Journal of Cleaner Production 172 (2018) 2636e2645

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Journal of Cleaner Production

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Synthetic zeolites as potential sorbents of mercury from wastewater

occurring during wet FGD processes of flue gas
_
Dorota Czarna a, *, Paweł Baran b, Piotr Kunecki a, Rafał Panek c, Robert Zmuda d
,
Magdalena Wdowin a
a w, Poland
Mineral and Energy Economy Research Institute, Polish Academy of Sciences, Wybickiego 7A, 31-261, Krako
b w, Poland
AGH University of Science and Technology, Av. Mickiewicza 30, 30-059, Krako
c
Lublin University of Technology, Nadbystrzycka 40, 20-618, Lublin, Poland
d
SBB Energy S.A., Łowicka 1, 45-324, Opole, Poland

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

Article history: This paper evaluates the suitability of fly ash-derived zeolites as sorbents of mercury in water and
Received 23 June 2017 wastewater. The tested materials were type X and type A synthetic zeolites obtained by hydrothermal
Received in revised form synthesis of Class F fly ash. Silver-modified type X fly ash-derived zeolites were also used to check the
1 November 2017
need for structural modification. The commercial products 4A and 13X zeolites were used as reference
Accepted 19 November 2017
materials. Mercury sorption experiments were carried out under static conditions in an artificial solution
Available online 20 November 2017
with an Hg concentration in the range of 13.20e575 mg dm
3. In each case, the sorption efficiency was
achieved at a level of above 90%. A second experiment involved the removal of mercury from real
Keywords:
Fly ash
wastewater using the wet desulphurization process for flue gas. The results for the tested samples show
Zeolites extremely high sorption efficiency at a level of 99%. Based on these results, it can be stated that fly ash-
Mercury derived zeolites have similar sorption properties to commercial products in terms of their used as
Wastewater mercury sorbents for liquid waste and are therefore a cost-effective substitute for commercially available
WFGD products. The X and A types of the zeolite structure were found to remove mercury at a similar level.
Isotherms © 2017 Elsevier Ltd. All rights reserved.

1. Introduction is becoming an increasingly important issue. One of the main

Mercury is one of the most toxic pollutants found in the aqueous
system, which is transformed into methylmercury by biochemical
reactions (Attari, 2015). In wastewater, mercury occurs in metallic
forms, undissociated molecules, Hg2þ and Hg2þ 2 ions and complex
ions (Da˛ browski et al., 2004).
Mercury occurs naturally in volcanoes that produce half of the
mercury emissions released into the atmosphere. In addition, this
toxic metal is generated by human activities, such as combustion
(65%), the production of gold (11%), the production of non-ferrous
metal (6.8%) and the production of cement (3%) (Shafeeq et al.,
2012). Moreover, as it is not a biodegradable compound, it is
particularly dangerous to human health, the environment and
other living organisms (Somerset et al., 2008).
In light of new restrictions contained in the Minamata
Convention (2013), reducing anthropogenic emissions of mercury
* Corresponding author.
E-mail address: dczarna@meeri.pl (D. Czarna).
sources of mercury pollution is the combustion of fossil fuels, i.e.,
coal and lignite, which are still the main fuels used in power plants
(Wang et al., 2010). Throughout coal combustion, mercury is
released into the flue gases (in the elemental [Hg0] forms, as well as
in oxidized [Hg2þ] and particulate-bound mercury [Hgp] forms, due
to various thermochemical reactions) (Yang et al., 2007; Wdowin
et al., 2014a).
The new regulations will contribute to addressing current needs
related to the modernization of Polish and European industrials
sectors, which must comply with them. Adapting to the planned
regulations will be a major challenge for the Polish energy sector.
The expected timeline for the publication of the Large Com-
bustion Plants BAT (Best Available Techniques) Reference Docu-
ment (BREF) is the second quarter of 2017. As agreed in the draft
document (published in 2015), the largest emission restrictions will
apply to combustion plants with a total rated thermal input
exceeding 50 MW. Additionally, emission standards have been
extended with new types of pollutants, including CO, HCl, HF, N2O
and Hg. In the case of Hg, coal-fired power plants will need to
obtain the following levels (BAT, 2013):

https://doi.org/10.1016/j.jclepro.2017.11.147
0959-6526/© 2017 Elsevier Ltd. All rights reserved.
 D. Czarna et al. / Journal of Cleaner Production 172 (2018) 2636e2645
Abbreviations
BAT/BREF the BAT (Best Available Techniques) Reference
Document (BREF)
WFGD wet flue-gas desulphurization
XRD X-ray diffraction
EGU electricity generating units
SD standard deviations
SBET BET surface area
qe the equilibrium amount of Hg2þ exchanged by tested
materials [mg g
1]
Ce the equilibrium Hg2þ concentration in the solution
[mg dm
3]
qmax the maximum uptake of mercury exchanged [mg g
1]
KL the Langmuir constant [dm3 mg
1]
 <1e3 mg/dNm3 for new installations with a capacity below
300 MW (<1e2 mg/dNm3 for lignite coal),
 <1e9 mg/dNm3 for existing plants with a capacity below
300 MW (<1e10 mg/dNm3 for lignite coal),
 <1e2 mg/dNm3 for new plants with a capacity of 300 MWtt
(<1e4 mg/dNm3 for lignite coal),
 <1e4 mg/dNm3 for existing plants with a capacity of 300 MWtt
(<1e7 mg/dNm3 for lignite coal).
One of the primary methods of mercury capture from exhaust
gas is wet flue-gas desulphurization (WFGD); however, data eval-
uation suggests that sulphur complexes are major drivers for the
chemical reduction of oxidized mercury into elemental mercury,
which can result in the re-emission of mercury from the WFGD
absorber (Miller et al., 2006).
It is known that over 50% of the existing coal-fired electricity
generating units (EGUs) based on capacity currently utilize wet flue
gas desulphurization (WFGD) systems to reduce sulphur dioxide
emissions (EPA, 2013). The failure of WFGD systems to consistently
facilitate compliance with mercury emission limitations can be due
to the phenomenon known as mercury re-emission (Blythe et al.,
2008, 2010; Keiser et al., 2012; Sankey et al., 2013; Smokey et al.,
2012; Srivastava et al., 2006; Winter et al., 2010). Forms of mer-
cury in the boiler are affected by the type of fuel fired at the unit, fly
ash characteristics and boiler flue gas, as well as the configuration
of pollution control equipment. Generally (as previously noted),
during combustion most Hg is present in its elemental form (Hg0).
All the combustion processes result in oxidized gaseous forms of
Hg, primarily mercuric chloride (HgCl2) or particulate-bound Hg
(Hgp). Given that it is difficult to capture Hg0 in the boiler, and also
because oxidized mercury has a tendency to associate with par-
ticulate matter and is water-soluble, the preferred method of
removal is to use electrostatic precipitators and fabric filters for
particulate control, and desulphurization scrubbers; two speciation
that cause the re-emission of Hg to WFGD wastes (Omine et al.,
2012). The re-emission of elemental mercury (Hg0) gas occurs
when aqueous divalent ionic mercury, [Hg2þ]aq, is chemically
reduced to elemental mercury and released back into the gas. The
ionic mercury reduction reaction that occurs is shown below (eq
(1)) and (eq (2)), (Keiser et al., 2014):
[HgSO3]aq þ H2O /[Hg0]aq þ [H2SO4]aq (1)
[Hg0]aq / [Hg0]gas (2)
2637
KF the Freundlich constant [dm3 g
1] and 1/n is the
heterogeneity factor
AT the Temkin isotherm equilibrium binding constant
[dm3 g
1]
B the Temkin isotherm constant
R the universal gas constant 8.314 J/mol/K
T the temperature 298 K
BT the constant related to the heat of sorption [J/mol]
Na-X synthetic zeolite about faujasite group,
Ag-X synthetic zeolite about faujasite group modified by
silver ions
13X commercial zeolite about faujasite group,
Na-A synthetic zeolite about tschertnichite group,
4A synthetic zeolite about tschertnichite group.
Based on the above information, it is concluded that the control
of mercury re-emission across WFGDs using active scrubber liquor
mercury management is a strategy that does not enable electricity
generating units to comply with mercury emission limitation reg-
ulations. Thus power plants must seek an efficient solution to the
problem of mercury removal from WFGD wastewaters.
Due to the toxicity of mercury, to date, a variety of techniques
and cost-effective technologies have been developed for the
treatment of wastewater (Wang and Peng, 2010); the general
classification of which is as follows (Azimi et al., 2017):
electrochemical treatments (Tran et al., 2017; Bazrafshan et al.,
2015):
electrocoagulation,
electro-flotation,
electrodeposition,
physicochemical processes (Kurniawan et al., 2006):
chemical precipitation,
ion exchange,
adsorption (Bobade and Eshtiagi, 2015):
activated carbon,
carbon nanotubes,
wood sawdust adsorbents,
membrane filtration (Abu- Qudais and Moussa, 2004),
photocatalysis processes (Chowdhury et al., 2014),
nanotechnology (Wang et al., 2012).
Adsorption is one of the most effective, suitable, economic and
healthy methods for mercury removal from wastewater (Liu et al.,
2013). An important feature, other than its low cost, high effi-
ciency and ease of application, is the availability of adsorbents
(Ramadan et al., 2010). As shown in Table 1, many different sorbents
have been examined for the removal of mercury from aqueous
solutions and removal efficiency close to 100% has been found.
In addition to those listed above, other materials that have been
tested are: clay (Atsar et al., 2013), silica gel (Tzvetkowa and
Nickolov, 2012), zeolites (Erdem et al., 2004; Wdowin et al.,
2014b) and sorbents derived from waste materials such as black
tea (Mohammed, 2012), rice husk (Ajmal et al., 2003), coal ash
(Wang et al., 2006), sugar cane bagasse (Ayub et al., 2001) and
wheat straw (Gong et al., 2008). However, because the need to
reduce anthropogenic emissions of mercury is a new requirement,
no sorbents have as yet been tested for the treatment of WFGD
wastewaters. Some of the promising materials for this purpose
appear to be zeolites.
2638 D. Czarna et al. / Journal of Cleaner Production 172 (2018) 2636e2645

Table 1
The mercury removal efficiency from aqueous solutions using different types of adsorbents.

Adsorbent Initial Hg2þ Contact pH Adsorbent Removal Ref.

concentration [mg/ time [h] dosage [g] efficiency [%]
L]

Activated carbon from organic sewage sludge without 200 7 5 10 83.4 Zhang et al., 2005
activation treatment
Activated carbon from organic sewage sludge after H3PO4 200 7 5 6 100 Zhang et al., 2005
activation treatment
Activated carbon from organic sewage sludge after H2SO4 200 7 5 8 100 Zhang et al., 2005
activation treatment
Activated carbon from organic sewage sludge after ZnCl2 200 7 5 4 100 Zhang et al., 2005
activation treatment
Weathered coal 3 48 6 0.8 99.8 Meena et al., 2004
Chitosan- coated magnetite nanoparticles 6.2 e 5 0.67 99.91 Rahbar et al., 2014
Coal based activated carbon, raw coconut husk based 40e450 e 4 4.0 94.1e99.5 Guo et al., 2017
activated carbon, raw peach stone based activated carbon
Ag/graphene 100 2 5 0.1 98 Qu et al., 2017
Marine microalga Cystoseira baccata 500 4 4.5 0.25 83 Herrero et al., 2005
Ornamental rock solid waste 100 24 4.76 2 greater than 90 Dos Santos et al., 2015
Thiolated cross- linked polyethyleneimine 40 0.5 8; 3 0.2 97 Saad et al., 2013
Flower- like titanate nanomaterial 100 1 5 0.01 98.2 Liu et al., 2015

Zeolites are porous, hydrated aluminosilicates of alkali ele-
ments, alkaline earth metals or other cations (Wdowin et al.,
2014b). Their properties, such as thermal stability, ion exchange,
molecular sieve and catalyst properties, make these materials
useful for a variety of applications (ion exchange, catalysis, adsor-
bents, medicine, odour removal, sensors) (Franus et al., 2014;
Auerbach et al., 2003). For zeolites, ion exchange is the main
mechanism of adsorption in wastewater purification from mercury
(Chojnacki et al., 2004).
The ability to obtain synthetic zeolites from different silica
sources was developed at the end of the last century and waste
materials were often used to produce a cost-effective zeolite
product. The most common source for zeolite synthesis is fly ash,
which forms the highest percentage of coal combustion products.
Zeolites can be produced in the reaction between sodium silicate,
sodium aluminate, mineral resources and some by-products of
combustion. The products of these reactions are porous materials
such as analcime, chabazite, cancrinite, gmelinite, Na-P1, ZSM-5,
ZSM-28, Na-X, Na-Y, phillipsite and sodalite (Franus et al., 2014).
The aim of the study presented here was the evaluation of the
suitability of synthetic zeolites (commercial 4A and 13X, as well as
those obtained by the hydrothermal reaction of Na-X, Na-A and Ag-
X fly ash), as potential sorbents of mercury compounds in aqueous
solutions, such as wastewater, which are produced during WFGD
processes. To date, no significant papers have been published on
the removal of mercury from WFGD wastewater. This is due to the
fact that BREF requirements are only obligatory from 2017.
The innovative aspects of the research presented in this article
primarily relate to the purification of WFGD wastewaters from
mercury by means of zeolites. Until now there have been no re-
strictions that require the purification of Hg from this type of waste.
However, the Minamata Convention (UNEP, 2013), as well as new
BAT/BREF restrictions, now oblige power plants and other emitters
to reduction this form of pollution. Most power plants focus on
reducing mercury emissions from flue gas and the majority treat
the re-emission of mercury to WFGD wastes as a way of solving the
problem of Hg emission into the air. Thus, to date, no power plants
have attempted to solve the problem of purification of such wastes.
As a consequence, no methods have been developed for the puri-
fication of WFGD wastes from mercury, and it is also difficult to find
any new research in this area. In fact, there are no significant papers
or patents that describe the problem (most conference papers are
presented by the industry) because most of the energy sector has so
far avoided the problem of re-emission due to the lack of any re-
striction or requirements for mercury emission reduction. How-
ever, in light of the new restrictions contained in the Minamata
Convention (2013) and the BAT/BREF restrictions, reducing
anthropogenic emissions of mercury is becoming an increasingly
important issue.
2. Materials and methods
2.1. Materials
The tested materials used as potential mercury sorbents mainly
constituted fly ash-derived zeolites obtained by the hydrothermal
synthesis of fly ash, i.e., the Na-A type (tschernichite group) and the
Na-X type (faujasite group). X type silver-loaded (silver modifica-
tion was carried out using the ion exchange method) zeolite was
also used in order to check whether such modification is favourable
in the removal of mercury from water, similar to the case of Hg
uptake from flue gas (Wdowin et al., 2014a).
2.1.1. Preparation and characteristics of fly ash-derived zeolites
The zeolites were obtained by the hydrothermal synthesis
method in a PP bottle according to the schemes presented below
(Figs. 1e2):
According to the American Society for Testing and Materials
(ASTM), during conventional combustion of hard coal fly ash the
synthesis of zeolites was Class F (SiO2 þ Al2O3þ Fe2O2 >70%
(Blissett and Rowson, 2012) This finding was taken from Polish
power plant. The zeolites obtained by hydrothermal synthesis
presented the X and A structures. Additionally, in the synthesis of
fly ash, X type zeolite was activated by silver, using the ion ex-
change method described by Wdowin et al. (2014a, 2015): 100 g of
zeolite flooded with a 500 ml 0.5 M solution of AgNO3. The sample
was then shaken in a dark room for 24 h (h) at room temperature
and air-dried in the dark. The amount of zeolite in the derived
products was approximately 60 wt% in all cases, whereas the
remainder of the products constituted residuum (quartz, mullite
and carbonates) (Wdowin, 2015). The ratio of SiO2 to Al2O3 for all
tested zeolites was 1.2e1.58, which indicated that these structures
are characterized by low-silica zeolites. The materials were also
characterized by different textural properties, as presented in
Table 2, where the surface area for type X zeolites was much higher
than for type A zeolites.
 D. Czarna et al. / Journal of Cleaner Production 172 (2018) 2636e2645 2639

A zeolite phase in the reaction products was determined based on

the main d-spacing, dhkl ¼ 12.2, 8.66, 7.08, 4.08, 3.70, 3.28 Å. Using
calculations based on Rietveld methods, the quantity of zeolite
content from XRD was 75 wt% for fly ash-derived structures. The
presence of a Na-X zeolite phase in the reaction products was
determined based on the main d-spacing, dhkl ¼ 14.47, 3.81, 5.73,
8.85, 4.42, 7.54, 4.81, and 3.94 Å. Again, using calculations based on
Rietveld methods, the quantity of zeolite content from XRD analysis
was 70 wt% for fly ash-derived structures.
As shown in Fig. 5, observation of the morphology, using SEM
analysis, shows that zeolite products obtained from fly ash have
structures that are characteristic of crystal habits (cubic crystals for
type A, isometric, cubic crystals for type X).

2.2. Methods

Powder X-ray diffraction (XRD), using a Panalytical X'pert APD

Fig. 1. Scheme for the Na-A zeolite synthesis procedure.
diffractometer with the data processed by Philips X'Pert and Clay-
Lab software, ver. 1.0, was used for mineralogical analysis of the
tested materials. The identification of zeolite phases was verified
based on the PCPDFWIN ver. 1.30 database formalized by JCPDS-
ICDD. The morphology of the grain, as well as the crystal habits
and chemical composition of the main mineral components, was
investigated using an FEI Qanta 250 FEG scanning electron micro-
scopy and energy dispersive spectroscopy (SEM/EDAX).
The Si/Al ratio for tested zeolites was calculated based on the
chemical compositions determined by an X-ray energy dispersive
fluorescence spectrometer (XRF, PANalytical Epsilon 3 spectrom-
eter). The analysis was carried out on the range of Na-Am (sodium
to americium) and the instrument was equipped with an X-ray tube
Rh 9 W, 50 kV, 1 mA, 4096-channel spectrum analyser, 6 mea-
surement filters (Cu-500, Cu-300, Ti, Al-50, Al-200, Ag), the high-
solid state detector SDD (Be window, a thickness of 50 mm) and
cooled by a Peltier cell.
The BET specific surface area was determined based on the re-
sults obtained by ASAP 2020 using N2 as the adsorbate at
196  C.
N2 sorption isotherms were acquired from 0.01 to 0.99 relative
pressure (P/P0). This value was calculated based on the SBET
multilayer adsorption model, where P/P0 was between 0.05 and
0.20, providing positive BET constants.

2.3. Adsorption experiments

A number of static sorption experiments on artificial solutions

Fig. 2. Scheme for the Na-X zeolite synthesis procedure. were carried out within the framework of this study. In each case,
10 g of the zeolite was added to 100 cm3 of HgCl2 solution con-
taining different concentrations of Hg2þ ions
The XRD diffraction pattern is present (Figs. 3 and 4) in the (13.20e575 mg dm
3), with the mixture agitated for 1 h at room
tested materials that derive from fly as well as those that are temperature using a mechanical shaker. Following the adsorption
commercial in origin. Figs. 3 and 4 show that type X and type A process, the suspension was filtered through a membrane filter
zeolites were present in the tested materials. The presence of a Na- (AlfaChem LABORATORIA, size 389). Finally, the pH was established
at the level of 5e6 using acetic acid. The residual solution (con-
taining mercury ions) was analysed with an Inductively Coupled
Table 2 Plasma Mass Spectrometry (ICP-MS, ELAN DRC-e Perkin Elmer
Textural properties of the adsorbents. Sciex ELAN 6000 instrument), the detection limits being below
Sample BET Surface area (m2 g
1) Si/Al ratio Pore volume (cm3 g
1) 0.01 mg dm
3 for the analysed metals.
Commercial products (zeolites 13X and 4A) were used as
Na-A 39 1.42 0.07
Na-Xa 260 1.43 0.22 reference materials and these were supplied by Sigma Aldrich,
Ag-X 203 1.58 0.16 while NaOH and acetic acid were supplied by POCH and HgCl2
4A 583 1.44 0.31 solution by Chempur.
13X 635 1.8 0.60 The equilibrium adsorption qe (3) and % uptake (4) were
a
Wdowin et al., 2014a. calculated using equations (3) and (4) below:
2640 D. Czarna et al. / Journal of Cleaner Production 172 (2018) 2636e2645

Fig. 3. XRD diffraction patterns of zeolites type X.

Fig. 4. XRD diffraction patterns of zeolites type A.

uses lignite as the main fossil fuel in the production of electricity.

ðC
Ce Þ  V The pH of this waste was 7.00 and its chemical composition,
qe ¼ 0 (3)
W determined using the same equipment used for the artificial solu-
tions, was (in mg dm
3): Ca 623.75 (SD 5.031); Mg 879.41 (SD
C0
Ce 2.810); Na 286.69 (SD 4.591); S 4810.96 (SD 16.018); Si 89.32
% uptake ¼  100 (4) (1.492); K 32.12 (0.676); B 2.02 (SD 0.012); Hg 0.538 (SD 0.003).
C0

where qe is the adsorption capacity [mg g
1], C0 is the initial con-
centrations of solution [mg dm
3], Ce is the equilibrium concen-
tration of the solution [mg dm
3], V is the volume of the aqueous
solution [dm3], and W is the mass of adsorbent [g].
In all these cases the mass of adsorbent was W ¼ 10 g and
V ¼ 0.1 dm3. The models of Freundlich, Langmuir and Temkin were
used for the obtained results.
The final test was carried out on real wastewater, rich in mer-
cury and other compounds, produced during the application of
WFGD methods. The wastewater came from a power plant that
3. Results
The results of the static sorption experiments are presented in
Table 3. It can be seen that the sorption of mercury from artificial
solution is at an average level of 90%, both for fly ash-derived ze-
olites and for commercial products. It is noteworthy that the
sorption for real wastewater, which contains other pollution com-
pounds, is higher at the level of 99% (Table 4). This is due to the fact
that the concentration of mercury in such waste is significant lower
(0.5 mg dm
3) than in the tested artificial solution.
 D. Czarna et al. / Journal of Cleaner Production 172 (2018) 2636e2645 2641

Na-A Na-X Ag-X

4A 13X

Fig. 5. Morphology of tested zeolite materials.

Table 3
Sorption results for prepared HgCl2 solutions.

SAMPLE C0 [mg dm
3] Ce [mg dm
3] qe [mg g
1] Uptake [%] Average value of uptake [%]

Ag-X 13.20 1.07 0.12 91.93 89.60

237.14 25.40 2.12 89.29
575.00 71.50 5.04 87.57
Na-A 13.20 0.58 0.13 95.61 90.57
237.14 21.21 2.16 91.06
575.00 86.00 4.89 85.04
Na-X 13.20 0.51 0.13 96.17 89.41
237.14 39.43 1.98 83.37
575.00 65.00 5.10 88.70
13X 13.20 1.52 0.12 88.49 90.18
237.14 13.04 2.24 94.50
575.00 71.50 5.04 87.57
4A 13.20 1.43 0.12 89.17 90.30
237.14 15.28 2.22 93.56
575.00 71.00 5.04 87.65

3.1. Mercury exchange isotherms
For the obtained results, numerous isotherms according to the
models of Langmuir, Freundlich and Temkin were found.
3.1.1. Langmuir adsorption isotherm
Freundlich and Langmuir isotherms are the most common way
to describe adsorption phenomena. Langmuir isotherms are based
Table 4
Sorption results performed on the wastewater.
on monolayer adsorption without interaction between adsorbed
ions (Eldefrawy et al., 2014). The important assumption of Lang-
muir isotherm theory is the stability of heat adsorption regardless
of surface coverage. In the case of heterogeneous surfaces, this
assumption will not be met because the heat of adsorption de-
creases with surface coverage. However, despite the idealized na-
ture of the Langmuir isotherm, it is important to determine the
adsorption equilibrium. This type of isotherm is often the basis for
more complicated models of adsorption. This relation is described
by Equation (5):

SAMPLE C0 Ce qe % uptake Ce 1 Ce
¼ þ (5)
[mg dm
3] [mg dm
3] [mg g
1] qe qmax KL qmax
Ag-X 0.538 0.0050 0.005 99.065
Na-A 0.538 0.0011 0.005 99.794 where qe is the equilibrium amount of Hg2þ exchanged by tested
Na-X 0.538 0.0035 0.005 99.346 materials [mg g
1], Ce is the equilibrium Hg2þ concentration in the
13X 0.538 0.0090 0.005 98.318 solution [mg dm
3], qmax is the maximum uptake of mercury
4A 0.538 0.0013 0.005 99.757
exchanged [mg$g
1], and KL is the Langmuir constant [dm3 mg
1].
2642 D. Czarna et al. / Journal of Cleaner Production 172 (2018) 2636e2645

3.1.2. Freundlich adsorption isotherm  

The Freundlich model assumes the adsorption of metal ions on RT
qe ¼ $lnðAt Ce Þ (7)
the heterogeneous surface by monolayer adsorption (Eldefrawy b
et al., 2014). This isotherm is the limit form of the Langmuir
   
isotherm equation. The Freundlich model isotherm is described by RT RT
qe ¼ $lnAT þ $lnCe (8)
Equation (6): b b

1 RT
ln qe ¼ ln KF þ ln Ce (6) BT ¼ (9)
n b
where: KF is the Freundlich constant [dm3 g
1] and 1/n is the
qe ¼ BT lnAT þ BT lnCe (10)
heterogeneity factor.
The constant n in the Freundlich equation characterizes the where AT is the Temkin isotherm equilibrium binding constant
heterogeneity of the surface adsorption energy, while its value [dm3 g
1], B is the Temkin isotherm constant, R is the universal gas
should be greater than 1. When n ¼ 1, the complete energy ho- constant 8.314 J/mol/K, T is the temperature 298 K, and BT is the
mogeneity of the surface can be assumed, which means that constant related to the heat of sorption [J/mol].
(similar to the case involving Langmuir theory) the heat of The fitting parameters and constants for each model are pre-
adsorption is independent of the surface coverage. sented in Tables 5 and 6.
Experimental sorption isotherms are presented in a formal way
with models of isotherms described above. Experimental data were
summarized in the appropriate coordinate systems in such a way
that the linear form of the isotherms was the basis to determine the
3.1.3. Temkin adsorption isotherm characteristic values of constants, which were shown in Table 6
The Freundlich adsorption isotherm describes the heterogeneity (including the R2 parameter).
of the adsorbent surface (n parameter) by assuming that relation- Based on the determined constant values, the Langmuir,
ship between the heat of adsorption and surface coverage has a Freundlich and Temkin isotherms were drawn in a linear form (for
logarithmic form. Very often, the decrease in the heat of adsorption each zeolite-solution system). The points indicate the experimental
is closer to a linear than logarithmic form. This shape is the basis of data (Figs. 6e7).
the Temkin isotherm. This type of isotherm was derived from the By analysing the obtained results, it can be stated that the
Langmuir isotherm on the assumption that the heat of adsorption Langmuir model adsorption isotherm characterized the worst
decreases linearly with an increase in the surface coverage. Equa- fitting parameters, mainly for the 4A and 13X zeolites. For this
tions (7)e(10) describes this type of adsorption isotherm. The basis reason, the interpretation of Langmuir constants was impossible.
of this equation is the uniform distribution of binding energies This is particularly relevant to the monolayer capacity, which is best
(Tempkin and Pyzhev, 1940). at differentiating parameters in analysed systems.
The best fitting parameters were obtained by the Freundlich
adsorption isotherm. Analysis of the experimental data shows a
Table 5 similar sorption capacity for each sample. The model of the
Fitting parameters of adsorption model isotherms for tested materials.
Freundlich isotherm allows for differentiated samples. For a higher
SAMPLE C0 LANGMUIR FREUNDLICH TEMKIN equilibrium of Hg2þ concentration, the sorption capacity for the
Ce 1/Ce 1/qe log Ce log qe qe ln Ce Na-X and Na-A samples will be significantly lower compared to the
commercial zeolites.
Ag-X 13.20 1.07 0.935 8.333 0.029
0.916 0.121 0.068
237.14 25.40 0.039 0.472 1.405 0.326 2.117 3.235 The modification of zeolite by silver compound did not espe-
575.00 71.50 0.014 0.198 1.854 0.702 5.035 4.270 cially exhibit properties relative to the Hg2þ ions. The same argu-
Na-A 13.20 0.58 1.724 7.692
0.237
0.899 0.126
0.545 ment can be made for the Temkin adsorption isotherms, which are
237.14 21.21 0.047 0.463 1.327 0.334 2.159 3.054
similar, but will be more favourable in low concentrations of
575.00 86.00 0.012 0.204 1.934 0.689 4.890 4.454
Na-X 13.20 0.51 1.961 7.692
0.292
0.897 0.127
0.673
commercial zeolites.
237.14 39.43 0.025 0.505 1.596 0.296 1.977 3.675
575.00 65.00 0.015 0.196 1.813 0.708 5.100 4.174
3.2. Mercury removal efficiency
13X 13.20 1.52 0.658 8.333 0.182
0.933 0.117 0.419
237.14 13.04 0.077 0.446 1.115 0.350 2.241 2.568
575.00 71.5 0.014 0.198 1854 0.702 5.035 4.270 Fig. 8 illustrates the relation between the type of zeolite and its
4A 13.20 1.43 0.699 8.333 0.155
0.929 0.118 0.358 ability to remove mercury from an aqueous solution. In general,
237.14 15.28 0.065 0.450 1.184 0.346 2.219 2.727 mercury removal efficiency ranges from 83 to 95% in an initial
575.00 71.00 0.014 0.198 1.851 0.702 5.040 4.263
concentration from 13.20 to 575.00 mg dm
3. Despite the similar

Table 6
Langmuir, Freundlich and Temkin isotherm constants for mercury.

Sample qmax KL R2 1/n n KF R2 AT BT B R2

Ag-X 14.026 0.008 0.929 0.891 1.123 0.115 0.999 0.820 2375.9 1.043 0.854
Na-A 6.870 0.027 0.966 0.743 1.346 0.196 0.996 1.506 2828.3 0.876 0.893
Na-X 6.277 0.024 0.417 0.711 1.407 0.198 0.976 1.908 3134.9 0.794 0.703
13X 16.354 0.007 0.265 0.994 1.006 0.099 0.938 0.625 1959.0 1.265 0.979
4A 16.354 0.006 0.349 0.986 1.015 0.098 0.964 0.639 2016.3 1.229 0.958
Langmuir isotherm constants for Freundlich isotherm constants for mercury Temkin isotherm constants for mercury
mercury
 D. Czarna et al. / Journal of Cleaner Production 172 (2018) 2636e2645 2643

Fig. 6. Adsorption isotherms for commercial zeolites: a) 4A, b)13X

Fig. 7. Adsorption isotherms for fly ash-derived zeolites: c) Ag-X, d) Na-A, e) Na-X.

results, the highest efficiency (90.57%) was achieved for the Na-A
sample, as shown in Table 3. However, as all tested materials
(commercial and fly ash-derived zeolites) showed a very high ef-
ficiency of Hg ion removal, their efficiency in the purification of
wastewater resulting from WFGD was also examined. In this sce-
nario, the differences in mercury removal efficiency were insig-
nificant and within the range of 99.065% for Ag-X to 99.794% for
Na-A zeolite. Therefore, we can conclude that zeolites are prom-
ising sorbents for the removal of mercury pollution from waste-
water resulting from the WFGD.
4. Conclusions
The focus of this paper is an evaluation of the suitability of
synthetic zeolites, obtained in the hydrothermal synthesis of fly
ash, as potential sorbents in the removal of mercury from WFGD
wastewater. Based on our research findings we draw the following
main conclusions:
 Based on the isotherms identified, it can be stated that in the
case of zeolite-mercury ion solution systems, the best fit was
observed in the Freundlich adsorption isotherm, where the R2
for all samples was above 0.9 (the best values were obtained for
Na-A and Na-X, at almost 1).
 For a higher equilibrium of Hg2þ concentration (575 mg dm
3),
the sorption capacities of all the samples were lower, i.e., from
85.04% to 88.70%, although sorption capacity is not very
different under test conditions. For WFGD waste, the values of
sorption capacity were at the level of 99% for all tested samples.
Therefore, fly ash-derived zeolites are a promising substitute for
commercial zeolite products for the removal of mercury pol-
lutants from WFGD wastewater.
 The application of fly ash-derived zeolites significantly reduces
the production costs of such sorbents. The cost of commercial
2644
105.000
100.000
Merury removal efficiency [%]
95.000
90.000
85.000
80.000
75.000
NaX+Ag
Fig. 8. Mercury removal efficiency for prepared HgCl2 solutions and wastewater, depending on the type of zeolite.
zeolites is approximately 300 euro per kg (prices are taken from
Sigma Aldrich), whereas in the case of fly ash-derived products
the costs are at the level of 5 euro per kg. Therefore, fly ash
development offers the potential for new profit streams.
 Zeolites with either an A or X structure removed mercury pol-
lutants efficiently at a level of above 90%.
 The modification of zeolites by silver compound did not improve
their efficiency, a factor that should be regarded as a benefit (if
zeolites need no modification, their application will be more
cost-effective).
The use of fly ash-derived zeolites in the purification of waste-
water containing mercury pollutants, which is produced by power
plants, can be profitable for this sector while also enabling it to
meet BAT/BREF requirements.
The research presented here reports the preliminary results;
therefore the next stage of the investigation will entail further tests
of sorption in static and dynamic conditions. This will allow the
authors to calculate the kinetics of sorption and to identify, in
detail, a suitable adsorption model. Dynamic sorption will allow for
the determination of the bed values necessary for the purification
of an appropriate amount of WFGD waste. Further, desorption ex-
periments will be carried out in order to access the possible
regeneration of tested sorbents. If the results are promising, the
construction of a demonstration installation will be considered in
order to check the efficiency of the proposed solution on a semi-
industrial scale. A Life Cycle Assessment will be described for the
proposed solution, as well as ways of utilizing the resultant waste.
Conflicts of interest
There are no conflicts of interest to declare.
Acknowledgements
This work was financed by the National Centre for Research and
Development project Lider contract number LIDER/384/L-6/14/
NCBR/2015.
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