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A perspective of the interlamellar region of organo-clays

by adsorption of aromatic hydrocarbons


R. Vijayalakshmi Puranik Prakash Kumar
Y. S. Bhat B. S. Jai Prakash
Published online: 25 July 2009
Springer Science+Business Media, LLC 2009
Abstract Adsorption of aromatic hydrocarbons has been
investigated on montmorillonite with and without surfac-
tant modication. The enhanced space created in the sur-
factant modied organo-clay using quaternary ammonium
species increased the amount of adsorption of aromatics
depending on the size of the alkyl group attached to ben-
zene ring. The diffusivity values calculated, indicate that
diffusivity of all the aromatics studied decreased in the
organo-clay. The extent of interlayer space available in the
modied clay is compared with that in zeolites having
different pore dimensions. A bulky molecule like nitron,
though enhanced the interlayer distance, simultaneously
blocked the access to newly created space in the hexadecyl
trimethyl ammonium (HDTMA)-modied clay. Thus the
increase in the interlamellar distance may not reveal the
effective interlamellar space but depends on the type of
quaternary species used. The available interlamellar space
in the modied clay is best studied by adsorbing hydro-
carbons of different dimensions.
Keywords Organo-clays Interlamellar space
Aromatic hydrocarbons Adsorption
1 Introduction
Like zeolites, clays are also alumino silicates. A type of
clay called smectite possesses a combination of cation
exchange, intercalation and swelling properties, which
make them unique from others. The smectites have layer
lattice structures in which two dimensional oxyanions are
separated by layers of hydrated cations. These cations are
readily exchangeable and can be replaced by a wide range
of positively charged chemical groups. Quaternary
ammonium salts can be used to modify the clays to produce
organo-clays. The organic cations occupy interlamellar
space in the organo-clays.
The organo-clays are of signicance in current context
specically concerning two aspects, viz. (i) polymer clay
nano-composites and (ii) environmental remediation. In the
former, the synthesized materials exhibit improvement in
properties over the virgin polymer. These include high
moduli, increased strength and heat resistance, decreased
gas permeability and ammability. In the environmental
remediation of water, the organo-clays have been
employed for controlling chemical pollution of ground
water, removal of organic compound from oileld waters
and removal of pathogens from sewage efuent. Each
application requires different type of organo-clays with
different gallery height or interlamellar space. These can be
synthesized by incorporating quaternary ammonium or
phosphonium species containing organic chains of different
lengths. A prior knowledge of the space available in the
interlamellar region will be useful to decide whether an
organo-clay is suitable or not for a specic application. In
their natural forms both clays and zeolites are hydrophilic
and they are made hydrophobic by incorporating organo-
cations for removal of pollutant species such as hydrocar-
bons from the various streams. For such applications, the
R. Vijayalakshmi Puranik P. Kumar
Research Center Vadodara Manufacturing Division, Reliance
Industries Limited P.O. Petrochemicals, Baroda 391346, India
Y. S. Bhat B. S. Jai Prakash (&)
Department of Chemistry, Bangalore Institute of Technology,
K.R. Road, V.V. Pura, Bangalore 560004, India
e-mail: jprak27@yahoo.com
1 3
J Porous Mater (2010) 17:485490
DOI 10.1007/s10934-009-9311-6
extent of effective space available for adsorption is of
importance. One of the best approaches to have an inner
view of interlamellar/channel space is to carry out
adsorption of different organic compounds. The size and
shape of the organic compound can provide an insight into
the space available within the interlamellar/channel region.
Lee et al. [1] have studied the adsorption of benzene,
toluene, and o.xylene as vapours by the dry-tetramethyl-
ammonium(TMA)clay complexes and as solutes from
water by the wet TMAclays. The adsorption of the
organic vapours by the dry TMA-smectite samples was
strong and apparently consisted of interaction with both the
aluminosilicate mineral surfaces and the TMA exchange
ions in the interlayers. In the adsorption of organic vapours,
a somewhat higher degree of shape selectivity of benzene,
toluene and xylene was noticed.
Redding et al. [2] studied the sorption on benzene on
bentonite and two organo-clays synthesized with the qua-
ternary ammonium organic cations, hexadecyl trimethyl
ammonium (HDTMA) and benzyltriethylammonium
(BTEA). They found that for HDTMA clay, the benzene
sorption increased as the total organic carbon content
increased. In contrast, the sorption of benzene to BTEA
clay decreased due to the formation of the positively
charged dimers on the clays surface which blocked the
access to the positive sites.
Cosultchi et al. [3] have studied adsorption of petroleum
organic compounds on natural Wyoming montmorillonite.
Similarly Piras et al. [4] have studied adsorption of volatile
organic compounds in Y zeolite and pillared clays. It was
shown that the total amounts adsorbed were in line with the
respective total microporous volume of the samples. Org-
ano-zeolites were prepared from synthetic ZSM-5 and
natural zeolites and used to remove benzene, toluene and
phenol from aqueous solution. The maximum adsorption
was observed on natural clinoptilolite [5]. Sorption of
polycyclic aromatic hydrocarbons on organo-zeolites was
investigated to determine sorbentsorbate interaction [6].
Application of surfactant modied zeolites to environ-
mental remediation particularly for the removal of con-
taminants from water was reported earlier [7]. Le Van Mao
et al. [8] have determined xylene isomer diffusivity in ZSM-
5 zeolite by vapour adsorption under constant conditions.
Considering the diffusion data and other sorptive properties,
attempts were made to correlate the crystallite characteris-
tics of the zeolite with its catalytic activity. Equilibrium
adsorption isotherms of ethylene, ethane, propylene and
propane were measured on a Ag
?
-impregnated clay based
alkene-selective sorbent and published [9].
Adsorption properties of selected sorbent materials such
as sand, swelling clays, organo-clays and cotton bers was
studied and the mechanism involved adsorption on the
external surface of the material in the pores or capillaries
[10]. Zhou et al. [11] have carried out a comparative study
of adsorption of p-nitrophenol on mono-, di- and tri-alkyl
surfactant intercalated organo-clays. Differences in the
surfaces and the interlayer of these organo-clays resulted in
differences in the adsorption efciency. The work of Liu
et al. [12] showed that surfactant intercalated Wyoming
montmorillonite can be effective for the removal of phenol
from an aqueous solution. Para-nitrophenol adsorbed on
HDTMABr organo-clay was studied by TEM and IR
spectroscopy. It is proposed that the phenol is adsorbed onto
the water in the cation hydration sphere of organo-clay [13].
A polynomial relationship between basal spacing and the
CEC loading described by the equation y = 0.3232
x
2
? 0.2052 x ? 1.2834 was proposed based on XRD and
TG study of adsorption of para-nitrophenol on HDTMA
organo-clay [14]. Adsorption of hydrocarbons on organo-
clays and its implication for oil spill remediation was dealt
by Carmody et al. [15]. According to them the hydrocarbon
sorption capacity of the organo-clay depended upon the clay
material and surfactants used in the organo-clay synthesis.
He et al. [16] have concluded that the distribution of
adsorbed surfactant and the arrangement of adsorbed
HDTMA
?
within the clay interlayer space control the
efciency and mechanism of sorption by the organolayer.
Sudies have been made to characterize the organo-clays by
different techniques [1719]. Based on changes in mor-
phology observations of organo-clay intercalated with
HDTMA
?
it was suggested that the organo-clay with lower
surfactant packing density are mainly composed of irregular
layer stacking with a number of curved organo-clay layers,
while those with higher surfactant packing density are
mainly composed of regularly intercalated and at layers.
The present study is an outcome of another work in which
we have been developing organo-clays basically to trap
specic inorganic anions. However, we could not achieve the
desired result and further we started a detailed investigation
to nd out why the results are not as expected. This has lead
us to look at the extent of space available in the interlamellar
region of the organo-clay. The study reported here deals with
our systematic approach of adsorbing different aromatic
probe molecules like benzene, toluene, ethylbenzene and n-
propylbenzene on organo-clays prepared by intercalation of
two different organic cations and evaluation of their diffu-
sivities to assess the effective interlamellar space available
for possible use in separation of organic molecules.
2 Materials and methods
2.1 Materials
The clay mineral used in the study was a swelling type
smectite rich clay from Bhuj area of Gujarat, India supplied
486 J Porous Mater (2010) 17:485490
1 3
by Ashapura Chemicals containing mainly montmorillon-
ite. The cation exchange capacity (CEC) of the clay sample
as determined by BaCl
2
method was 90 meq/100 g of clay.
The clay was transformed into organo-clay using two
organic cationic species viz. (i) hexadecyl trimethyl
ammonium (HDTMA) bromide (SD Fine Chemicals,
India), (ii) Nitron [4,5 dihydro-2,4-biphenyl-5-(phenyl
imino)-1H-1,2,4-triazolium hydroxide] (Acros Organics).
2.2 Preparation of modied clays
2.2.1 HDTMA clay
Known amounts of HDTMA bromide ranging from 0.135
to 0.85 mg corresponding to 0.5 to 2.0 CEC per gram of
clay were dissolved in water and used to prepare the
HDTMA-clay following the procedure reported elsewhere
[20]. Fifteen grams of the clay sample suspended in ace-
tone was added to the aqueous HDTMABr and the
resulting suspension was thoroughly mixed using magnetic
stirrer for 60 min. The mixture was centrifuged and the
residue was washed several times with acidied water to
remove excess of HDTMABr on the surface of the clay.
The resulting modied clay was ground, sieved to obtain
particles less than 2 lm and was nally dried at 105 C in a
hot air oven.
2.2.2 Nitron clay
0.5 g Nitron was dissolved in 0.5 cm
3
of acetic acid and
the solution was made up to 100 cm
3
. To this 2 g of clay
was added and stirred for 2 h. The resulting mixture was
centrifuged, washed several times with distilled water,
dried at 110 C for 2 h and ground to a ne powder.
2.3 Characterization
2.3.1 X-ray diffraction measurement
X-ray diffraction measurements were carried out to eval-
uate the interlamellar distance in the modied clays. The
X-ray patterns were obtained using Philips PW 3710 dif-
fractometer (Cu-K
a
radiation: k = 1.542 A

) for randomly
oriented powder samples. A step size of 0.02 (2 theta) was
used with a time of 1 s per step.
2.3.2 Surface area determination
Nitrogen adsorptiondesorption measurements were car-
ried out in liquid nitrogen temperature at 77 K using
NOVA 1000 Quantachrome (USA) for the analysis of BET
surface areas and pore size distribution. All samples were
preheated at 100 C for 2 h before the measurement.
2.3.3 Adsorption measurements
Gravimetric method was used for the measurement of
uptake of organic compounds and equilibrium adsorption.
McBain-Bakr gravimetric balance equipped with a sensi-
tive (25 cm/g) quartz spiral (Thermal Syndicate Ltd., UK).
A cathetometer with a precision of 0.001 cm was used
for measuring the spring extension. The details of the
adsorption system used in the study are reported elsewhere
[21]. Aromatic compound was degassed by freeze-pup-
thaw cycles before use. Vapour pressure of the com-
pound was determined with a pressure transducer (range
0100 Torr) from KS, USA. The adsorbent sample was
activated in situ at 150 C under vacuum (1 9 10
-5
Torr).
The sample was cooled to the desired temperature. The
aromatic hydrocarbons used in this study were obtained
from Aldrich Chemicals, USA.
2.3.4 Diffusion constant, D/r
2
The adsorption uptake data were used to calculate apparent
diffusivity, D/r
2
using the well known equation [22]
M
t
=M
1
1 6=p
2
X
1=n
2
expn
2
p
2
t D=r
2

where M
t
and M
?
are the amounts adsorbed at time t and
at innite time, respectively, r is the particle radius. D/r
2
was calculated by non-linear tting of the adsorption curve
to the solution of above equation.
3 Results and discussion
The amount of HDTMA sorbed between the montmoril-
lonite layers at different initial loadings, with respect to
CEC, of quaternary ammonium salt was measured by CHN
analyzer. The modied clays were found to retain increased
amounts of HDTMA as initial loadings of HDTMA
increased up to 2 CEC. Powder X-ray diffraction (XRD)
patterns of the clay material resulting from HDTMA and
nitron intercalation showed a clear swelling of the inter-
layers. The interlayer spacings of montmorillonite with and
without modication are reported in Table 1. HDTMA
added would locate themselves in the hydrophobic inter-
layer region resulting in the swelling of the clay layers.
Assuming that there is an increase of the basal spacing by
3.1 nm, for 2 lm clay particle size, there is a calculated
increase of the total pore volume by more than 10 times.
This also means that the space made available by swelling
is more than enough to accommodate 10 times the
observed amount of adsorbed HDTMA. The latter is
however restricted by the CEC even at higher loadings.
The HDTMA molecules in excess of CEC are weakly held
in the interlayer and get removed after washing. Formation
J Porous Mater (2010) 17:485490 487
1 3
of a bilayer would keep the clay layers apart with ample
free space in the interlayer.
3.1 Diffusivity in unmodied clay
Figure 1 presents the fractional uptake of benzene, toluene,
ethylbenzene and n-propylbenzene over unmodied
montmorillonite. The calculation based on this data
(Table 2) suggests the diffusivity (D/r
2
) to be in the order
benzene \toluene \ethylbenzene \n-propylbenzene.
Whatever adsorption that takes place on the unmodied
sample of clay, is outside the interlayer space where there
is no space restriction. The external surface of the clay
essentially consists of O and OH groups attached to tetra-
hedral silicate and also of the edges of the layers that form
this crystal. As the clay does not swell in hydrocarbons
they are not able to diffuse into the interlamellar space. The
diffusivity purely depends on the extent of interaction
between clay surface and aromatic molecules. Amount of
aromatic hydrocarbons adsorbed after 3600 s is reported in
Table 3. Amount of benzene adsorbed was highest and
n-propylbenzene was lowest, toluene and ethylbenzene
showed intermediate values.
3.2 Diffusivity in modied clay
The clay was modied to different extent by intercalating
HDTMABr, which resulted in varying interlamellar
spacing. The opening up of interlayer space enhanced the
length of diffusion path for the aromatic molecules in the
modied clay samples resulting in a decrease in diffusivity
(Table 2) as they have to now overcome the alkyl chains of
HDTMA occupying different locations in the interlamellar
region. Fractional uptake of aromatic hydrocarbons over
modied clay, montmorillonite-HDTMA-2CEC, is pre-
sented in Fig. 2. Table 3 depicts results of amount of
aromatics adsorbed on the modied clays after 3600 s.
These values are higher than that for unmodied clay
except in case of the aromatic having longer alkyl chain,
n-propylbenzene. One can easily make out the contribution
of interlamellar space towards adsorption by subtracting
unmodied clay adsorption values from the modied ones.
This contribution works out in case of montmorillonite-
HDTMA-2CEC to be almost three times that of unmodied
montmorillonite for the adsorbate benzene. Further the
contribution is two times for toluene and one time for
ethylbenzene, but almost the same for n-propylbenzene.
This is in line with size and shape of aromatic molecules.
3.3 Adsorption on zeolites and comparison with clays
In order to have an idea how the space available for dif-
fusion of aromatic molecules in the gallery of modied
clay is equivalent to system in which space is free of
HDTMA cation, the results have been compared with that
of zeolites 4A, ZSM-5 and beta. The rst zeolite has
channel dimension 3.8 9 4.0 A, the second one possesses
channel dimension 5.3 9 5.6 A, straight and zig-zag
channels intersecting each other, and last mentioned is a
large pore zeolite having three dimensional channel system
with dimension 6.0 9 7.3 A. Interesting feature about
these zeolites is 4A cannot adsorb inside its channels any of
the aromatic molecules we have studied, only they can get
adsorbed on the external surface sites, whereas, ZSM-5 and
beta can adsorb all of them. The results of adsorption of
benzene, toluene, ethylbenzene and n-propylbenzene on
4A, ZSM-5 and beta along with montmorillonite with and
without modications are presented in Table 4. Adsorption
Table 1 d(001) spacing and surface area of clay samples modied
with HDTMA and nitron
Clay sample Basal spacing,
d(001) (A)
Surface
area (m
2
/g)
Montmorillonite 9.5 21.0
Montmorillonite-HDTMA-0.5CEC 14.5 4.8
Montmorillonite-HDTMA-1CEC 18.2 3.5
Montmorillonite-HDTMA-2CEC 40.5 2.6
Montmorillonite-nitron 15.6 19.0
0.2
0.4
0.6
0.8
1
0 900 1800 2700 3600
Time, seconds
F
r
a
c
t
i
o
n
a
l

u
p
t
a
k
e
Benzene
Toluene
Ethylbenzene
n-Propylbenzene
Fig. 1 Fractional up take of aromatics over montmorillonite
Table 2 Diffusivity of aromatic hydrocarbons in montmorillonite
and montmorillonite-HDTMA-2CEC
Hydrocarbon Diffusivity (D/r
2
), s
-1
Montmorillonite
(untreated)
Montmorillonite-
HDTMA-2CEC
Benzene 7.40 9 10
-5
2.74 9 10
-5
Toluene 8.62 9 10
-5
7.10 9 10
-5
Ethylbenzene 1.08 9 10
-4
1.05 9 10
-4
n-Propylbenzene 1.22 9 10
-4
6.92 9 10
-5
488 J Porous Mater (2010) 17:485490
1 3
of benzene on montmorillonite-HDTMA-2CEC is more
than the three zeolites, while for toluene and ethylbenzene
it is in between that of ZSM-5 and beta zeolite. So, the
space available within the interlamellar space in modied
clay can be expressed in terms of zeolite channel space for
a specic adsorbate. Only one point we have not consid-
ered here is crystallite size variation of the zeolite. It is well
known that the diffusivity in zeolites is inuenced by the
crystallite size. Hence we are mentioning the crystallite
size of the zeolites used in our study, which is about 1lm.
3.4 Adsorption on nitron clay
Initially we started carrying out adsorption study to
understand our work on incorporation of a specic reagent
in the smectite clay (montmorillonite) to use it for trapping
a specic inorganic ion. As we could not achieve the
desired results it was decided to look at the interlayer space
of the clay after incorporation of organic reagent. Nitron
(Fig. 3), a specic reagent for nitrate ion (NO
3
-
) was
incorporated into the clay. XRD results conrmed inter-
calation of nitron in the clay. However, when nitronclay
was added to a solution containing NO
3
-
ion, it did not
reduce its concentration. It looks that Nitron is rmly held
in interlamellar region and is not able to interact with
NO
3
-
ion. Best way to nd out availability of space within
lamellar space is by carrying out adsorption study. It is
quite indicative from the results in Table 4 that nitronclay
has adsorption characteristic similar to unmodied clay.
That means though interlamellar space is opened up (basal
spacing 15.5 A from XRD) it is not accessible to benzene,
toluene or ethylbenzene. This can be explained based on
the fact that nitron is a bulky molecule containing three
phenyl groups and a ve membered heterocyclic ring
containing quaternary ammonium center, the latter has
entered the lamellar region partially and opened it up but
Table 3 Amount of aromatic hydrocarbons adsorbed on HDTMA-modied clays after 3600 s exposure
Clay sample Aromatic Hydrocarbon
Benzene (mmol/g) Toluene (mmol/g) Ethylbenzene (mmol/g) n-Propylbenzene (mmol/g)
Montmorillonite 1.483 0.838 1.116 0.554
Montmorillonite-HDTMA-1CEC 1.722 1.918 0.955 0.405
Montmorillonite-HDTMA-2CEC 5.574 2.539 2.060 0.562
0
0.2
0.4
0.6
0.8
1
0 900 1800 2700 3600
Time, seconds
F
r
a
c
t
i
o
n
a
l

u
p
t
a
k
e
Benzene
Toluene
Ethylbenzene
n-Propylbenzene
Fig. 2 Fractional up take of aromatics over montmorillonite-
HDTMA-2.0CEC
Table 4 Comparison of amount of aromatic hydrocarbons adsorbed on montmorillonite with and without modication and zeolites
Clay/zeolite Aromatic hydrocarbon
Benzene (mmol/g) Toluene (mmol/g) Ethylbenzene (mmol/g) n-Propylbenzene (mmol/g)
Montmorillonite 1.483 0.838 1.116 0.554
Montmorillonite-HDTMA-2CEC 5.574 2.539 2.060 0.562
Montmorillonite-nitron 1.168 0.625 0.975 0.619
4A 0.586 0.429 0.400 0.203
ZSM-5 1.779 1.359 1.536 0.853
Beta 4.354 3.912 4.007 2.108
Fig. 3 Structure of Nitron
J Porous Mater (2010) 17:485490 489
1 3
phenyl groups are not able to enter and hence has blocked
the accessibility completely. Redding et al. [2] observed a
similar blocking by benzyltriethyl ammonium ion for
benzene adsorption.
4 Summary
HDTMABr modied montmorillonite showed higher
adsorption capacity for benzene, toluene and ethylbenzene
than unmodied montmorillonite. The diffusivity
decreased on modication due to enhanced diffusion path
resulting from opening up of interlamellar space on inter-
calation. The space available within the interlamellar space
in modied montmorillonite can be expressed in terms of
zeolite channel space for a specic adsorbate. Adsorption
of benzene on montmorillonite-HDTMA-2CEC is more
than ZSM-5 and beta zeolite, while for toluene and ethyl-
benzene it is in between that of the two zeolites. Though
interlamellar space is opened up in case of nitronclay, it is
not accessible to benzene, toluene and ethylbenzene due to
complete blocking of space by the nitron. Adsorption of
organic compound of different size and shape is a good
technique to provide an insight into the interlamellar space
of organo-clay.
Acknowledgements YSB & BSJ would like to thank Principal and
Management of Bangalore Institute of Technology for the encour-
agement and facility to carry out this work. The authors express their
thanks to Department of Science & Technology, New Delhi for
nancial assistance. VRP and PK are thankful to Dr. A.B. Halgeri,
Head (R&D), Vadodara Manufacturing Division, RIL for continuous
encouragement and interest in the work. Authors are also thankful to
Mr. G.C. Patel for his assistance during experimental work.
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