogging. Furthermore, utilization of the
production, and can also be regenerated and reused effortlessly. Cation synthesized zeolite in the pre-treatment step in seawater desalination
exchange is an alternative process to the use of lime in hard water can help prolong membrane lifespans. The synthesized zeolites can also
softening. In most water treatment plants, cation exchange resin is be regenerated and help facilitate the circular economy of the materials
commonly used in a fixed bed reactor vessel at the end of a treatment contained within the zeolite as they can be directly reused again with
process [10]. A well-known disadvantage of saturated ion-exchange high value and performance for 2–3 runs. Herein we maintain the
resins is their high power-consumption of supplies needed for period- synthesized zeolites, and this is ideal for the circular economy as no
ical regeneration [11]. energy leakage or down-cycling occurs.
Numerous categories of ion exchange materials are commercially
available and renowned as resins or zeolites [12]. Zeolites are con- 2. Materials and methods
sidered as micro-porous minerals which have the capability to exchange
ions. Zeolite materials are unique when comparing to other inorganic 2.1. Chemicals and reagents
oxides due to its properties like strong ion exchangeability, high
thermal stability with high temperature, the micro-porous character- Discarded aluminium waste materials (scrap wire cables, takeaway
istic with uniform pore dimensions, ability to evolve interior acidity, foil containers, cans and spray aerosol bottles) were obtained from our
and intensity of internal surface area. Owing to their cage-like con- local recycling centre in Egypt. Firstly, the raw aluminium waste was
struction, zeolites are used as water softeners or ion exchangers. cut into consistent size and homogenous pieces to increase the surface
Zeolitic materials are a group of substances with a rationally de- area-to-volume ratio of the particles, maximizing the reaction rate with
signed pore framework and active sites distribution. Synthetic zeolites NaOH. Furthermore, disposed of silica gel particles were used without
have some advantageous properties over the natural analogues. The any further purification or milling process.
synthetic materials are manufactured in a regular pure phase. It is also The stock solutions of Ca2+ were 4000 mg. L−1. The desired pH
possible to produce different zeolite structures contrary to naturally values of solutions were fixed by either 0.1 M NaOH or 0.1 M HCl.
occurring zeolites. The basic chemical structure of zeolite is hydrated Sodium hydroxide was analytical grade and used as received.
crystalline aluminosilicate with the formula Na2O.Al2O3.nSiO2.xH2O
[13]. Zeolites are categorized based on the ring size and their pore 2.2. Method for synthesized zeolite samples
diameter. Among zeolitic materials, Zeolite-A contains 8 rings and
possesses pore diameters in the range of 3−5 Å [14]. Furthermore, The method for the 6 synthesized zeolite samples (101Z to 106Z) is
faujasite X and Y have 12 rings with a larger pore diameter of 7−8 Å. outlined in Fig. 1 below and is described as follows:
Zeolite-X, Zeolite-A, and Zeolite-Y are classified under the same family Solution 1): the different raw aluminium sources (scrap wire cables,
of zeolites due to their crystallographic units required to construct their takeaway foil containers, cans, bottles and two types of spray aerosol
structures [15]. The Si/Al ratio is responsible for the chemical com- bottles [105R&106R]) was dissolved in 10 % NaOH solution whilst
position of the zeolite type and strongly affects the selectivity for continuously stirring to obtain sodium aluminates (NaAlO2) solution.
sorption species [16]. Then after filtration, a clear solution was produced. Solution 2):
Zeolite A does not form naturally in nature but can be industrially Disposed of silica gel was dissolved in 10 % NaOH to produce sodium
produced. Synthetic zeolites have received great attention globally for silicates (Na2SiO4) solution. Solution 2 was added to solution 1 slowly
their wide application of molecular sieving in gas and liquid phases with continuous stirring until a white homogenous precipitate was
systems [17]. Synthetic zeolites are distinguishable in that they contain formed. The gel was stirred under magnetic agitation for 1 h before
a high surface area and possess great ability for ion exchange compared transferring the gel into a domestic home microwave for only 15 min at
with natural zeolites [18]. There are many methods for zeolite synthesis 170 W. All synthesis was achieved at a fixed temperature (25 °C), except
using different chemical reagents such as bases, sodium aluminates and sample 104 Z, which was carried out at a very low temperature of ∼
sodium silicate. These methods are costly and sometimes not econom- 5 °C (in an ice bath). The resulting zeolite sample was aged for 20 h at
ically viable [19]. Whereas, there is great global demand on conversion 40 °C. Finally, the collected zeolites were filtered, rinsed with de-io-
of waste and disposed of materials (e.g. aluminium waste) to resources. nized water, and then dried at 110 °C overnight.
These can be used in innovative applications and help locate more
economically viable materials for desalination of water sources (i.e. 2.3. Characterization
groundwater and seawater) [20]. Most developed countries have a
throwaway culture of waste materials and this has a negative impact in The synthesized zeolite samples were characterized by various
terms of environmental issues that are associated with increasing the analytical devices such as FTIR (Fourier Transform Infrared) of which,
landfills of disposed of materials [21]. Recycling of Al waste to more measurements were taken by a (Nicolet) Magna-FTIR – 560 (USA) with
beneficial products was reported by Osman et al. for the successful KBr technique. Powder X-ray Diffraction Analysis (XRD) of the zeolite,
conversion of Al foil to useful γ-Al2O3 which was used as an acidic aluminium raw materials and Ca-zeolite samples were detected by a
catalyst [22]. Furthermore, El-Nahas et al. showcased the recycling and Brucker Axs-D8 Advance Diffractometer (Belgium) at ambient tem-
valorization of Al building wire scraps (AlBWS) and Al takeout food perature in the 2θ range between 10°-70°. TGA and DSC curves were
container waste (AlTFC) to active alumina for the removal of nitrate used with an automatic recording model (50H Shimadzu thermal ana-
ions from water supplies [23]. lyser, Japan). While the morphology and elemental analysis of the
Herein we synthesized zeolitic materials using a facile and afford- synthesized zeolite was characterized using SEM & EDX (Model FEI
able process from readily available and abundant aluminium waste. INSPECT S50) operating at 20 kV. BET was utilized for surface area
During the preparation procedure, a domestic microwave along with measurements, total pore volume and pore radius. These were

2
S. El-Nahas, et al. Journal of Water Process Engineering 33 (2020) 101104

Fig. 1. Method for preparation of zeolite samples (101Z-106Z).

determined by Automatic ASAP 2010 Micromeritics sorptometer (USA) 2.5. Study of point of zero charge (PZC)
at liquid nitrogen temperature (77.350 K) (Quanatachrome
Instruments, version 11.04). XPS was performed in a Thermo-Fisher 0.1 g of dry zeolite sample was added to 50 mL of an aqueous so-
Scientific Instruments (East Grinstead, UK) with a quartz mono- lution of NaCl (0.01 M), then the pH was adjusted in the range of 2–10
chromator Al Kα radiation of energy 1486.6 eV. For construction and and stirred for 2 h. The suspension was kept for 48 h at room tem-
fitting of synthetic peaks of high-resolution spectra, mixed Gaussian- perature to reach equilibrium, then the final pH was measured derived
Lorentzian functions with a Shirley-type background subtraction were from the methodology described elsewhere [25]. Calculated ΔpH was
used. according to equation (ΔpH = pHi – pHf) and then ΔpH was plotted
versus pHi.

2.4. Adsorption studies

2.6. Regeneration of zeolite samples
2+
For purposes of studying sorption of Ca ions onto tested zeolite
0.5 g of the spent materials after calcium adsorption was left in
samples, the sorption experiments occurred under the batch mode, se-
contact with 100 mL of 1 M of NaCl overnight. The spent adsorbent was
parately because of its simplicity, reliability and ease to extrapolate at a
filtered, washed, and dried at 40 °C.
larger scale for practical application. The adsorption experiments ex-
amined the individual effects of initial concentration (1000–4000 ppm),
pH (2–10), contact time (1–180 min), adsorbent dosage (0.05 – 0.7 3. Result and discussion
gm.50 ml−1) and operating temperature (25–60 °C) have on the re-
moval efficiency of Ca2+ by the synthesized zeolite. 0.5 g of zeolite 3.1. Characterization of the synthetic zeolite
samples were mixed with 50 ml of known Ca2+ solution in closed vials,
continuously shaking at different time intervals to attain equilibrium at 3.1.1. XRD analysis
room temperature. The solutions were filtered, and the final Ca2+ The XRD results revealed the composition and the proper structure
concentrations were determined according to the standard method for of the tested zeolite samples. The raw materials of Al waste (scrap wire
23nd Edition no: 3500- Ca B [24]. The percentage of Ca2+ adsorbed by cables, takeaway foil containers, cans and two types of spray aerosol
the zeolite materials was calculated by the following equation [1]: bottles [105R & 106R]) were examined by XRD analysis. The results are
presented in Fig. 2a, while the composition of the synthetic zeolite in
(Co − Ce ) this work is shown in Fig. 2b. Based on the XRD pattern, the result
% Remova l= × 100
Co (1) detected only pure synthetic aluminium sheet for all types of raw ma-
terials of aluminium waste according to (JCPDS card no.: 04-0787). The
The value (qe) (mg. g−1) denotes the amount of the adsorbed Ca2+
XRD analysis obtained for zeolite (101Z, 102Z, 103Z, 104Z, 105Z and
onto the zeolite and was calculated according to the equation:
106Z) in Fig. 2b confirmed and matched the standard card for the
(CO − Ce ) V chemical structure of zeolite type X, A and Y. The major constituent
qe = ⋅ phase structure was recognized as a mixture of crystalline phase of
m 1000 (2)
zeolite A and X according to (JCPDS no.: 38- 0241), (JCPDS no. :39-
Where, the Co and Ce are the initial metal ion concentration and the 0222) and (JCPDS no.:83- 2319), respectively. Zeolite A had the highest
final metal ion concentration at equilibrium (mg.L−1), respectively. m intensity among all XRD peaks for all samples (101Z-106Z), and the
is the mass of adsorbent dose (g) and V is the volume of the solution characteristic peaks of zeolite A at 2θ values were 7.2°, 10.3°, 12.6°,
(mL). 16.2°, 21.8°, 24°, 26.2°, 27.2°, 30°, 30.9°, 31.1°, 32.6°, 33.4° and 34.3°.

3
S. El-Nahas, et al. Journal of Water Process Engineering 33 (2020) 101104

Fig. 2. XRD pattern for a) raw aluminum waste b) synthesized zeolite samples.

Table 1
Chemical structure, phases and the crystallite size for synthesized zeolite samples.
Sample name Major phase Produced phases Chemical structure JCPDS card Crystal shape Crystallite size nm

Z101 Zeolite A Sod. Aluminum silicate hydrate Zeolite A Na2 Al2 Si1.85 O 7.75 H2O 5.1 38- 0241 83- 2319 cubic 32.62
Sod. Aluminum silicate hydrate Zeolite X Si7 Al5 O24 Na7.4 H2O 5.2
Z102 Zeolite A Sod. Aluminum silicate hydrate Zeolite A Na2 Al2 Si1.85 O 7.75 H2O 5.1 38- 0241 83- 2319 cubic 58.91
Sod. Aluminum silicate hydrate Zeolite X Si7 Al5 O24 Na7.4 H2O 5.2
Z103 Zeolite X Sod. Aluminum silicate hydrate Zeolite A Na2 Al2 Si1.85 O 7.75 H2O 5.1 38- 0241 83- 2319 cubic 21.0
Sod. Aluminum silicate hydrate Zeolite X Si7 Al5 O24 Na7.4 H2O 5.2
Z104 Zeolite X Sod. Aluminum silicate hydrate Zeolite A Na2 Al2 Si1.85 O 7.75 H2O 5.1 38- 0241 83- 2319 cubic 14.39
Sod. Aluminum silicate hydrate Zeolite X Si7 Al5 O24 Na7.4 H2O 5.2
Z105 Zeolite A Sod. Aluminum silicate hydrate Zeolite A Na96Al96Si96O 384.216 H2O 39-0222 cubic 21.70
Z106 Zeolite A Sod. Aluminum silicate hydrate Zeolite A Na96Al96Si96O 384.216 H2O 39-0222 cubic 69.73
Sod. hydrogen Aluminum silicate Zeolite Y Na0.275 H6.725 Al7 Si17 O48 76-0110

Exceptions were considered for samples 103Z and 104Z, which showed regular cubic crystals were exhibited in samples 101Z, 102Z, 105Z and
zeolite X phase as a major content at 2θ values of 5.7°, 11.41°, 19.59° 106Z, respectively. The cubic shape is regular in zeolite type A, as il-
and 23.02° [19]. Zeolite-X, Zeolite-A, and Zeolite-Y are a member of the lustrated by many published papers [26,27,34,35]. Sample 103Z, on
same zeolite family according to the crystallographic units and their the other hand, gave cabbage-like structures which are constructed by
compositions [15]. Extending the reaction time & Si/Al molar ratio and many straight nanosheets. Sample 104Z, interestingly, showed a flower-
increasing the degree of temperature are the main reasons in the like shape as reported by other authors [36,37]. The flower-like shape
transformation of zeolite X, A and Y [26,27]. The confirmed chemical morphology for sample 104Z is likely assigned to the formation of the
structure of zeolite samples from XRD technique are shown in Table 1. amorphous phase which affected the growth of crystals at a low oper-
Sample 106Z was the only sample which showed a small fraction of ating temperature (5 °C).
zeolite-Y. Similar results were reported in the literature [28–31]. Increasing crystallinity and grain size of the zeolite strongly depends
The crystallite size is conventionally determined by XRD analysis. on the Si/Al molar ratio [26,38]. As a result of utilizing different pre-
All of the prepared zeolites were crystalline materials in a cubic cursors from disposed of raw aluminum waste, distinguished changes in
structure, as indicated by sharp XRD peaks, except for sample 104Z the morphology of the samples was due to change in Si/Al molar ratio
which gave amorphous structure and had a different crystallite size. All for the zeolite samples. This ratio is ranged from 1.06 to 1.27 and is
samples were ranged in nano-scale and have cubic crystal shape (as close to the corresponding ratio to synthetic NaA zeolite. Additionally,
shown in Table 1). Sample 104Z (prepared in an ice bath), had the the cubic shape and high crystallinity were confirmed from XRD results
smallest crystallite size in nano-scale (14.39 nm). This is likely due to (Table 1) which are recognizable for NaA Zeolite [27,35,39,40]. Ob-
the synthesis in low temperature, which has been reported to slow tained results pointed to factors which have a great influence on the
down the nucleation process and the growth of the crystal, leading to a structure and morphology of the synthetic zeolite as precursors of used
small particle size [32,33]. Conclusively, zeolite materials can be suc- raw material and the temperature used herein in the preparation pro-
cessfully synthesized from different aluminium waste resources, with cess.
no negative impact on the final products by using raw waste materials EDX analysis confirmed the elemental composition and constituents
in terms of purity and morphology of the produced zeolites. of the tested types of zeolite. It is noteworthy that EDX analysis Fig. 3
showed only Na, Al, Si and O elements existing in all tested samples.
This confirms the purity composite phase with no impurities in all
3.1.2. SEM and EDX analysis
zeolite samples. Table 2 indicates that the calculated (Si/Al) molar
Scanning Electron Microscopy (SEM) was utilized to show the
ratios from the experiments were approximately 1.1 which is close to
morphology of the synthesized zeolite materials using Everhart-
the theoretical calculation (1), except for sample 103Z (Si/Al), which
Thornley Detector (ETD) at different magnification levels as shown in
was 1.27. The major difference between Na-X, Na-A and Na-Y zeolites
Fig.3. SEM images showed a marked change in the morphology of
were due to the corresponding ratio of Si/Al and were similar to the
samples 101Z to 106Z. The SEM images for the synthetic zeolite sam-
theoretically calculated values of the synthesis [41].
ples showed fully granulated uniform fine particles. The well-defined

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S. El-Nahas, et al. Journal of Water Process Engineering 33 (2020) 101104

Fig. 3. SEM morphology for synthetic zeolite samples (1–6).

Table 2
EDX analysis for synthesized zeolite samples (101Z-106Z).
Samples Elemental Analysis % Si/Al pH Z

Si Al Na O

101 Z 13.01 11.03 12.20 63.76 1.16 8.20

102 Z 12.65 11.91 12.63 62.81 1.06 7.90
103 Z 14.83 11.68 11.58 61.91 1.27 8.90
104 Z 14.82 12.35 11.99 60.84 1.20 8.01
105 Z 15.41 13.51 13.34 57.74 1.14 8.28
106 Z 15.19 13.49 13.80 57.52 1.13 8.01

3.1.3. FTIR analysis

Fig. 4 illustrates the IR spectra of all synthesized zeolite samples
(101Z-106Z). IR spectrum given absorption bands at 3498.6, 1639.1,
1000.2, 660, 557.8 and 456.7 cm−1, respectively. The 1000.5 cm−1 Fig. 4. FTIR spectra for synthesized zeolite samples (101Z-106Z).
bands for zeolite samples may be attributed to antisymmetric stretching
of TeO bonds (where T = Si or Al) for aluminosilicates in the zeolite
composition. Furthermore, the band around 1000 cm−1, is attributed to HeOeH bond [11,40,42].
Si–O–Al bonds in the TO4 tetrahedra, which indicates the (SiO4)2-
groups for the symmetric stretching vibration of Si–O–Si [11,26]. A
3.1.4. Nitrogen adsorption isotherms and surface area measurements
broad peak with low intensity is present around 547.7 cm−1, this peak
SBET was used to determine the porous properties: such as specific
indicates the existence of zeolite A band, assigning the cubic shape as
surface area, pore volume and pore size. This helps in recognizing the
indicated before in its SEM image (Fig. 3). Also, the absorption band
structure, formation and possible applications of different materials as
located at 557.8 cm−1 is attributed to Al−OH vibrations [19]. The
shown in Fig. 5 (a, b) and Table 3. The results exhibit that sample 104Z
bands at 456.7 and 660 cm−1, respectively, are characterized to the
has the greatest BET surface area (294.6 m2. g−1) and total pore volume
internal linkage vibrations of the tetrahedral TO4 (T = Si or Al) and to
(0.13 cm3. g−1) from all the prepared products. These results agree
the asymmetric stretching bending vibrations of Si–O–Si bond of zeo-
strongly with results obtained from the XRD analysis, and it seems
lite, respectively. Furthermore, the broadband at about 3498 cm−1 and
reasonable that sample preparation in low-temperature conditions can
a band at 1639 cm−1 are assigned to water bending vibration of the
lead to the formation of some amorphous particles besides the

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S. El-Nahas, et al. Journal of Water Process Engineering 33 (2020) 101104

produced from loss of water hydration that is highly bound in the

zeolite structure [49]. While sample 105Z shows a shoulder in the DTG
trace at approximately 74.63 °C and sample 102 Z has two significantly
small shoulders in the DTG trace that occurs at approximately 52.9 and
82.9 °C, respectively. It is commonly known that peaks between
40−50 °C and 70−100 °C can be referred to the release of weakly
bound water [26]. Fig. 6 for DSC curves shows two endothermic peaks,
the strongest and sharpest one was between 160 and 185 °C and the
other broad peak was around 350 °C. The highly sharp DSC peak de-
scribed the exclusion of surface, physically adsorbed water when being
below 200 °C. While the broad DSC peak around 350 °C may be at-
tributed to the removal of chemical adsorbed water in the pores
[50,51].

3.1.6. XPS analysis

The XPS analysis was performed on the synthesized zeolite mate-
rials (Z101-Z106) to detect the composition and oxidation states of the
oxygen surface species along with the binding energies as shown in
Fig. 7. The C1s peak for both of them was mainly at the binding energy
Fig. 5. Texture properties for zeolite samples a) N2 adsorption isotherm b) of 284.6 eV (CeC, C–H) as shown in Fig. S1 (supplementary informa-
surface areas by BET theory. tion) along with small peaks at around 288.1, 285.9, 284.2, 282.3 eV
which are attributed to the C]O, CeO, sp2 hybridized carbon and Si-C
Table 3 bonding in the surface structure of the synthesized zeolites [52]. On the
Surface properties for synthesized zeolite samples. other hand, the O1s spectra revealed that most of the oxygen species are
Sample BET Surface Area Total Pore Volume= Average pore Radius
oxygen lattice in all the six samples (Z101-Z106) at a binding energy of
(m2. g−1) (cm3. g−1) (Ao) 530.0 eV as shown in Fig. 7. The zeolite samples of 101Z and 104Z
showed also OH group or CO2 adsorbed in the form of carbonate on the
101 Z 183.5 0.09 5.78 surface at a binding energy of 531.4 eV. While zeolite samples of 102Z
102 Z 110.7 0.05 9.88
and 103Z showed Al-O-Al or Si-O-Al bonding at a binding energy of
103 Z 285.2 0.13 5.69
104 Z 294.6 0.13 6.19 531.6 eV. Finally, samples of 105Z and 106Z showed similar surface
105 Z 275.3 0.13 5.86 oxygen species at binding energies of 527.9 and 532.6 eV which at-
106 Z 102.4 0.04 10.36 tributed to nucleophilic oxide and oxygen in the SiO2 structure, re-
spectively.

crystalline structure, thus all the crystallite size of zeolite particles ex- 3.2. Softening of water from Ca2+ ions
ists in nano-sized scale. This result is in agreement with the work done
by Mori et al. who reported that zeolite preparation at low temperature Nowadays, a significant challenge in developing countries that has
is affected the growth and size of the crystal formation. Thus during the gained attention is to manage and solve water problems. Based on re-
crystallization process, the growing of crystal size is governed by tem- cent technologies, researchers and industries are concerned with
perature and time leading to the formation of amorphous along with finding and utilizing economically viable and inexpensive techniques
crystalline structure [43]. The surface area follows the order of for softening hard water supplies. Zeolitic material has a unique prop-
104Z > 105Z > 101Z > 103Z > 102Z > 106Z. The synthetic zeo- erty to be used as ion exchanger in an aqueous solution [14]. Based on
lites in this study have a higher surface area than others published in this specific property, our zeolite samples (101Z-106Z) shows an ef-
the literature [14,20,44]. fective affinity for the elimination of Ca2+ from solution. The removal
Fig.5a has exemplified shapes of N2 adsorption curves isotherm efficiency reached 85 % at a very high level of Ca2+ content
which exhibits the characteristic of type (I) isotherm in accordance with (1000 ppm). Based on the XRD analysis of loaded Ca-zeolite (Fig.S2),
the nomenclature of International Union of Pure and Applied Chemistry we proved undoubtedly that the tested zeolites were able to uptake
(IUPAC), which is typically featured for mesoporous materials [45]. Ca2+ ions from aqueous solution, according to the cards no.: 47-0003
Primary adsorption increment of volume of N2 occurs at relative pres- (I), 76-1509(c), 88-0188(c) and 11-0589. All zeolite samples (101Z-
sures P/Po (< 0.35), which pointed to a highly microporous structure 106Z) changed their structure from Na-zeolite (mainly NaX, NaA) to
with a probability distribution of narrow pore size. Also, a sharp uptake Ca-zeolite and appear as sodium calcium aluminium silicate hydrate
indicating the rapid adsorption of N2 on the textural surface of zeolite zeolite, calcium aluminium silicate hydrate zeolite A, calcium alumi-
[46]. The linear absorbance from 0.1 to 0.4 relative pressures P/Po is nium silicate hydrate zeolite X and calcium aluminium silicate hydrate
responsible predominantly due to the mesoporous region. Mesoporous Zeolite linde A, respectively. Two essential factors influence in the ca-
substances are known to be wonderful host substructures, due to bulky, tion exchangeability of the zeolite. The first one is the Si/Al ratio.
symmetrical pore diameters and large surface area [47,48]. It is inter- Zeolite samples with low Si/Al ratio below 2 have excellent ion ex-
esting to note that by application BET model onto the tested zeolite change capability in water treatment. Another factor that affects cation
proved excellent adsorption ability of N2, taking account of good sur- exchange properties is the size and arrangement of cavities in channels
face area in the adsorbent sample [46]. and cages in the crystal structure of the zeolite. This allows the cations
with a specific size to transport inside them. The common rule is that
3.1.5. Thermogravimetric analysis ion-exchange selectivity of zeolites is elevated for higher valance ca-
Fig. 6 (A–F) evaluated TG, DTG and DSC thermograms for tested tions [13]. In this study, the zeolites have a Si/Al ratio around 1.1,
zeolite samples. All zeolite samples have total weight loss calculated making them a suitable adsorbent for the softening of water. Type A
from the TG curve to be approximately 18 % at a temperature below zeolite is considered the lowest Si/Al ratio with value equals 1 and
200 °C. A sharp main DTG peak occurs at range (149−156 °C) for all display a good cation exchange capacity and high sorption attainment
synthesized zeolite samples. This main peak around 140−200 °C is [53]. In addition, tested zeolite samples have high crystallinity that

6
S. El-Nahas, et al. Journal of Water Process Engineering 33 (2020) 101104

Fig. 6. TG, DTG and DSC curves for zeolite samples a) 101Z, b) 102Z, c) 103Z, d) 104Z, e) 105Z and f) 106Z.

dominates a narrow range of pore sizes indicating the selective ability distinguishable ways. One effect was on the metal solubility and evo-
of the solid phase better than non-crystalline particles [54]. It is simple lution of distinct species onto the solution, the other is on the total
to understand the mechanism of ion exchange based on the negative charge of adsorbents [13]. The removal intensity of Ca2+ ions from the
charge in zeolite structures as AlO4 and SiO4 are balanced by Na ions, solution had been illustrated in Fig. 8B. First of all, zeolite samples
which is exchangeable with an external medium such as Ca2+ present showed a good removal ability in the entire range of pHs studied. De-
in the solution [13,54]. Negatively charged zeolite molecules will easily spite the fact that a slight decrease was observed at pH 2 (strong acidic
withdraw positively charged calcium Ca2+ ions in their channels and medium) still, the removal of Ca2+ ions was high and removed 65 % of
monovalent sodium ions are substituted by divalent calcium ions. Only the total. Taking into consideration, a pH value lower than 2, the zeolite
10 g.L−1 of zeolite samples are sufficient to remove 85 % of Ca2+ may undergo deformation due to the dissolution of Al atoms [57]. Final
present in aqueous solutions. Others feature of the tested zeolite sam- pH values after mixing synthesized zeolite samples with the CaCl2 so-
ples is the ability for using 3 sequence cycles in the aqueous solution lution (1000 ppm) were illustrated in Table (4 ). The values of the pH
and it can be regenerated again effortlessly. increased significantly after the addition of adsorbents for the initial
step of pH 2 to pH 4. This may be attributed to the competition between
3.3. Effect of initial concentrations for calcium ions the large amount of H3O+ with the Ca2+onto the active sites [58]. At
further increase in initial pHs of more than 4, no significant change was
Considering the great effect of initial concentration values of water observed in final pH and remained constant around pH 7. It is notable,
samples in the adsorption process, we investigated our zeolite samples that zeolite samples have a buffer capacity over the studied pH range
at very high Ca level in water solution (1000 ppm–4000 ppm) at 20 °C. from 2 to 10. The buffering behaviour of zeolite samples may be ex-
The effects of initial metal ions concentration had been explored and plained by the surface charge on zeolite materials, which can be mea-
demonstrated in Fig. 8A. It is clear from obtained data, that all samples sured by the point of zero charge for the tested zeolite surfaces. The
have high affinity to capture Ca2+ from aqueous solutions and is highly point of zero charges (pHpzc) values for the prepared zeolite are shown
influenced by the concentration of loaded Ca ions in solution. With in Fig. 8F and Table (2). The pHpzc values were 8.2, 7.9, 8.9, 8.0, 8.3
increasing the initial Ca2+ concentrations, the extent of Ca2+ ions re- and 8.0 for zeolite samples from 101Z to 106Z, respectively. At pH
moval is decreasing in most cases. This is maybe due to there are no values below the pHpzc, the surface of the zeolite will have a positive
more sites are available at fixed zeolite dose. It can be understood that charge, while at a pH value higher than the pHpzc, the exterior surface is
the ion exchange sites are saturated with Ca2+ cation species and about dominated by negative charges [13,59]. The zeolite surface charges,
to exhaust nearly all its exchange aptitude [7,55,56]. caused by ionization of external hydroxyl groups (Si−OH and Al−OH),
is strongly dependant on acid/base reduction when the zeolite is ex-
3.4. Effect of pH posed to water solution [14]. Firstly, increasing the initial pH up to
4.0 gave rise to raise the final pH. This may be explained as zeolite
pH values affected the adsorption capacity of zeolite samples in two samples dominated alkalinity and ion exchange reaction between the

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S. El-Nahas, et al. Journal of Water Process Engineering 33 (2020) 101104

Fig. 7. XPS spectra of O1s for the synthesized zeolites Z101-Z106.

Na ions in the zeolite and Ca2+ ions in the solution, which could in- Otherwise, metal uptake capacity in the adsorption process is
crease the pH value readily at acidic pH [60]. Further increase in the strongly influenced by partial dissolution of the zeolite material as an
initial pH did not cause any changes of final pHs and the solution stayed adsorbent in the solution used. Electrical conductivity (EC) measure-
constant at pH 7. The plateaus of the curve indicated that adding of the ments were illustrated in Table 4. The Electrical conductivity has a
H+ ions or OH− ions have no effect on the final pHs and they are close slender increase than the blank run of Ca2+ solution in the entire pH
to point of zero charge of samples. This phenomenon shows buffer range tested. This increase is ranged from 5.05 to 5.21 μs.cm−1 in most
properties of the zeolite samples according to the total acidity of a cases and can be ascribed to the change of some soluble parts from the
zeolite (i.e. the total Lewis & Brønsted acidic site). Similar data were adsorbents achieved by the ion exchange performance of Na+ by Ca2+
published by other authors [61]. The obvious observation from the ions. Furthermore, structures containing zeolite units will be considered
above results is that the synthesized zeolite contained a high efficiency as promising future materials, due to their high resistance of pH and
for the capture of Ca2+ in a broad range of pH values [62]. approximately constant EC values which allows them to be utilized in

8
S. El-Nahas, et al. Journal of Water Process Engineering 33 (2020) 101104

Fig. 8. Factors affect the adsorption of Ca2+ ions: A) Effect of initial concentration, B) Effect of pH C) Effect of time D) Effect of dose E) Effect of temperature F)
pHpzc.

different acidic (achieved approximately 65 % removal) and basic surface of zeolite (Brønsted & Lewis acidic and basic sites). The Si/Al
mediums (more than 80 % removal). The buffer capacity of the zeolite ratio in the framework is the reason for the cation exchange capacity of
samples is attributed to the presence of acidic and basic sites on the zeolites. The high performance of the tested zeolites over the wide

Table 4
Final pH and final electrical conductivity (EC) measurement for aqueous solution.
pH initial pH final Conductivity uS

101Z 102Z 103Z 104Z 105Z 106Z 101Z 102Z 103Z 104Z 105Z 106Z

2 6.2 5.86 6.2 4.81 5.74 5.94 5.05 5.07 5.14 5.54 5.07 5.07
4 7.18 7.25 7.62 7.76 7.46 7.34 5.15 5.12 5.14 5.18 5.15 5.19
6 7.33 7.03 7.70 7.88 7.56 7.31 5.12 5.16 5.16 5.18 5.29 5.36
10 7.18 7.65 7.94 8.32 7.57 7.30 5.12 5.12 5.10 5.2 5.07 5.21
Blank 7.5 5.01

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S. El-Nahas, et al. Journal of Water Process Engineering 33 (2020) 101104

Table 5
Thermodynamic constants for sorption system of Ca2+ ions onto zeolite.
Sample ΔH (kJ.mol−1) ΔS J.mol−1.K Δ G (kJ.mol−1)

26 oC 37 oC 40 oC 50 oC 60 oC

101 Z 10.83 44.06 −2.33 −2.82 −2.95 −3.39 −3.83

102 Z 9.27 38.18 −2.14 −2.56 −2.68 −3.06 3.44
103 Z 13.95 52.74 −1.81 −2.39 −2.54 −3.07 −3.60
104 Z 16.33 59.59 −1.48 −2.13 −2.31 −2.91 −3.50
105 Z 11.81 48.07 −2.55 −3.08 −3.22 −3.70 −4.18
106 Z 7.96 36.33 −2.89 −3.29 −3.40 −3.77 −4.13

initial pH range is related to their buffering capacity. zeolite A phase as a major content as shown in Fig. 2 in the XRD section.
It also had the smallest crystallite size of 14.39 nm as shown in Table 1
3.5. Effect of contact time along with the largest surface area of 294.6 m2/g (Table 3) among the
synthesized zeolite materials. It is well known that zeolite type X has
The equilibrium time is an indispensable parameter for economical more tendency and selectivity toward CO2 capture from the air than
water and wastewater treatment plant application of new adsorbent other types of zeolite A and Y, which makes it less active in water so-
technologies [63]. It can be used in successful practical implementa- lution application [69,70].
tions, such as designing of the reactor and optimization the operation
process [64]. The influence of contact time on Ca2+ ions removal was
carried out over a period of time extended from 1 to 180 min. The re- 3.8. Thermodynamic parameters
sults are shown in Fig. 8C. The removal of Ca2+ ions was very fast
within the first-minute corresponding to > 50 % removal. With an in- Determination of thermodynamic constants is of significant use to
creased contact time, the adsorption increased slowly to attain equili- investigate the spontaneity of the adsorption system and the probability
brium at 30 min. The rapid initial stage is perhaps due to the accessi- of the process at a given temperature [67]. The thermodynamic ad-
bility of plentiful active sites on the zeolite surface, and with the sorption parameters ΔG°, ΔH° and ΔS° are expressed with the help of the
progressive occupation of these sites, the sorption then became lower in Eq. (3–5) and written in Table (5 ).
the later stage. Rapid Ca2+ uptake by zeolite samples may be attributed
Cad
to its highly porous and mesh structure of the binding sites [58,65]. Kc ∘ =
There was no need to elapse more time than 60 min, as there is no
Ce (3)
considerable variation in the reduction of Ca2+ after this period [62].

ΔG o
= - RT 1n Kc° (4)
3.6. Effect of adsorbent dose
ΔG∘ = ΔH ∘ − TΔS ∘ (5)
Sorption capacity is strongly influenced by the adsorbent mass in
solution or the Solid/Liquid ratio (S/L). The removal of Ca2+ is affected Where Cad is the concentration of metal ion (mg.L−1) on the adsorbent
by (S/L) ratio as illustrated in Fig. 8D. The solid amount of the ad- at equilibrium and Ce is the concentration of metal ion (mg.L−1) in
sorbent is varying from 1 g.L−1 to 14 g.L−1 and the liquid volume was solution at equilibrium. The change in standard free energy, enthalpy,
kept constant. It is clear from the obtained results that the removal of and entropy of the adsorption process is denoted as ΔGo, ΔHo and ΔSo,
Ca2+ ion increased with increasing the S/L ratio. The increase in the respectively.
Ca2+ uptake may be due to the greater availability of the exchangeable Table 5 shows the thermodynamic parameter values of ΔG°, ΔH° and
sites and different types pore on the surface of the zeolite [66]. ΔS°, as these are used to recognize the characteristic of the sorption
system. Sorption of Ca2+ ions has negative values for ΔG° for all studied
3.7. Effect of temperature zeolite samples. This illustrates the favorability and spontaneity of the
adsorption process at all operating temperatures. Thus, increasing the
The sensitivity of changing the temperature on the Ca2+ ions negative sign of ΔG° by increasing the temperature, confirms preferable
sorption process is demonstrated in Fig. 8E. The temperature range that adsorption at elevated temperature. The sign of ΔH° values for all
was applied herein ranged from 25 to 60 °C. Increasing the temperature zeolite materials are positive and emphasize the endothermic nature for
led to a slight augment in Ca2+ ions removal implying that the ad- the adsorption process [19]. Another parameter, ΔS° has positive sign
sorption process will be endothermic in nature, thus enhances the ad- values for all the tested zeolites, and the increase of entropy is a result
sorption of metal ions on the surface of the adsorbent substance [67]. It of adsorption. This arises from the energy redistribution among the
was evident from the obtained data that varying temperature values adsorbate and the adsorbent. Displaying a positive value of ΔS°, the
(25–60 °C), didn't strongly influence the adsorption capacity of the rotational and translational energy distributed amongst a small number
zeolite. This phenomenon may be a good and suitable feature for the of molecules will have augmentation in adsorption, leading to a rise of
utilization of these zeolites in contaminated groundwater and surface the randomness at the solid-solution interface during the adsorption
water with hardness ions in situ management. Interestingly, the syn- process [71]. In general, the value of ΔH° is observed in the range of
thesized zeolites could be used with a good performance in various 7.9–10.83 kJ.mol−1 and was < 40 kJ.mol−1, which refers to physical
water resources globally, where the water temperature varies with the adsorption. An ion exchange process would have an exothermic or
climate and nature of location [68]. Furthermore, the endothermic endothermic nature. In the exchange process, the limits of the adsorp-
nature was demonstrated from the results of thermodynamic calcula- tion energy have ranged between 0.6 kJ.mol−1 and 25 kJ.mol−1 [72].
tions in section 3.8. The obtained results belong to the same range; indicating ion-exchange
In Fig. 8, sample 104 Z behavior is almost different than other taken place herein.
samples that may be due to the various reasons. It showed zeolite X
phase as a major content, unlike other zeolite samples which showed

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S. El-Nahas, et al. Journal of Water Process Engineering 33 (2020) 101104

Fig. 9. Competitive adsorption in mixture Mg2+ & Ca2+ ions a) mixture (1:1) b) mixture (2:1).

3.9. Competitive adsorption in binary solution competing between Mg2+ &

Ca2+ ions

Ions of calcium and magnesium usually exist concurrently in most

water supplies and can be expressed as total water hardness. With a
view to studying the competing effect of Ca2+ and Mg2+ ions on ad-
sorption capacity of zeolite samples, tests were undertaken for a mix-
ture of Ca2+and Mg2+ cations (1:1) with total concentration 1000 mg.
L−1 and mixture (2:1) with high total hardness 3800 ppm. Results were
demonstrated in Fig. 9 (a,b). The removal of cations were 92 % and 89
% for calcium and magnesium, respectively. As a result, the total water
hardness was eliminated by 90 %. Without doubt, increasing the total
hardness to 3800 ppm in a mixture of Ca2+ and Mg2+ (2:1), showed
selective removal of Ca2+, rather than Mg2+ ions. Therefore, the total Fig. 10. Removal of Ca2+ ions in consequence cycles.
hardness decreased by 55 %, while the average removal of Ca2+ was
about 80 % and only 18 % for Mg2+ ions. The decrease in ion exchange
process preferred simple and low-price reagent. Saturated Ca-zeolite
of Mg2+ ions by zeolite type A may be due to size and charge of Mg2+
samples (Ca-adsorbed zeolites) were impregnated in 1 M of NaCl solu-
ions. Mg2+ ions surrounded by large hydration zone makes it hard to
tion, shaken for 6 h at room temperature and then filtered and dried.
enter and pass through the sodalite cages of zeolite- A [73]. Notably,
Regeneration did not require a high temperature or costly solvent, only
adsorption efficiency decreased when compared with the observed
NaCl solution is used as a facile way. The regenerated zeolites after 4 h,
values in single ion adsorption measurement. This can be explained by
showed an increase in the adsorption efficiency by up to 40 %. This may
fast occupation and saturation of the active sites of the adsorbent by the
be due to the magnitude of the ion-exchange ability of sodium ions to
competitiveness between Ca2+ and Mg2+ ions on the surface of the
replace calcium ions inside the zeolite samples when using the NaCl
zeolite. Regarding the tests observed for single ion adsorption, zeolite
solution [60]. According to the rules of cation exchange capacity (CEC)
materials have great adsorption capacity and showed higher selectivity
on zeolite previously published [13], all aluminous zeolite prefer
toward Ca2+ rather than Mg2+ ions [11]. Other publications showed
trading NH4+ and/or Na+ ions from solution. In this research, we chose
that zeolite of NaA type exhibited higher Ca2+ removal more than
to use NaCl to regenerate synthesized zeolite samples for lowering the
Mg2+ from solution at ambient temperature [41].
cost of the regeneration process. Our result assured us that the zeolites
samples are distinctly reusable. The regeneration of the spent zeolite
3.10. Cycles and regeneration of exhausted zeolite materials was performed using a sodium chloride solution, this means
that the brine solution left after the softening of the seawater could be
An additional and unique characteristic for zeolite samples is having used to regenerate the zeolite materials.
a tendency for regeneration and utilization for more than a few cycles
after sorption of metal. Adsorption and desorption experiments were 3.11. Equilibrium studies
applied to reprocess the tested zeolite samples for a more economically
viable utilization in consecutive sorption cycles. The synthesized zeolite Adsorption isotherm means a correlation between the quantity of a
samples can be used competently for consecutive cycles at high Ca substance adsorbed (mg. g−1) from the liquid phase and its equilibrium
content (1000 ppm) without washing or regeneration of the samples. concentration at a fixed temperature. Information from adsorption
The 1st cycle of zeolite removed more than 83 % of Ca2+, while, in the equilibrium constants and the fundamental thermodynamic hypotheses
2nd cycle removed about 24 % and in the 3rd cycle removed about 6 % of the used equilibrium models often help in understanding the ad-
as displayed in Fig. 10. The decrease in the adsorption capacities for sorption mechanism and explaining the characteristic of sorbent sur-
recycled zeolites may be attributed to saturation of the zeolite pores face. They are useful to determine the characteristics of an adsorbent if
with the overflow of Ca2+. It is better to reactivate the zeolite after the they suitable for application related to design purposes [13].
2nd cycle, especially at very hard water content to be reused once more The adsorption behaviour of prepared zeolites for the removal of
with high capability for Ca2+ adsorption. Ca2+ was analyzed in terms of isotherm models. There are three
Cost-saving regeneration and performance capacity in the sorption commonly used isotherm models namely; Langmuir, Freundlich and

11
S. El-Nahas, et al. Journal of Water Process Engineering 33 (2020) 101104

Temkin isotherms which were applied to fit the experimental data. The quite complex and more than one mechanism is involved [75]. It is
linear and non-linear forms of these equations are given by: widely known that the Langmuir isotherm model illustrates the ion-
Freundlich isotherm Eq. (6): exchange mechanism, while the Freundlich isotherm confirmed com-
1 plex reactions going on in the adsorption process [76]. These models
1
qe = Kf Cen and linear form log qe = log Ce + log Kf cannot totally demonstrate all interactions occurring in an adsorption
n (6)
system or explain the fundamental mechanism. That may be under-
Langmuir isotherm Eq. (7): stood, because the interaction between the active functional groups on
qmax K a Ce 1 1 1 1 the adsorbents surface and the metal ions in solution may be associated
qe = and linear form = ⋅ + by involving electrostatic attraction, adsorption/precipitation, hy-
1 + K a Ce qe K a qmax Ce qmax (7)
drogen bonding, ion-exchange or chemical interaction [4].
Temkin isotherm Eq. (8): Curves in Fig. 11 (A–F) show concave downward (type I), which can
be referred to as favorable behavior for the uptake process. This shows
qe = B ln A + B ln Ce B= RT/b (8) the advantage of the expected regenerative operations. Favorable iso-
RL = 1/(1 + K a Co) therm may be also suitable for effective regeneration [77]. The ex-
(9)
perimental data showed good fitness on Freundlich and Temkin on non-
Where: linear curves rather than Langmuir curve.
Ce (mg.L−1) and qe (mg. g−1): are the equilibrium concentrations in
liquid and solid phase, respectively. 3.12. Kinetic studies
qmax: is the maximum metal uptake (mg. g−1), Ka: is Langmuir
constant, Kf (L. g−1) and n: are Freundlich constants, b: is Temkin Various kinetic models illustrate and classify the order of ad-
constant related to the heat of sorption (J. mol−1.) and A is the Temkin sorbent–adsorbate interactions, where traditionally, the pseudo-first
equilibrium binding constant (L. mg−1). Co is the initial Ca ion con- and pseudo-second-order model are used as shown in Eqs. (10), (11)
centration. and (12), respectively. To identify the intraparticle diffusion, Weber-
In addition, the non-linear regression modality was used to set the Morris equation [12] was applied.
alternative isotherm parameter. Comparisons between Langmuir,
Freundlich and Temkin, isotherm linear regressions for equilibrium K1
Log (qe − qt ) = log qe − t
2.303 (10)
data of the present work were shown in Fig. S3, while the nonlinear
fitted curves were demonstrated in Fig. 11 (A–F) and their correlating t 1 1
parameters were presented in Table (6 ). The experimental data fitted = + ⋅t
qt k2q 2e qe (11)
well to Langmuir, Freundlich and Temkin isotherm models for all
zeolite samples in linear and nonlinear forms. Nevertheless, Freundlich qt = K d t 0.5 + C (12)
and Temkin's isotherm gave the highest regression coefficients, with R2
closest to unity compared to Langmuir isotherms. This result confirmed Where qe and qt (mg. g−1) are the amounts of sorbate that are ad-
the ion exchange effect in the adsorption process [74]. Moreover, the sorbed at equilibrium and at any time (t). K1 (min−1) and K2
three tested models were close in the regression values, and this sug- (g. mg−1. min−1) are the equilibrium rate parameters of pseudo-first
gested the surface of the adsorbent contained a heterogeneous structure and pseudo-second-order sorption, respectively. The calculated values
[11]. Based on data derived from the Langmuir isotherm model, the of correlation coefficients (R2) based on the obtained data demonstrate
maximum monolayer adsorption capacity of synthetic zeolite to Ca2+ very good linearization to the pseudo-second-order model more than
ions have high values are 90.9, 90.9, 85.47, 85.0, 105.2 and 111.1 mg. the pseudo-first-order model as illustrated in Table (7 ). Furthermore,
g−1 in zeolite samples (101Z-106Z), respectively. High discerned qmax the computed qe values derived from the pseudo-second-order model
values were observed, compared with different adsorbents materials are more sensible than those of the pseudo-first-order, by comparing to
published for hard water softening [1,2,19,49,68]. Therefore, all syn- those of qe calculated from the experimental data. Thus, pseudo-first-
thesized zeolites can be regarded as a promising material that can be order kinetics might not be adequate to describe the mechanism of the
successfully used in desalination processes. interactions of Ca2+ ions–adsorbent.
According to RL (equilibrium constant or dimensionless separation Many publications relating to salt ions on zeolite samples fitted well
factor), values derived from the Langmuir isotherm model is referred to with the pseudo-second-order among the kinetic models and always
the nature of adsorption (Table 6). RL values were ranged from 0.03 to referred to chemisorptions as the rate-controlling step. Therefore, a
0.067 and fall between 0 > RL > 1. This indicated adsorption of Ca2+ more detailed future work is needed to shed light on the nature of
ion on the zeolite surface is a favourable operation [2,49]. Based on the chemisorption sites. Furthermore, the pseudo-second-order kinetics are
results Freundlich model, the affinity coefficient (Kf) values were high not exclusively emphasis of chemical sorption [2,13]. It is explicit from
and ranged from 38.8 to 51.64 for samples 101Z to 106Z, this indicated the antecedent results of thermodynamics (Table 5) and from Timken
the high affinity for cation in the present medium. Also, the Freundlich constant isotherm (Table 6), that adsorption of Ca2+ ions tested with
constant (n) were > 1. 0 and this indicated the favorable adsorption zeolite was well-thought-out as physical adsorption. Thus, we suggested
process. A similar trend was reported by [55]. that the mechanism for adsorption of Ca2+ ions onto the zeolite surface
At a fixed temperature (298 K), the obtained Temkin constants b can be explained by the electrical double layer (EDL) theory. This hy-
(J.mol−1) (b = RT/B) for all zeolite samples were less than 80 pothesis is based on an existing electrical double layer around each
KJ.mol−1, which revealed that the heat of adsorption of Ca2+ onto zeolite particle when dispersed in the salty solution. The first layer is
zeolite is considered a physical adsorption behavior [2]. Furthermore, engaged by strongly bound ions (Stern layer), while the next layer is
the constant A (L. g−1) has high values (Table 6) and refers to its strong surrounded by less strongly bound ions (diffuse layer). When zeolite
bonding of Ca2+ ions onto the zeolite samples [55]. In addition, high b particles have a higher electrical charge, then the diffusion layer will be
values indicated rapid sorption of adsorbate at the initial stage that fast greater and more cations will be easily adsorbed [2,13,78].
sorption equilibrium was achieved in 30 min and has been previously Based on the previous results that confirmed rapid removal of Ca2+
discussed (Fig. 8C). The fitting of the three isotherm models to the Ca2+ ions by zeolite surface, the intra-particle diffusion model (Weber and
ion zeolite samples system suggested that both monolayer sorption and Morris equation) were illustrated to identify the diffusion mechanism of
heterogeneous surface co-exist under these experimental circumstances. the adsorption processes. The adsorption mechanism may be governed
This indicated that the adsorption of Ca2+ ions on these adsorbents is by single or multiple steps. These processes are predominantly external

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S. El-Nahas, et al. Journal of Water Process Engineering 33 (2020) 101104

Fig. 11. Non-linear form of Freundlich, Langmuir and Temkin Isotherm on adsorption of Ca2+ on: A) sample 101Z, B) sample 102Z, C) sample 103Z, D) sample 104Z,
E) sample 105Z, F) sample 106Z.

or film diffusion, pore diffusion at macropore (or micropore), surface participate in the ion exchange processes [49,79]. Furthermore, the C
diffusion, adsorption on the pore surface, or all together [49]. Ac- value derived from the intercept of the equation [12] described the
cording to results from the intra-particle diffusion model (Fig. 12 IV), thickness of boundary layer [80]. The thickness of the boundary layer is
the adsorption of adsorbate on zeolites is dominated by more than one the region of the surface adsorbent that is responsible for adsorption
mechanism, thus this yields a multi-phase step for sorption mechanism. ability to attract the sorbent. The higher intercept C value gave a better
This indicated that both intra-particle diffusion and film diffusion impact on the boundary layer, which is responsible for fast adsorption

Table 6
Langmuir, Freundlich and Temkin Isotherm constant.
Sample Langmuir constants Freundlich constant Temkin constant

−1 −1 −1
qmax (mg. g ) KL (L. mg ) R 2
RL n Kf (mg. g ) R 2
B J. mol−1 B A R2

101 Z 90.90 0.037 0.873 0.030 13.51 51.64 0.971 403.18 6.145 1306 0.958
102 Z 90.90 0.028 0.842 0.039 11.76 46.99 0.948 356.99 6.94 204.9 0.927
103 Z 80.645 0.0124 0.79 0.037 9.71 38.82 0.842 306.28 8.089 19.34 0.811
104 Z 83.33 0.014 0.99 0.067 10.58 38.79 0.968 364.2 6.803 58.66 0.973
105 Z 105.26 0.016 0.842 0.06 8.85 43.35 0.956 234.84 10.55 8.52 0.936
106 Z 111.1 0.015 0.833 0.062 9.09 44.06 0.947 241.95 10.24 10.68 0.922

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S. El-Nahas, et al. Journal of Water Process Engineering 33 (2020) 101104

Table 7
Kinetic Studies, pseudo-first, pseudo second and intraparticle diffusion constant.
Sample Pseudo-first order Pseudo-second order Intraparticle diffusion qe
(Exp)
2 2 2
K1 qe R K2 qe R Kad R C

101 Z 0.014 4.68 0.613 0.033 71.43 0.999 0.914 0.715 62.34 72.8
102 Z 0.014 3.09 0.647 0.039 71.43 0.999 0.481 0.792 64.88 70.6
103 Z 0.015 4.14 0.626 0.034 66.67 0.999 0.777 0.732 57.78 66.7
104 Z 0.025 19.95 0.918 0.006 68.39 0.999 1.517 0.853 49.98 68.2
105 Z 0.023 16.59 0.808 0.0076 81.04 0.999 0.518 0.894 73.83 80.7
106 Z 0.019 17.49 0.769 0.0072 83.33 0.999 0.433 0.859 76.13 82.8

Fig. 12. Kinetic Studies: I) pseudo-first, II) pseudo-second and intra diffusion (III, IV).

[49]. All zeolite samples have fast adsorption within 30 min and re- hardness ions of approximately 96 % for Ca2+, around 50 % for Mg2+
duced the hardness significantly. The interpreted C values had greater ions in groundwater well samples and removing 75 % of the total
values, which indicated a quick adsorption process for all synthesized hardness. While efficiency for hardness removal in seawater was
zeolites. The ion exchange mechanism may involve more than one step around 45 % for removing Ca2+ ions and only about 10 % for Mg2+
and is comprised of both film diffusion and intra-particle diffusion resulting in a decrease of 15 % in the total hardness. The results are
processes [12]. Fig. 12 IV of intraparticle diffusion, the graph domi- demonstrated in Fig. 13. The reduction in percentage removal of hard
nated more than one step that was involved in the sorption mechanism ions by some tested adsorbents in the field samples compared to the
[49,80]. The uptake of salt ions may be ascribed to ion-exchange as well pure solutions may be due to the competing effect of some interference
as adsorption mechanisms. Calcium ions moved through the pores and anion such as Cl, SO4 or NO3 and existence of suspended organic sub-
channels of the zeolite lattice to be exchangeable by sodium ions during stances. This data may be used for wide application in the reduction of a
the ion exchange process. Furthermore, diffusion through the smaller large amount of seawater hardness in the pretreatment process, helping
diameter channels is achieved rapidly when the ions moved [79]. to prolong the lifespan of membranes used in wastewater companies. A
similar trend was published in works by Hatas et al. and Song et al.
[58,80].
3.13. Applications in field study and real samples

Expediency of the recently synthesized zeolite materials was used in 3.14. Removal comparison with literature
hard water experimental samples obtained from two different real
water sources: 1) A groundwater well in the surrounding area where the Table 8 shows the comparison between capacity of the tested zeolite
total hardness was measured to be 1326 ppm 2) Seawater samples ob- materials herein and other published adsorbent materials for the
tained in Hurghada City, Egypt and has a measured total hardness of elimination of hardness ions in literature. The efficiency of the zeolitic
7506 ppm. The preliminary data displayed an elimination efficiency for materials derived from waste showed excellent removal affinities even

14
S. El-Nahas, et al. Journal of Water Process Engineering 33 (2020) 101104

Fig. 13. Removal efficiency for Ca2+and Mg2+ ions removal from a) groundwater well b) seawater.

Table 8
Comparison between tested zeolite materials with other published materials for removal of Ca2+ and Mg2+ ions.
Materials Max adsorption Initial conditions %Removal efficiency Ref

Modified bentonite 14.63 mg/g for Ca 14.63 mg/g for Ca 120 ppm 66.6 % for Ca and Mg [1]
Mg Mg 120 ppm
Time 90 min
natural zeolite 27. 1 mg/g for salt Saline 9.0 g/L, 2.2 % [2]
dose 35 g/L
Time 24 h
MFI-type zeolite 0.0006 mmol for Ca Ca 150 ppm 0.2 % for Ca [3]
0.0001 mmol for Mg Mg 9500 ppm 0 % for Mg
modified sugarcane bagasse coffee husk 46.8–52.9 mg/g for Ca Ca 120 ppm 88- 90 % for both Ca and Mg [8]
Mg 120 ppm
Dose 2 g/L
37.35–41.23 mg/g for Mg Time 2h
Raw pine cone modified pine cone Not included Ca 230 ppm total hardness 11.6 % Raw [9]
Mg 155 ppm;
dosage: 5 g/L; 85 % modified
time: 12 h
MIEX-Na resins Not included Total hardness 12.3 % single dose [10]
275 ppm
Ca 103 ppm 55 % total hardness with Combined ion
Dose 4 ml/L exchange treatment
Time 20 min
Natural pumice modified pumice stones 57.2–62.3 mg/g for Ca 150 ppm for Ca 83 % - 94 % for Ca [11]
150 ppm for Mg
44.5–56.1 mg/g for Mg Dose 6 g/L 48 % - 73 % for Mg
Time 5 h
Zeolite Na-X(Mod) Na-Y (Mod) Not included Ca 80.2 ppm 85.7–80.4 % for Ca [40]
Mg 24.2 ppm. 43.1 - 34.1 % for Mg
natural zeolite Not included Ca 220 ppm 80.2 % Ca [57]
Mg 26 ppm.
dose 50 g/L 84.8 % Mg
60 min
modified zeolite A 129.3 mg/g for Ca Ca 100 ppm 95.0 % for Ca [58]
Dose 1 g/L
Time 1 h
commercial zeolite synthesized zeolite NaA 17 mg/g Ca 80 ppm 95 % for Ca [61]
31 mg/g Dose 1–4 g/L
Time
Grafting copolymerization of acrylic acid 90.7 mg/g for Ca 20 ppm from each metal 86.6 % for Ca [65]
34.6 mg/g for Mg Ca &Mg 81.1 % for Mg
0.5 g/L of the polymeric
ligand
Natural and modified zeolite and bentonite 26.2 mg/g for Mg Mg 250 ppm 85.21 % for Mg [81]
35.6 mg/g for Mg Dose 20 g/L 81.73 % for Mg
synthetic Zeolite 101 Z 90.9 mg/g for Ca Ca 1000 ppm 85.7 % for Ca This study
Dose 10 g/L 83.4 %
102 Z 90.9 mg/g for Ca Time 1 78.6 %
103 Z 80.6 mg/g for Ca 70.8 %
104 Z 83.3 mg/g for Ca 80.0 %
105 Z 105.2 mg/g for Ca 82.0 %
106 Z 111.1 mg/g for Ca

15
S. El-Nahas, et al. Journal of Water Process Engineering 33 (2020) 101104

more than other available low-cost materials. Most of the previously 4. Conclusion
reported hardness removal in the literature were performed at low in-
itial hardness concentration such as 80 ppm [40,61], 100 ppm [58], Synthesized zeolites are required for wider applications in the
120 ppm [1], 150 ppm [3,11], 220 ppm [57] for Ca2+ ions and marketplace globally. The mass-production price until now has been a
250 ppm for Mg ions [81]. Furthermore, other low- cost materials for barring factor for large-scale implementation. An eco-friendly metho-
reduction of Ca2+ were attained as modified sugarcane bagasse & dology was utilized for the synthesis of nanopowder (14 nm) zeolite
coffee husk [8], Raw pine cone & modified pine cone [9], MIEX-Na using an inexpensive, non-toxic reagent and readily available abundant
resins [10] and grafting copolymerization of acrylic acid [65]. The waste raw materials with the assistance of a domestic-microwave to
aforementioned materials, again have been tested in solutions con- produce zeolite materials that can be used to reduce the hardness of the
taining small Ca2+ content (120, 230, 103 and 20 ppm, respectively) water in groundwater and in seawater desalination applications. Herein
which is not considered hard water. While the zeolite materials herein a successful conversion of disposed Al raw material (scrap wire cable,
exhibit great benefits for application in water remediation at extremely foil takeaway, cans, and spray aerosol bottles) along with disposed of
high salt concentrations (1000–4000 ppm) and are the as promising silica gel were used to produce active zeolitic materials (type X and A
substances for removal of hardness from water supplies. Furthermore, it zeolite phases). The synthesized zeolites were used to eliminate the
is worth noting that the Ca2+ removal herein was achieved in such a hardness of water (> 1000 ppm), which showed 90 % rapid removal of
short time about 30 min along with the synthesized zeolite materials Ca2+and Mg2+ within 30 min using small amount of materials
were effective in acidic, basic and neutral solutions. It can also be used (10 g.L−1). Zeolite samples can be used for 3 consequent cycles, in-
at different temperature range from 25−60 °C, alongside the ease of dicating a high capacity with successful elimination of Ca2+ was
activation using cheap materials is another advantage. Finally, con- achieved in a broad range of pH values, then spent zeolites can be easily
sidering the circular economy, time savings and inexpensive chemicals regenerated by 1 M NaCl at room temperature. Freundlich and Temkin's
are factors that need to be taken into considerations. Herein we aimed isotherm were more suitable than the Langmuir isotherm model herein.
to achieve three of the SDGs such as the human health (goal no. 3), The physical adsorption process was verified by Temkin approach for
clean water (goal no. 6) and responsible consumption and production all used zeolite samples along with the positive value of ΔH° which was
(goal no. 12). below 40 kJ.mol-1. The obtained data fitted pseudo-second-order model
and intraparticle diffusion model. Zeolite sample can be used either in a
single or binary metals system simultaneously and achieve > 85 %
3.15. Cost assessment of synthesized zeolite decrease in salt ions. The synthesized zeolite materials showed excellent
capacity in reducing hardness of water in a real sample of seawater and
Demand for synthetic zeolites is strong globally. One such area of groundwater. According to our approach, the total price for the
application is the wastewater sector in which zeolites can be used to synthesis of 1 kg of zeolite is only 14 $/kg which is 70 % lower the
remove water hardness allowing water to be consumed again by hu- commercial price of zeolite materials. Herein we aimed to achieve three
mans and improving its overall quality. Couple with this, the fact that of the Sustainable Development Goals (SDGs) including human health,
synthetic zeolites can be regenerated easily using reagents at room clean water and responsible consumption and production.
temperature without the need for additional energy. Decreasing the
production price is required for its utilization in industrial purposes. Declaration of Competing Interest
The inexpensive technique and reasonable price of chemical reagent
(NaCl solution) were the emphases of this study in which successfully The author declares no competing financial interests.
prepared zeolites was made from abundant aluminium waste in a low
cost and facile way. For each 1 kg of synthesized zeolite, only 1 kg of Acknowledgements
NaOH is needed (price about 6.5 $/kg). The charged ensued with the
disposal of waste Al sources is very low, approximately 10 EGP/Kg The authors would like to acknowledge the support given by the
(0.56 $/kg) compared with other sources for Al salts. One of the fun- EPSRC project “Advancing Creative Circular Economies for Plastics via
damental costs of production within the industry is electricity. A do- Technological-Social Transitions” (ACCEPT Transitions, EP/S025545/
mestic home-microwave running at 170 W for just 15 min without 1). AO wish to acknowledge the support of the Sustainable Energy
auxiliary calcinations was utilized for this preparation method. Research Centre, at Queen’s University Belfast Pioneering Research
Electricity cost for the synthesis and ageing of zeolite samples is about Programme. The authors also wish to acknowledge the support of The
6.5 $/kg. The total price for production of 1 kg of zeolite is no more Bryden Centre project (Project ID VA5048) which was awarded by The
than 14 $/kg. Manufacturing zeolite from waste and disposal materials European Union’s INTERREG VA Programme, managed by the Special
decreases the production price by at least 70 % compared to commer- EU Programmes Body (SEUPB), with match funding provided by the
cial zeolites available in the market. The published production price of Department for the Economy in Northern Ireland and the Department of
zeolite NaA from rice husk was 26.092 $.100g−1 [82]. While in this Business, Enterprise and Innovation in the Republic of Ireland. The
work, the fabrication cost for NaX, NaA or NaY type is only 1.4 authors would like to thank Charlie Farrell and Patrick McNicholl who
$.100 g−1. An extra feature for these synthesized zeolites in this study is assisted in the proof-reading of the manuscript.
the affordable regeneration using a low price and readily available re-
agent such as NaCl. Just 2 $/kg is enough to make zeolite samples Appendix A. Supplementary data
reusable for more than one cycle by NaCl solution. In addition, a
miniscule amount of zeolite achieved high performance for captivating Supplementary material related to this article can be found, in the
and reducing 90 % of the high hard water concentration. The cost as- online version, at doi:https://doi.org/10.1016/j.jwpe.2019.101104.
sociated with such an effective amount (10 g.L−1) is approximately
0.14 $. 10 kg of tested zeolite could be utilized in the treatment of 1 ton References
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