ELSEVIER Applied Clay Science 10 ( 1995) 247-258

Acid activation of a palygorskite with HCl:

Development of physico-chemical, textural and
surface properties
M. Suhrez Barrios a, L.V. Flores Gonzhlez b, M.A. Vicente
Rodriguez b, J.M. Martin Pozas a
aDepartanento de Geologia, Area de Cristalografia y Mineralogia, Facultad de Ciencias, Vniversidad de
Salamanca, E-37008 Salamanca, Spain
b Deparmmento de Quimica Inorgdnica. Facultad de Ciencias Quimicas, Vniversidad de Salamanca, E-37008
Salamanca, Spain

Received 30 March 1994; accepted 17 March 1995

Abstract

A palygorskite from Bercimuel (Segovia, Spain) was treated with 1.0,3.0,5.0 and 7.0 N solutions
of HCl for 1 hour under reflux. The solids obtained were characterized by XRD, FT-IR spectroscopy,
thermal <analyses, TEM and nitrogen adsorption-desorption isotherms at 77 K. The acid treatment
runs with the removal of the octahedral cations -Mg( II), Al( III) -and the formation of amorphous
silica from the tetrahedral sheet. An important increase in the specific surface area was observed
during treatment, reaching a maximum of 286 m2/g in the sample treated with 5.0 N HCl. The silica
obtained after the treatments maintains the fibrous morphology of natural palygorskite. No creation
of microporosity is observed during the treatment.

1. Introduction

Palyg;orskite is a clay mineral that together with sepiolite form the group of fibrous clay
minerals. The structure of palygorskite was first proposed by Bradley ( 1940), who described
a theoretical formula of [ Si,Mg,OzO( OH) J ( H20) 4 *4H,O. As observed, there are three
different types of molecules of water in this formula: adsorbed water, water bonded to
octahedral cations and hydroxyl groups. About four (average value) of the five theoretical
octahedral positions are occuppied (Newman and Brown, 1987), Mg( II) and Al( III) being
the usuall octahedral cations.
Due to its sorptive and rheological properties, palygorskite is widely used in different
industrial fields. The mineral finds important uses as an animal waste adsorbent, as pesticide

0169-131’7/95/$09.50 0 1995 Elsevier Science B.V. All rights reserved

SSDIO169-1317(95)00007-O
248 M. Sudrez Barrios et al. /Applied Clay Science 10 (1995) 247-258

carrier, as decolorizing agent, in the oil refining and pharmaceutical industries, and as
catalyst and catalyst support.
The physico-chemical behaviour of clay minerals has been studied because of its relation
to their adsorbent and/or catalytic properties. This behaviour is governed by the extent and
nature of their external surface, which can be modified by suitable acid and thermal treat-
ments. Acid and thermal treatments increase the catalytic and adsorbent activity of certain
clay minerals but further and stronger treatments decrease this activity (Jimenez Lo pez et
al., 1978; Bonilla et al., 1981; Lopez Gonzalez et al., 1981; Cetisli and Gedikbey, 1990;
Pesquera et al., 1992). The silica obtained after intense acid treatments would compete in
different industrial uses with that obtained by precipitation, as Xianzhen and Chuyi ( 1990)
have reported for sepiolite.
The behaviour of palygorskite when treated with acid solutions has been studied from
different points of view ( Abdul-Latif and Weaver, 1969; Singer, 1976; Corma et al., 1987,
1990; Gonzalez et al., 1989b, 1990). However, the literature concerning acid treatment of
this mineral is less abundant than that addressing sepiolite or different smectites. The first
question that arises when considering the mechanism of acid attack is whether protons are
able to penetrate into the channels of the silicate, attacking both the internal and external
surface at the same time. Abdul-Latif and Weaver have reported a continuous reaction,
which is similar over the whole of the surface of the solid because of its very porous structure
but one that would change from one point to another. On the other hand, Corma et al. found
difficulties when considering the diffusion of protons to the pores. These authors reported
that the removal of Mg( II) and Fe( III) was easier than that of Al( III), the latter occupying
the centre of the ribbons and hence are more difficult to remove.
Recently, we have reported on the palygorskite deposit at Bercimuel (Segovia Province,
Spain), describing its mineralogy and genesis (Sukez Barrios et al., 1993, 1994). In the
present paper, the development of physico-chemical, textural and surface properties of this
palygorskite is studied under progressive acid treatment.

2. Experimental method

The clay mineral used was the above-mentioned natural palygorskite from Bercimuel
(Segovia, Spain). The original sample is the < 2 pm fraction, obtained by aqueous decan-
tation (designated as 2M). The composition of this fraction, studied by XRD, is palygorskite
(82%)) illite ( 14%)) smectites (4%) and traces of quartz and feldspars.
Five grams of pulverized clay were treated under mechanical stirring with 100 ml of 1 .O,
3.0,5.0 and 7.0 N solutions of HCl, for 1 hour under reflux. The solids obtained after these
treatments were washed until no chloride anions could be detected, dried at 50°C and kept
over H2S04 solutions (R.H. = 45%). These solids are designated as 2M-IN, 2M-3N, 2M-
5N and 2M-7N.
The X-ray diffractograms (XRD) were obtained on a Siemens D-500 diffractometer
using Cu-Ka radiation (h = 1.54050 A). The equipment has a graphite monochromator
and a DACO-MP data station.
Elemental analyses were carried out by plasma emission spectroscopy, using a Perkin-
Elmer Plasma II model emission spectrometer. Solid samples were previously digested
 M. Sudrez Barrios et al. /Applied Clay Science 10 (1995) 247-258 249

under pressure with a mixture of nitric and hydrofluoric acids, in a PTFE autoclave. Results
were ob’tained with a relative error of 1%.
The Fourier-Transform infrared (IT-IR) spectra of KBr pellets were recorded in the
4000-3.50 cm- ’region on a Perkin-Elmer IT-IR M- 1700 2B spectrophotometer.
Thermal analyses were carried out on Perkin-Elmer analyzers, TGS-2 and 1700 for
thermogravimetric (TGA) and differential thermal analyses (DTA) , respectively.
The specific surface area of the samples were determined by the nitrogen adsorption-
desorption isotherms at 77 K, in a conventional high vacuum volumetric system equipped
with a B#alzers AP6100 pressure transducer. The samples were outgassed at 70°C for 2 hours
at a pressure of 10e6 mm Hg. These conditions were previously found to be ideal for the
outgassmg process (Su&rez Barrios et al., 1992). The BET method was used for the
corresponding calculations. The relative error in these measurements is about 5%.
The free silica in the samples was digested following the method described by Ross and
Hendricks ( 1945). The solids obtained were studied by XRD and TEM techniques.
Morphologic analyses were carried out on a Zeiss EM 902 transmission electron micro-
scope on samples dispersed in water and deposited on a grid.

3. Results and discussion

3. I. X-ray diffraction

The X-ray diffractograms of natural and acid activated palygorskite are shown in Fig. 1.
When the concentration of the acid solution was increased, the crystallinity of the palygor-
skite decreased, as observed in the f.w.h.m. index of their peak at 10.4 A. Their diffraction
effects dissappeared completely when the mineral was treated with 7.0 N HCl. The small
amount of smectite in the original sample - identified by the peak at 15 A - disappears
even when the more diluted acid solution ( 1.O N) is used. However, micas - identified in
the original sample by their peak at 5 A because their main peak at 10 A is masked by
palygorskite - remain even after the most intense treatments. In the sample 2M-7N, the
(001) reflection of micas is clearly identified at 10 A. The formation of an amorphous silica
phase cam be deduced from the appearance of a broadened band (between 20= 16-30”,
with a maximum at about 21”). This silica is generated by destruction of the silicates
(mainly palygorskite) and is present in the resulting solids owing to its insolubility in acid
solutions. Thus, after treatment with 7.0 N HCl, palygorskite is not found in the solid
obtained and only the band characteristic of silica, with peaks of micas, quartz and feldspars,
is observed in the X-ray powder diffractogram.

3.2. Chemical composition

The chemical composition of the resulting solids is given in Table 1. With increasing
acid concentration, the content of SiO, (91.23% after treatment with 7.0 N HCl) increases
and the content of Al,O,, MgO and Fe,O, decreases.
The d’ecrease of the content of Fe203 and MgO is significant. In the more intensely treated
solid (2M-7N) only traces of these oxides are found (about 0.1%). The percentage of
 M. Sudrez Barrios et al. /Applied Clay Science 10 (1995) 247-258

Fig. 1. XRD of natural and activated palygorskite ( P = palygorskite; S = smectites; Q = quartz and I = illite)

A1,03 also decreases strongly, accounting for 6.3% of its weight in the more intensely
treated samples. The content of Na,O and K20 in the solids remains almost constant during
treatment. The presence of these elements in the sample together with an important amount
of Al is due to impurities such as micas and feldspars, which are both very insoluble in the
acid solutions.
The observed increase in the percentage of SiO, and the decrease in Al,O,, MgO and
Fe,O, is related to the progressive dissolution of palygorskite. The octahedral cations pass
into the solution while silica, owing to its insolubility in acid solution, remains in the solids
obtained.

Table 1
Chemical analyses of different samples of palygorskite, expressed in oxide form

Sample SiO, MgO AlAA Fe& TiOz CaO Na,O

2M 59.12 10.75 15.98 6.34 0.56 2.89 0.22 1.65

2M-1N 72.32 7.23 12.85 3.50 0.49 - 0.27 1.74
2M-3N 78.74 5.34 11.11 2.51 0.46 - 0.27 1.74
2M-5N 83.95 2.7 1 9.37 1.25 0.41 - 0.29 1.47
2M-7N 91.23 0.11 6.35 0.14 0.40 _ 0.29 1.37
 M. Sudrez Barrios et al. /Applied Clay Science 10 (1995) 247-258

5% Weight loss

50 200 400 600

Temperature (“C)
Fig. 2. DTA and TGA curves of naturaland activated palygorskite.

3.3. Thermal analyses

The thermal curves (TGA and DTA) of natural and activated palygorskite are given in
Fig. 2. Natural palygorskite shows a thermal behaviour similar to that usually found in the
literature for this silicate. In the low-temperature region, a first endothermal effect between
40 and 180°C is due to the loss of adsorbed and zeolitic water (8.1%) . Coordination water,
bound to octahedral cations, is lost in two different endothermal steps. The first occurs
252 M. Sudrez Barrios et al. /Applied Clay Science 10 (1995) 247-258

between 250 and 350°C with the loss of two water molecules (2.9% weight loss), and leads
to the formation of semi-anhydrous palygorskite. The second step occurs at 350-550°C
with the condensation of the two remaining water molecules and, simultaneously, of
hydroxyl groups. The weight loss in this step is 4.6%. The last process, which takes place
up to 550°C is the loss of silanol groups, formed by hydroxyl groups bonded to Si atoms
(Si-OH) (Gonzalez et al., 1989a). ,As the intensity of acid treatment is increased, the
intensity of these effects decreases. Thus, only two effects are observed in the 2M-7N
sample. The first (less to 200°C) is the loss of the water adsorbed by the free silica originated
and the second, a very modest slope in the high temperature region of the TG curves, is due
to the elimination of silanol groups. This last process goes without important energetic
effects.

3.4. FT-IR spectroscopy

The FT-IR spectra (Fig. 3) comfirm the presence of free silica in the activated solids.
There are three important modifications in the spectra. In the high wavenumber region, the
intensity of the bands occur in the natural sample at 3620-3550 cm- ’ (assigned to (Me-
Me)-OH) and at 3450-2900 cm-’ (corresponding to adsorbed water molecules)
decreases. Thus, in the more strongly activated samples only a broad band centered at 3425
cm-‘, with a small shoulder at 3634 cm-‘, is seen; this latter is related to (Al-Al)-GH
bonds of the remaining micas.
In the same way, the intensity of the band at about 1660 cm- ‘, assigned to the deformation
mode of water molecules, decreases as the treatment progresses. The bands between 1400
and 400 cm- ’(in the natural silicate corresponding with the vibration of octahedric cations)
disappear, new bands appear at 1200,1090,950,800 and 470 cm- i, all of them are assigned
to free silica. The broad band at 120&1000 cm-’ remains at the same position but its
appearance changes, from that characteristic of the tetrahedral sheet in natural palygorskite
to that of silica in the more strongly attacked samples.
These results are consistent with the changes reported by other authors studying the acid
activation of both palygorskite and other silicates. Mendelovici ( 1973), studying by IR
spectroscopy Georgia palygorskite treated with 5.0 N HCl, considered the band that appears
in treated samples at 1090 cm- ’ as the main variation in the spectra and assigned the band
at950cm-’ to the vibration of silanol groups. Suquet ( 1989) found the same bands when
studying the very porous, non-crystalline silica obtained by acid leaching of chrysotile.
Similar results are found by Komadel et al. ( 1990) when treating smectites.

3.5. BET surface

The nitrogen adsorptiondesorption isotherms at 77 K for natural and activated palygor-

skite (Fig. 4) correspond to type II in the IUPAC classification with small hysteresis loops.
The c-values are always up to 0.999. The type of these isotherms is the same in palygorskite
and activated solids and persists even in the 2M-7N sample, which is mainly formed by the
silica generated during acid attack.
The value of surface area (calculated by application of the BET equation) increases as
treatment progresses. Natural palygorskite has a surface area of 186 m’/g. Samples treated
 M. Sudrez Barrios et al. /Applied Clay Science 10 (1995) 247-258 253

.
woo woo 2noo lpoo cm
Fig. 3. FT-IR spectra of natural and activated palygorskite.

with 1,3 and 5 N HCl have, all of them, values about 275 m’/g. The maximum is 286 m*/
g in sample 2M-5N. The surface area of the sample treated with 7 N HCl slightly decreases
to a value of 250 m*/g (Table 2).
The increase in the surface area from natural palygorskite to samples treated with 1, 3
and 5 N is mainly related to the elimination of exchangeable cations and generation of silica.
The decrease observed in the sample 2M-7N, mainly formed of silica, is due to the relatively
higher amount of insoluble impurities, such as micas and feldspars. These impurities have
a very :small surface area. No creation of microporosity is observed when studying the
corresponding “t?’ representations.
The :increase in surface area until a maximum value and further decrease has been
described in the literature for the acid activation of sepiolite (Lopez Gonzalez et al., 1981;
254 M. Sudrez Barrios et al. /Applied Clay Science 10 (1995) 247-258

Ads. Vol.
(ml/g)

0:
.
0.
2M-7N .
0.
0.

2M-3N p Q
0.0 *
2tl-5N P*
aQ*
_&G+Q

2M-IN n .o

2M-3N

2fl-IN

2M’ : ’ ; ’ I ’ : ’ ;
0.1 0.3 0.5 0.7 0.9
P/PO
Fig. 4. Nitrogen adsorption+lesorption isoterms at 77 K of natural and activated palygorskite. In the vertical axis,
the “zero” of each representation is indicated.

Vicente Rodriguez et al., 1994) and also even montmorillonite (Mendioroz et al., 1987;
Pesquera et al., 1992). This behaviour is usually explained by occlusion of the pores created
during acid activation, an effect that we have not observed in the present work.

3.6. Free silica digestion

As indicated before, free silica is an important component of the solids obtained after
acid treatment. Accordingly, it was digested following the method proposed by Ross and
Table 2
Specific surface area (S) and weight loss observed after free silica digestion ( W) in samples of palygorskite

Sample

2M 186 0.1
2M-1N 268 22.3
2M-3N 267 40.5
2M-5N 286 59.8
2M-7N 250 66.2
 M. Sudrez Barrios et al. /Applied Clay Science 10 (1995) 247-258

2 Theta
Fig. 5. XlRD of samples of activated palygorskite after free silica digestion (P = palygorskite; I = illite; Q = quartz
and F = feldspars)

Hendricks ( 1945). The digestion process elicits significant weight losses in the samples;
the data are shown in Table 2. The weight loss progresses in parallel with the increase in
the intensity of the treatment and reaches almost 70% in the sample treated with 7.0 N HCl.
In the X-ray diffractograms of the solids obtained after silica digestion (Fig. 5), the peaks
corresponding to palygorskite and silica have disappeared and only those corresponding to
illite, quartz and feldspars - both impurities insoluble in the acid and alkaline solutions
used -. can be observed.

3.7. Electron microscopy

The different solids were studied by TEM in order to determine how the acid treatments
modify their morphology (Fig. 6). The silica obtained after acid treatment maintains the
fibrous morphology of natural palygorskite. There is a certain “textural continuity”, in
agreement with the persistence in the shape of the N2 adsorptiondesorption isotherms. The
persiste:nce in the morphology of the silica obtained by acid treatment of fibrous silicates
was firs,t found by Gonzalez et al. ( 1984) after treating sepiolite with HCl. The amorphous
structure of the silica obtained was comfirmed by the electron diffraction technique. The
fibres lengths cannot be exactly measured, since they are aggregated parallel to their c-axis.
256 M. Sudrez Barrios et al. /Applied Clay Science 10 (1995) 247-258

Fig. 6. TEM micrographsof palygorskitetreated with 1 N HCl (a), 3 N HCI (b), 7 N HCl (c) and the latter
sample after free silica digestion ( d)

In addition, the method used to prepare the samples for TEM studies -dispersion in water
by ultrasounds -can modify the fibres. When free silica is digested with Na,CO,, insoluble
impurities are observed in the photomicrographs, such as rounded particles of micas.

4. Summary

Progressive removal of the octahedral cations of palygorskite, the destruction of its

structure, and the formation of silica from its tetrahedral sheet by acid treatment of this
 M. Sudrez Barrios et al. /Applied Clay Science 10 (1995) 247-258 257

silicate have been observed. All the techniques used show that the more intense the acid
treatment, the more the structure of the palygorskite is affected; after treatment with 7.0 N
HCl the structure of the palygorskite is completely destroyed.
The data obtained suggest that acid attack is uniform, i.e., the reaction proceeds simul-
taneously both at the external and internal surfaces of the solid.
An important increase in the surface area of the solids obtained was observed, even with
the mos,t dilute solution used ( 1.O N HCl) , but no creation of microporosity in the activated
samples has been observed. Industrial treatment under these conditions would improve the
properties of the palygorskite.
The silica obtained after the most drastic treatments maintains the fibrous morphology of
palygorskite, with a “textural continuity” with respect to the natural silicate. The formation
of silica by acid attack of palygorskite would be competitive with the acquisition of this
compound by precipitation from solution.

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