This paper proposes a simplified method of pillaring of clays with iron to obtain new products, efficient
catalysts in phenol degradation processes. The process uses a minimum duration and is much easier to
operate than the conventional method of pillaring. The intercalated clay was aged using microwaves. To
simplify the preparation of pillared inter-layered clays (PILC), we used clay, without purification or chemical
pre-treatment in the laboratory. We described the optimum obtaining conditions of Fe-pillared clays using a
method that demand lower duration and expenditure, offering the potential for extension to an industrial
scale. The starting materials used to prepare the pillared clays were: sodium bentonite, montmorillonite KSF
and montmorillonite K10 provided by Sigma Aldrich. The starting clays and pillared clays were characterized
by N2 adsorption-desorption isotherms, measurement of the specific surface area, infrared spectra (FTIR)
and SEM-EDAX analysis.
Keywords: Fe-pillared clays; industrial pillaring process; Na - bentonite, microwave aging.
mineral clay. This indicates the incorporation of a polycation with a height of about 1 nm, but such cations have
not been isolated [11-15]. Some skepticism as to the ability
of Fe ions to produce ordered pillared clay structures was
explicitly stated by some authors [6, 16].
The conventional laboratory method of Fe-PILC
synthesis is essentially based on mixing a diluted clay
suspension with a diluted pillaring solution [4,17,18]. This
laborious, expensive, and time-consuming procedure
involves the following steps: clay purification clay drying
and then grounding; ion exchange reaction; clay drying;
dispersing the clay in water 1-2 % (% mass.); preparation
of the diluted pillaring solution; ageing diluted pillaring
solution (24 hour - one month); slow addition of the pillaring
solution previously aged to the clay suspension;
intercalation of the aged solution (24 hour - one month);
washing with deionised water until chloride free and
filtration; drying the concentrated paste; final heating of
the dried clay (calcination) [4,7,13].
To produce pillared clays at an industrial scale, the above
procedure must be simplified. For simplifying the Fe-PILC
preparation in the laboratory we use unpurified clay and
microwaves ageing. The use of microwave irradiation
during intercalation offers, against conventional
preparation, the advantage of the time decreasing of PILC
preparation. We described the optimum obtaining
conditions of Fe-pillared clays using a method that demands
lower duration and expenditure, offering the potential for
extension to an industrial scale.
Experimental part
Materials and methods
Mineral clays used as starting materials are: Na bentonite B 3378, montmorillonite KSF and montmorillonite
K10 provided by Sigma Aldrich. To obtain the pillaring
solution we used NaOH and FeCl3 . 6H2O (Lach-ner) and
for ion exchange reaction NaCl.
* email: nicoleta.platon@ub.ro;
REV. CHIM. (Bucharest) 62 No. 8 2011
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Methods
The simplified pillaring method proposed in this paper
was carried out following the stages: homoionization of
clay with a sodium chloride solution, intercalation of the
pillaring agent (previously obtained) in a aqueous clay
suspension 2 % (% mass.), ageing, washing, drying and
calcination of the intercalated clay. For Na bentonite case,
the stage of homoionization with sodium chloride solutions
was removed, because this is natural sodium clay. Two
pillaring methods, a conventional A - uses room
temperature (fig. 1) and a simplified method which use
microwaves ageing B (fig. 1) were carried out and
compared.
Ion exchange
KSF and K10 montmorillonite clays were homoionized
with a NaCl solution 2M, with a solid: liquid ratio of 1:50
(10 g clay/500 mL NaCl). The ion exchange was realized
at 353 K and was repeated three times. After each process,
the clay was washed with distilled water until no chloride
ions were found. To avoid the rapid evaporation of the water,
the ion exchanged samples were slowly dried at 333 K for
24 h.
Preparation of the intercalation pillaring agent
The polyhydroxocationic solution that contains Fe, was
prepared using a molar ratio (OH/Fe) of 2.2. This was
prepared by drop-wise addition of a NaOH solution to a
FeCl3 . 6H2O solution, at room temperature with vigorous
stirring. The stirring during the addition of NaOH was
necessary to prevent local accumulation of hydroxyl ions,
which invariably produce precipitation of iron hydroxyl [7,
9, 19]. The intercalation solution precipitated using NaOH
0.4 M and FeCl3 0.2 M. This impediment was removed by
using dilute solutions of NaOH (0.2 M) and of FeCl3 (0.2 M).
A temperature of 333 K during the preparation of the
pillaring agent determines precipitation, unfavorably for the
obtaining process of the pillaring solution. Instead, using
lower temperatures this disadvantage was removed and
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Table 1
SPECIFIC SURFACE AREAS FOR
DIFFERENT TIMES OF AGEING
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Table 2
DURATION OF EACH STAGE OF IRON PILLARED CLAYS OBTAINING PROCESS BY CONVENTIONAL
METHOD (A) AND BY MICROWAVES AGING (B)
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Table 3
RESULTS FOR EDAX ANALYSIS FOR Be-Na
Table 4
RESULTS FOR EDAX ANALYSIS FOR M0-10Be-Na-Fe
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12. BALCI, S., GKAY, E, Pore structure and surface acidity evaluation
of Fe-PILCs, Turk J.Chem, 33, 2009, p.843
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H., CHEN, T, A combined study by XRD, FTIR, TG and HRTEM on the
structure of delaminated Fe-intercalated/pillared clay, J. Coll Int Sci.,
324, 2008, p.142
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using the trinuclear Fe(III)-acetato complex as pillaring precursor,
Micropor. Mesopor. Mater., 4, 1995, p. 43
17. KLOPROGGE, J.T., DUONG, L.V., FROST, R.L., A review of the
synthesis and characterisation of pillared clays and related porous
materials for craching of vegetable oils to produce biofuels, Environ.
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18. BERGAYA, F., THENG, B.K.G., LAGALY, G., Handbook of clay
science, Elsevier Science, 2006
19. MOLINA, C.B., CASAS, J.A., ZAZO, J.A., RODRIGUEZ, J.J., A
comparison of Al-Fe and Zr-Fe pillared clays for catalytic wet peroxide
oxidation, J. Chem. Eng., 118, 2006, p.29
20. BANKOVI, P, MILUTINOVI, N., ROSI, A, JOVI JOVII, N.,
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Manuscript received: 20.12.2010
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