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Article history: The synthesis of needle/brous particles of analogue of heulandite with particle diameter of
Received 13 October 2008 0.08 m, length 48 m and high specic surface area (478 m2 g1 ) with cation exchange capacity
Accepted 27 December 2008 (3.27 mequiv g1 ) have been achieved. The heulandite needles were obtained by using inorganic salts
Available online 10 January 2009
as a source for silicon and aluminum in the hydrothermal synthesis of the material. Alkalinity of the
Keywords:
medium played an important role in the formation of heulandite bers, as it affects the nucleation rate
Analogue of zeolite synthesis. The analogue of heulandite was characterized using spectroscopic, thermal analysis,
Heulandite scanning and adsorption techniques. After mechanical grinding of crystals of heulandite, obtained powder
Sorption was used for the study of radionuclide recovery from aqueous waste. The adsorption experiments were
Isotherm carried out under batch process with, pH of medium, amount of sorbent, time of contact between sorbate
Morphology and sorbent, metal ion concentration and temperature as the variables. The adsorption was strongly
dependent on pH of the medium and the uptake of all the metal ions increased from pH 1.0 to 9.0 and
the maximum sorption was noticed in the pH range of 5.07.0. The optimum condition for these metal
ions (Th(IV), Eu(III), Sm(II), and Fe(III)) sorption on self synthesized analogue of heulandite was; 0.001 N
metal ion concentration, equilibration time of 4 h, 100 mg sorbent dose and 313323 K temperature.
This sorption process is t to both Langmuir and Freundlich sorption isotherm. Thermodynamic studies
predict the endothermic and spontaneous nature of the same.
2009 Elsevier Inc. All rights reserved.
1. Introduction basis of their framework topology, for which the structure are
known. According to this heulandite comes under group 7 [7].
Zeolites are playing a prominent role in nuclear waste pro- Heulandite is the name of a series of tectosilicate minerals of
cessing and in its management, as they are well known for their the zeolite group. Prior to 1997, heulandite was recognized as
stability at high temperature and radiation elds [1,2]. Meeting the a mineral species, but a reclassication in 1997 by the Inter-
stringent coolant purity requirements of the nuclear industry is national Mineralogical Association changed it to a series name,
solely attributable to inorganic ion exchangers. In the last decade, with the mineral species being named heulandite-Ca, heulandite-
zeolites have been used extensively in the chemical decontamina- Na, heulandite-K, and heulandite-Sr. Heulandite-Ca, the most
tion process for radionuclide recovery, regeneration of decontami- common of these, is a hydrous calcium and aluminum silicate,
nants and removal of the formulation chemicals from the coolant |Ca2 ,Na4 |[Al8 Si28 O72 ]24H2 O. It belongs to the monoclinic system
[36]. Therefore, there is a continuing need to synthesize ion se- with cell dimensions a = 17.70 ; b = 17.94 ; c = 7.42 ; and
lective zeolites with uniform morphology and porosity, which are = 116 24 . Its space group is C 2/m [8]. According to Boles [9],
capable of removing radioactive substances from aqueous euents, the Si/Al mole ratio for heulandite is below 4. The crystal structure
as they have good stability toward temperature, ionizing radiation, exhibits three types of structural channels conned by tetrahe-
and oxidizing solutions. dral ring systems. Ten-membered A-rings and eight membered
Zeolites are inorganic polymers that have great variety in their B-rings conne the A and B channels running parallel to the c-
structures and have been classied into seven groups, on the axis. Eight-membered C-rings border C channels running parallel
to [100] and [102] [10]. Two eight membered rings of channel B
and two additional eight membered rings of channel C form cage I.
* Corresponding author. Two ten-membered rings of channel A and two eight-membered
E-mail address: sharmapankaj47@yahoo.com (P. Sharma). rings of channel C form cage II. This porous solid is of scientic
0021-9797/$ see front matter 2009 Elsevier Inc. All rights reserved.
doi:10.1016/j.jcis.2008.12.074
P. Sharma et al. / Journal of Colloid and Interface Science 332 (2009) 298308 299
and technological interest because of their ability to interact with [Al(NO3 )3 , CDH] as the aluminum source and sodium hydrox-
atoms, ions and molecules not only at their surface but through- ide [NaOH, Merck] as the alkali sources. Other materials included
out the bulk of the material and their unique properties such as sodium nitrate and double distilled water. This synthesis process
the existence of high intracrystalline surface area, the microporous comprises two steps. The rst step includes the preparation of gel
character of the uniform pore dimensions, the ion exchange prop- that contains the silica, aluminum and sodium in the same com-
erties, the ability to develop internal acidity, the thermal stability, position as mentioned above. This gel was prepared in a 200 mL
the high internal surface area along with their ability to absorb borosil beaker by dissolving nely divided silica and aluminum in
chemicals/molecules/ionic species in to their structure, gives rise 2.0 M sodium hydroxide solution. For complete mixing of gel, the
to great variety of applications which makes them special [1113]. gel solution was magnetically stirred for two hours on a magnetic
There are only a few papers, which report the sorption charac- stirrer. In the second step, the resultant mixture was immediately
teristics of heulanite and so far reported literature on heulandite placed in a 100 mL Teon lined stainless steel pressure bomb ves-
mainly discussed about their structural properties and morpho- sel which was then kept in a preheated oven 443 K, at autogeneous
logical changes [1416]. Yilmaz et al. [17] examine the physical, pressure and for 24 h. After the completion of 24 h period of syn-
chemical, mechanical and microstructural properties of mortars thesis, the product was ltered and washed repeatedly with double
produced by blending clinoptilolite, which is a zeolite mineral distilled water until the pH of the remaining solution was less
abundantly found in nature, into Portland cement with increasing than 9. The samples were dried at 323 K and were stored in pow-
ratios and it was observed that plasticity times extend depending der form for further use.
on the blend ratios of clinoptilolite blended cements and that early
strengths change according to Blaine values. Stolz et al. registered 2.2. Characterization
the symmetric changes in SiAl framework of fully Cd-exchanged
heulandite obtained from a Na-heulandite sample by treatment Powder X-ray diffraction (XRD) patterns for was recorded
with 1 M cadmium acetate solution at 373 K [18]. Bresciani-Pahor at room temperature on a PANalytical XPert-PRO diffractome-
et al. [19,20] reported the structures of a partially and a fully Ag- ter. Samples were scanned using CuK radiation of wavelength
exchanged heulandite. Ag+ occupies the positions analogous to 1.5405 and diffractograms were recorded in the range 2 =
Ca2+ and Na+ in natural samples. In addition, a new site with 5 50 . Data were collected in a step mode every 0.1 for a 3 s
a low occupancy was assigned to Ag+ [21]. Research concerning duration. The phases were identied by comparing the diffrac-
the application of the heulandite to the removal of radionuclide tion peaks with the data reported in literature [36]. The chemical
from different aqueous waste systems has not been reported much. composition of the synthesized material was checked for metals
Fewer studies are available, that only explains the sorption charac- like Na, Al and Si using energy dispersive spectroscopy (EDS). The
teristics of heavy metals on the synthetic and natural heulandite, bulk EDS analysis was performed on a JEOL JSM 5800 scanning
and its family member clinoplilolite [2225]. Keeping this in mind microscope equipped with a microprobe analyzer LINK ISIS (Ox-
it is decided to study the sorption potential of heulandite for these ford instrument). The thermal stability and the number of water
radionuclides. molecules bound with the synthetic analogues of heulandite were
Environmental temperature, pH of the medium, metal ion con- ascertained by differential thermal analysis (DTA) and thermogravi-
centration, sorbent dose etc., have a remarkable effect on many metric analysis (TGA). DTA-TGA data were recorded simultaneously
processes in an ion exchange system, including service, back wash, on a Netzsch thermobalance STA-409 with an alumina crucible
and regeneration cycles. Integrating these effects into the oper- and alumina powder reference. The heating prole consisted of a
ation and design of an ion exchange system helps to minimize 10 K min1 in nitrogen atmosphere up to the desired temperature
leakage and aids in troubleshooting when problems arise. Under- (1600 K). FT-IR spectroscopy was performed on an Irprestige-21
standing the effect of temperature, pH of the medium, metal ion Shimadzu FT-IR spectrometer. The samples were prepared with
concentration, sorbent dose etc., can improve the operating ca- KBr and pressed into pellets. Spectra were collected in the mid-
pacity and euent quality levels of an ion exchange system to a IR range from 400 to 4000 cm1 with a resolution of 1 cm1 .
degree [2635]. It is reasonable to expect that increasing tempera- The cation exchange capacity (CEC) of the material was evalu-
ture will result in a sharper exhaustion zone, higher exchange rate, ated by the batch process. The morphology and crystal size of the
and, therefore, higher capacity and better quality. synthetic MOR were examined by scanning electron microscopy
The prime objective of the present work is to synthesize well (SEM). For SEM, the samples were dispersed onto carbon tape
organized, regular shaped with good morphological structured, and coated with gold using a sputter coater system to prevent
analogue of heulandite. Apart from this, another objective of this charge accumulation on the sample. The heulandite crystals were
work is to investigate the sorption characteristic of this synthetic then observed on a JEOL JSM-5800 microscope operating in the
analogue of heulandite for Th(IV), Eu(III), Sm(II) and Fe(III) metal SEM mode at 20 kV. The specic surface areas and micropore vol-
ions and to evaluate the effect of temperature, pH of the medium, ume were determined by physical adsorption of nitrogen with the
metal ion concentration, and sorbent dose on their sorption. This BrunauerEmmettTeller (BET) method at 77 K temperature using
paper also discussed the sorption isotherm model (Langmuir and a Micromeritics ASAP 2400 automatic analyzer.
Freundlich isotherm model) and various thermodynamic parame-
ters (Gibbs free energy change (G 0 ), heat of sorption ( H 0 ) and 2.3. Sorption studies
entropy change ( S 0 )) as applied to the sorption of Th(IV), Eu(III),
Sm(II) and Fe(III) ions onto the synthetic analogue of heulandite. The thoriumnitrate [Th(NO3 )4 5H2 O, CDH], europium(III) oxide
(Eu2 O3 , Himedia 99.99%), samarium metal powder [CDH] and fer-
2. Materials and methods ric nitrate [Fe(NO3 )3 , Rankem] were used as a source of Th(IV),
Eu(III), Sm(II) and Fe(III) respectively. Arsenazo-III [2,7-bis(2-
2.1. Material synthesis arsenophenylazo)chromotopic acid, C22 H18 As2 N4 Na2 O14 S2 4H2 O,
Merck] was used to determine the concentration of Th(IV). Ana-
Hydrothermal method is used to synthesize the desired ana- lytical grade alizarin red-S [sodium alizarinsulfonate, COC6 H4 CO-
logue of heulandite having composition; Na2 O:Al2 O3 :7SiO2 :nH2 O, C6 H(OH)2 SO3 NaH2 O, CDH] was used for the estimation of rare
and the reactants used for this synthesis were sodium silicate earth metal ions [Eu(III) and Sm(II)]. Other chemicals and re-
[Na2 SiO3 , Riedel-de Han] as the silica source; aluminum nitrate gents such as ammonium thiocyanate, hydrochloric acid, nitric
300 P. Sharma et al. / Journal of Colloid and Interface Science 332 (2009) 298308
acid, potassium hydroxide, potassium hydrogen phthalate etc used Freundlich isotherm:
were of analytical grade from Rankem, BDH, CDH, Aldrich and no
log qe = log K F + 1/n log C e (linear form) (3)
further purication was made before their use.
Sorption experiments were conducted by equilibrating weighed where, K F and 1/n are the Freundlich constants. The value of K F
amount of sorbent with 25 mL of metal ion solution of known (mmol g1 ) can be taken as a relative indicator of sorption capac-
concentration for 4 h (except kinetic study experiment) there- ity, while 1/n shows the energy or intensity of sorption. These are
fore metal ion sorption i.e. Th(IV), Eu(III), Sm(II) and Fe(III) on the experimental parameters which depend on the system of sor-
an analogue of heulandite in liquidsolid system was a stan- bent and sorbate.
dard and strictly adhered to batch technique. Constant stirring
and constant temperature of the liquidsolid system during the 2.5. Thermodynamic parameter
whole experiment was maintained with the help of reciprocating
thermostated water bath shaker. The shaking rate was the same Spontaneity of the sorption can only be predicted by study-
for all experiments. The pH of the solution was adjusted prior ing its thermodynamic parameters. The distribution coecient
to the experiments by adding a small amount of NaOH/HNO3 . (Eq. (4)) data were used for calculating the thermodynamic pa-
Once the equilibrium was established, supernatant liquid was l- rameters of each sorption system using the following equations
tered off using Whatman lter paper number 42, and care has [42,43]:
been taken to repeatedly centrifuge the solution at high speed
(10,000 rpm, German made Heraeus Biofuge Stratos Centrifuge D- K d = (C i C e )/C e x( V / W ) mL/g, (4)
37520 Osterode) to avoid any solid particle in the aqueous phase.
where, V is the volume of the solution in mL, and W is the weight
The metal ions concentration in the solution phase was deter-
of the exchanger in g.
mined spectrophotometrically. The percentage removal of metal
ions was estimated from the difference of the metal ion concen- ln K d = S 0 / R H 0 / R T , (5)
tration in the aqueous phase before and after the sorption and
expressed in terms of sorption percentage: Sorption percentage = where, R is the universal gas constant, 8.314 J mol1 K1 and T is
(C 0 C e )/C 0 100; where, C 0 denotes the concentration of the the absolute temperature in Kelvin. The free energy (G 0 ) for the
initial solution (mequiv mL1 ) and C e concentration of solution specic sorption was calculated by
(mequiv mL1 ) at equilibrium. To optimize the sorption process the G 0 = H 0 T S 0 . (6)
inuence of specic process parameters such as pH of the solution,
weight of sorbent, contact time, initial metal ion concentration, The apparent thermodynamic parameters, enthalpy change
and temperature, was investigated by changing one parameter and ( H 0 ), and entropy change ( S 0 ) for the Th(IV), Eu(III), Sm(II) and
keeping other parameters constant. All the experiments were car- Fe(III) sorption on analogue of heulandite were calculated from the
ried out in duplicate and each experimental result was obtained slopes and intercepts of the linear variation of ln K d vs. 1/ T by
by averaging the data for two parallel experiments. Eq. (5). The values of H 0 , and S 0 so obtained from the values
of slope and intercept respectively, are used to calculate the value
2.4. Sorption isotherm of G 0 by the use of Eq. (6).
Sorption process involves an array of phenomena that can al- 3. Results and discussion
ter the distribution of pollutants among the constituent phases
and interfaces of the subsurface system [37]. Sorption at surface 3.1. Heulandite characterization
or interface is mainly the result of binding forces between the in-
dividual atoms, molecules or ions of the sorbate and the surface. The stability of the laboratory synthesized analogue of heulan-
The behavior of the sorption process was studied by carrying out dite is checked by shaking weighed amount of material in acidic,
a set of experiments at pH 5 and three different temperatures. The basic and organic solvents. From the weight loss calculations we
nature of the sorption process and the relation between the equi- nd that this material is highly stable in basic solutions as well as
librium concentrations of the sorbate in the liquid phase and in the in organic solvents, but shows instability above 6.0 M HNO3 acidic
solid phase was tested with respect to the following well-known concentration.
sorption models [38,39]. Examination of the powder X-ray diffraction pattern (Fig. 1)
Langmuir isotherm: shows a characteristic peak of heulandite at 2 values of 9.85 . The
d-spacing values for this material correspond to 2 = 9.85 comes
C e /qe = 1/( K a qm ) + C e /qm (linear form) (1)
out to be 8.98 . In addition to heulandite phases (95%) pres-
where, qe is the amount of metal ion sorbed per unit weight ence of unreacted silicates, was also reported in the nal powder.
of sorbent (mequiv g1 ), C e (mequiv L1 ) is the equilibrium con- The crystallite size obtained with X-ray method (calculated from
centration of the metal ions in the solution. K a and qm are the Scherrers equation; D = 0.9/( B cos ), where, 0.9 is the Scher-
Langmuir coecients representing the equilibrium constant for the rer constant, is the wavelength of X-ray, B is the breadth of
sorbatesorbent equilibrium and the monolayer capacity respec- the pure diffraction prole and is the incidence angle of X-ray.
tively. The constants were obtained from the slope and intercepts The breadth B is calculated as the full width half-maximum of X-
of the plots of C e /qe against C e . The value of qm represents the ray diffraction pattern) comes out to be 27.08 nm, which is the
practical limiting sorption capacity, i.e. the maximum value of qe . effective length, measured in the diffraction vector, along which
Weber and Chakraborti suggested a method to evaluate the fea- diffraction is coherent [44]. The term crystal size is preferred over
sibility of adsorption processes [40]. Langmuir constants are also particle size, since individual particles may contain crystals or do-
used to obtain the dimensionless constant called equilibrium pa- mains having different orientations [45]. The crystal size obtained
rameter or separation factor, R L which can be calculated by the by applying Scherrers equation is interpreted as an average crys-
following equation [41]: tal dimension. The accuracy of crystal size determined is usually
of 6080%, in case of heulandite because of the uniformity in the
R L = 1/(1 + K a C 0 ), (2)
crystal size analyzed by scanning electron microscopy. Powders
where C 0 is the highest initial solute concentration (mequiv L1 ). with needle shape crystals tend to aligned with the specimen axis
P. Sharma et al. / Journal of Colloid and Interface Science 332 (2009) 298308 301
Fig. 6. Effect of pH on the sorption of Th(IV), Eu(III), Sm(II) and Fe(III) onto analogue
Fig. 4. FTIR spectra of laboratory synthesized analogue of heulandite. of heulandite.
Specic surface area (S BET ) and the total pore volume mea-
surements of nal product of synthetic analogue of heulandite are
478 m2 g1 and 0.026 cm3 g1 respectively. The preliminary inves-
tigation of the analogue of heulandite by the N2 sorption isotherm
data (obtained via Micromeritics ASAP 2400, automatic analyzer)
showed that analogue of heulandite may resolutely refer to meso-
porous material with mesopore diameter 30 nm.
M(OH)2 (H2 O)6 M(OH)2 + 4H2 O, (9)
M(OH)n (H2 O)6n M(OH)n + (6 n)H2 O, (10)
Fig. 10. Langmuir adsorption isotherm for Th(IV) sorption on synthetic analogue of
Fig. 9. Effect of initial metal ion concentration and system temperature on the sorp- heulandite at three different temperatures.
tion of Th(IV), Eu(III), Sm(II) and Fe(III) onto analogue of heulandite.
of the sorption process, as these R L values comes out less than Sorption data were also tted by Freundlich sorption isotherm
that of unity for each metal ion at all temperatures. (Figs. 1416, and 17) at all temperatures (R 2 values were greater
The results obtained from sorption of Th(IV), Eu(III), Sm(II), and than 0.96). The values of n were found to be less than unity at all
Fe(III) over synthetic analogue of heulandite have also been tried temperatures except for Th(IV) and Sm(II) sorption, indicating that
to correlated with Freundlich sorption isotherm (Eq. (3)). desorption may also occurs during the sorption process of these
metal ions. This implies that signicant sorption took place in case
of Eu(III) and Fe(III). The value of K F (Table 1), which is a measure
of the degree of sorption, is high at higher temperatures indicate
that more sorption would be expected at these temperatures.
Fig. 12. Langmuir adsorption isotherm for Sm(II) sorption on synthetic analogue of
heulandite at three different temperatures.
Fig. 14. Freundlich adsorption isotherm for Th(IV) sorption on synthetic analogue of
heulandite at three different temperatures.
Fig. 13. Langmuir adsorption isotherm for Fe(III) sorption on synthetic analogue of
heulandite at three different temperatures.
Table 2
R L values from Langmuir adsorption isotherm for Th(IV), Eu(III), Sm(II), and Fe(III)
sorption onto synthetic analogue of heulandite.
Table 1
Langmuir and Freundlich adsorption constants for Th(IV), Eu(III), Sm(II), and Fe(III) sorption onto synthetic analogue of heulandites at three different temperatures.
Fig. 16. Freundlich adsorption isotherm for Sm(II) sorption on synthetic analogue of Fig. 18. Plot of 1/ T vs. ln K d to calculate the thermodynamic parameters for Th(IV)
heulandite at three different temperatures. adsorption onto synthetic analogue of heulandite at ve different concentrations.
Fig. 17. Freundlich adsorption isotherm for Fe(III) sorption on synthetic analogue of Fig. 19. Plot of 1/ T vs. ln K d to calculate the thermodynamic parameters for Eu(III)
heulandite at three different temperatures. adsorption onto synthetic analogue of heulandite at ve different concentrations.
Th(IV), Eu(III), Sm(II), and Fe(III) by synthetic analogue of heulan- ness of the sorption process at solute sorbent interface. The G 0
dite are summarized in Table 3. These values of H 0 and S 0 values (Table 4) becomes more and more negative with rise in re-
were obtained from the slope and intercept of the plot of ln K d action temperature and decrease in initial metal ion concentration
and 1/ T (Figs. 1820, and 21), that satises Eq. (5). The free en- for each metal ion. These results represent the high feasibility and
ergy change, G 0 was calculated from H 0 and S 0 value at spontaneity of this exchange process at higher temperature and
each temperature using Eq. (6) and the obtained values were tab- low initial metal ion concentration. Based on the values of free
ulated in Table 4. The observed values of enthalpy change ( H 0 ) energy, Fe(III) sorption onto synthetic analogue of heulandite is
for each metal ion indicates that H 0 of each exchange process most spontaneous process in comparison to other three metal ions
is concentration dependent. The maximum H 0 values are ob- (Th(IV), Eu(III), and Sm(II)) sorption onto the same.
tained at initial metal ion concentration of 0.001 N and minimum
at 1.0 N. The positive values of enthalpy change reveal the process 4. Summary
to be endothermic and low magnitude of these values indicates
the physicosorption. The positive values of entropy ( S 0 ) as listed In this reported work we able to make the desired analogue
in Table 3 reects the anity of the ion exchange material for of heulandite by hydrothermal method and the reliability of the
the metal ion under consideration. It also conrms that random- material was conrmed by analyzing the material with different
Table 3
Enthalpy change and entropy change values for Th(IV), Eu(III), Sm(II), and Fe(III) sorption onto an analogue of heulandite at ve different initial metal ion concentrations.
Metal H 0 S0
ion (J mol1 ) (K J mol1 )
0.01 N 0.05 N 0.1 N 0.5 N 1.0 N 0.01 N 0.05 N 0.1 N 0.5 N 1.0 N
Th(IV) 474.14 291.08 263.29 283.62 216.86 2.22 1.58 1.39 1.34 1.06
Eu(III) 1084.20 178.25 267.02 235.27 280.01 4.49 1.35 1.46 1.24 1.32
Sm(II) 1323.31 312.12 147.46 165.02 112.58 5.33 1.83 1.12 1.05 0.81
Fe(III) 1261.73 646.26 338.59 270.39 262.21 5.27 2.93 1.80 1.44 1.33
P. Sharma et al. / Journal of Colloid and Interface Science 332 (2009) 298308 307
Table 4
Free energy change (G 0 , J mol1 ) values for Th(IV), Eu(III), Sm(II), and Fe(III) sorption onto an analogue of heulandite at ve different initial metal ion concentrations and
three different temperatures.
Acknowledgments
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