Applied Clay Science 32 (2006) 87 93

www.elsevier.com/locate/clay

Removal of gases by thermal-acid leached kaolinitic clays:

Influence of mineralogical composition
Cristina Volzone , Jos Ortiga
CETMIC (Centro de Tecnologa de Recursos Minerales y Cermica) CONICET-CIC, C.C. 49,
Cno. Centenario y 506, (1897) M.B. Gonnet, Prov. Buenos Aires, Argentina
Received 8 June 2005; received in revised form 5 November 2005; accepted 16 November 2005
Available online 20 December 2005

Abstract
Natural and modified kaolinitic clays were used as retention for gas adsorptions. The kaolinitic clays containing different
mineralogical compositions were used. The modifications were carried out by heating the clays at 600 C and then by acid
treatment with 2.5 mol/L sulphuric acid solution at boiling temperature for 180 min. Equilibrium adsorption was measured using a
volumetric apparatus, at 25 C and 0.1 MPa. The gases tested were N2, O2, CO, CO2, CH4, C2H2 and SO2. The samples were
characterised by chemical analysis, BET surface area, X-ray diffraction and infrared spectroscopy. The thermal-acid modifications
on kaolins improved the capacity of the clays for gas adsorptions. Retention of SO2 (0.9141.242 mmol/g), C2H2 (0.4500.721
mmol/g) and CO2 (0.4370.602 mmol/g) by modified clays were higher than the other gases previously mentioned. The external
surface area and amorphous silica developed by modified clays, due mainly to presence of kaolinite in raw clays, improved the
capacity for gas retention. Whereas the main cause for gas retention by raw kaolinitic materials was the presence of the illite phase
in raw kaolin clays. The thermal-acid kaolins could be potential solids for separations of gases mixtures.
2005 Elsevier B.V. All rights reserved.
Keywords: Kaolin; Adsorption; Gases; Clays

1. Introduction
Nowadays, studies of clays, zeolites and carbons
indicate that these solids may be used as adsorbents for
retaining different types of inorganic and/or organic
species from solutions or gaseous media (Yang, 1987;
Kapoor and Yang, 1989; Radovic and RodrguezReinoso, 1997; Volzone, 2004). The textural and
structural properties are taken into account for adsorbent
capacities. The literature indicates that adsorption
capacity of smectitic and kaolinitic clays could be
Corresponding author. Fax: +54 221 4710075.
E-mail address: volzcris@netverk.com.ar (C. Volzone).
0169-1317/$ - see front matter 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.clay.2005.11.001

improved after specific modifications. Adsorption

processes are of great importance for removal of
pollutants and more recently for separation of gases.
Yang and Baksh in 1991 were the pioneers in studies of
the gas separation processes by using clay minerals.
Studies of gas retention by clays indicate that pillared
smectites (Yang and Baksh, 1991; Yang and Cheng,
1995; Volzone et al., 1998), acid treatments (Volzone
and Ortiga, 1998, 2000; Venaruzzo et al., 2002), organic
intercalations (Volzone et al., 2002, in press) and
different cations in the interlayer spaces of smectites
(Volzone and Ortiga, 2004) influence and may improve
the adsorption capacity. Similarly, selective gas adsorption by amorphous kaolinite derivative (Volzone et al.,

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C. Volzone, J. Ortiga / Applied Clay Science 32 (2006) 8793

Fig. 1. X-ray diffraction of kaolinitic clays before and after

modifications.

1999; Melnitchenko et al., 2000) also influence as it has

been previously reported. Our specific search in
literature indicates that the influence of mineralogical
composition of natural kaolinitic clay on gas adsorption
has not been published up to the moment. In this paper,
we report the O2, N2, CO, CH4, C2H2, CO2 and SO2 gas
retentions at 25 C and 0.1 MPa by different untreated
and thermal-acid leached kaolin clays. Carbon monoxide (CO) is a dangerous pollutant gas, the oxides SOx are
contaminants and can be converted to sulphuric acid in
air, and CO2 gas may also be controlled for environment
protection. The analyses for nitrogen (N2), oxygen (O2),
acetylene (C2H2) and natural gas (CH4) were done for
comparing and evaluating the adsorptions by the kaolin
clays.
2. Materials and methods
Three kaolinitic clays were used as starting materials. The
kaolinite sample named in this paper as K was supplied by
Georgia Kaolin Co., USA (K2G-1). The other kaolins (K1 and
K5) come from Chubut province, Argentina, and were
supplied by Piedra Grande S.A.M.I.C.A. y F.
The acid treatment on the clay, previously heated at 600 C
for 1 h in air atmosphere, was obtained by contacting the clay
with a 2.5 mol/L solution of sulphuric acid at boiling
temperature for 180 min. After acid treatment, the solid was
separated and washed with distilled water. The samples were
named KM, K1M and K5M.
BET surface areas (BrunauerElmmett and Teller) were
obtained from N2 adsorption isotherms at the liquid nitrogen
temperature with a Micromeritics Accusorb instrument on
powder sample previously outgassed at 100 C for 12 h. BET
surfaces areas were calculated from the first part of the
isotherm P/Po b 0.3, where P is the vapour pressure of the

liquid adsorbate at the temperature of the isotherm. The

internal and free surface area were derived according to the
method of Delon et al. (1986).
Chemical analyses of the solids were obtained by
inductively coupled plasma emission spectrometry (ICP) by
fusion/dissolution technique.
Equilibrium adsorptions were measured using volumetric
apparatus, which was connected to a gas flow system. The
gases were dried by passing through presorbers before entering
the system. Samples were outgassed at 100 C for 12 h prior to
measurement. Adsorptions were measured at 25 C and 0.1
MPa. The gases tested were N2, O2, CH4, C2H2, CO, CO2 and
SO2.
The powder X-ray diffractograms were obtained with an
X'PERT equipment using the PW3710 Electronic Control Unit
with a Philips 3020 Goniometer, Cu K radiation at 40 kV and
20 mA and Ni filter. The infrared spectra were recorded using a
Spectrum One Perkin Elmer equipment by Universal ATR
(Attenuated Total Reflectance) method.

3. Results and discussion

3.1. Characterisation of samples
The powder X-ray diffraction profiles for the starting
kaolinitic clays are given in Fig. 1 and composition in
Table 1. The K sample showed a predominant simple
phase as kaolinite. K1 and K5 showed kaolinite and also
illite phases as clays, and quartz as impurity. Minor
quartz and major illite phases were present in K1
compared to K5 sample.
The percentage of majority mineral composition in
starting materials (Table 2) were estimated according to
Worral (1982) by using XRD information, chemical
analyses (Table 1), and taking into account the unit
formulae of mineral detected by XRD: Al2Si2O5(OH)4
kaolinite clay; Na2O3Al2O36SiO22H2O sodium illite
clay, K2O3Al2O36SiO22H2O potassium illite clay
and/or SiO2 as quartz present. This method provides the
so-called rational analysis of the clay and gives the
majority component. The amount of kaolinite phase in
K, K1 and K5 samples were 97.6%, 49.9% and 38.8%,
Table 1
Chemical analyses of starting clays and after modifications
Sample SiO2
(%)

Al2O3 Fe2O3 MgO CaO Na2O K2O TiO2

(%) (%)
(%)
(%)
(%)
(%) (%)

K
KM
K1
K1M
K5
K5M

38.54
4.12
31.94
7.48
24.29
10.62

43.98
74.28
52.45
72.00
68.04
78.31

1.12
0.26
2.31
0.70
1.73
1.43

0.03
0.02
0.63
0.55
0.44
0.33

0.01
0.01
0.44
0.03
0.32
0.05

0.01
0.01
0.22
0.02
0.14
0.02

0.01
0.01
3.43
2.40
2.54
1.79

2.34
4.22
0.17
0.20
0.18
0.21

C. Volzone, J. Ortiga / Applied Clay Science 32 (2006) 8793

Table 2
Majority mineralogical composition of the samples
Sample

Kaolinite (%)

Illite (%)

Quartz (%)

Amorphous
silica (%)

K
KM
K1
K1M
K5
K5M

97.6
10.4
49.9

38.8
6.0

29.1
20.3
21.5
15.2

14.8
14.8
39.4
39.4

69.2

47.1

27.4

89

The remained silica derived mainly from kaolinite was

assigned as amorphous/free silica. The kaolinite phase
of the K, K1 and K5 was reduced drastically from
97.6%, 49.9% and 38.8% to 10.4%, 0% and 6.0%
after the modifications (KM, K1M and K5M),
respectively (Table 2). A high proportion of illite
remained after acid modification (Table 2). The
amorphous or free silica appeared after treatment and
more amount of it was obtained, as higher kaolinite
content was present in the raw materials. Then, the K,
K1 and K5 samples, which contained 97.6%, 49.9%

respectively (Table 2). No quartz and illite were detected

in K sample. Nevertheless, the quartz contents of K1 and
K5 samples were 14.8% and 39.4%; and of illite was
29.1% and 21.5 %, respectively. The remainder is
assumed to be miscellaneous oxides, carbonates, or
organic matter (Worral, 1982).
The XRD diffractograms of the modified clays
(KM, K1M, K5M) are also shown in Fig. 1 and
composition in Table 1. Important structural changes
were obtained after thermal-acid modifications of the
clays. A great centred band at 4.07 (21.8 2)
assigned to amorphous silica was achieved for KM
sample and in minor proportion for K1M and K5M.
No visible XRD peak of kaolinite phase was shown in
K1M. Nevertheless, some little reflections of kaolinite
phase in KM and K5M samples were present (Fig. 1).
The chemical composition changed after the clays
were modified. The proportion of the octahedral
cations aluminum, iron and magnesium (expressed as
oxide in the Table 1) decreased due to proton of the
acid attack, and the silica content increased. The
calcium, sodium and potash were also released;
nevertheless, the amount of remained potash indicated
that the illite clay type was still in the structure of the
modified K1 and K5 samples (K1M and K5M) as it
was also confirmed by XRD patterns (Fig. 1). The
amount of each phase (kaolinite, illite and quartz) in
modified clays was also estimated similar to the
starting materials, and the results are given in Table 2.
Table 3
Surface and volume measurement of the samples
Sample

BET
surface area
(m2 g 1)

External
surface area
(m2 g 1)

Internal
surface area
(m2 g 1)

Total
volume
(cm3 g 1)

K
KM
K1
K1M
K5
K5M

5.0
198.0
38.0
154.0
15.0
109.0

152.0
25.0
129.0
6.5
82.0

5.0
46.0
13.0
25.0
8.5
27.0

80
137
90
106
112
144

Fig. 2. IR spectra of samples: (a) 35003800 cm 1 zone, (b) 6001300

cm 1 zone.

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C. Volzone, J. Ortiga / Applied Clay Science 32 (2006) 8793

Table 4
Retention gases of original and modified kaolin
Sample

N2 (mmol/g)

O2 (mmol/g)

CO (mmol/g)

CH4 (mmol/g)

CO2 (mmol/g)

C2H2 (mmol/g)

SO2 (mmol/g)

K
KM
K1
K1M
K5
K5M

0.039
0.060
0.068
0.088
0.074
0.095

0.017
0.039
0.064
0.085
0.065
0.110

0.028
0.065
0.067
0.101
0.068
0.117

0.017
0.066
0.075
0.131
0.076
0.130

0.044
0.602
0.150
0.534
0.104
0.437

0.071
0.721
0.235
0.595
0.135
0.450

0.201
1.242
0.542
1.111
0.403
0.914

and 38.8% of kaolinite phase, originated 69.2%,

47.1% and 27.4% amorphous/free silica, respectively.
The total surface area (BET surface) of K, K1 and K5
increased significantly after treatments from 5, 38 and
15 m2 g 1 to 198, 154 and 109 m2 g 1, respectively
(Table 3). These increases were due mainly to external
surface contribution originated after treatments, whose
final values were 152, 129 and 82 m2 g 1 for KM, K1M
and K5M, respectively. The total volume, measured at
P/Po = 0.986 on adsorption branch, also increased after
modification of clays.
The infrared analyses of the samples (Fig. 2)
confirmed the behaviour observed by XRD and
chemical analyses. The bands at 3698, 3671, 3652,
3624 cm 1 (Fig. 2a), 1029, 1004, and 915 cm 1 (Fig.
2b) are typical of kaolinite mineral. Different proportions of intensity bands are present in K, K1 and K5
samples. The bands at 790 cm 1 and at 698 cm 1
corresponding to quartz and illite phases (Farmer, 1974),
respectively, were more prominent in K5 sample.
Important changes in the spectra were observed after
treatments on samples, where the bands at higher than
3600 cm 1 zone (Fig. 2a) were drastically reduced. The
bands at 3698 and 3624 cm 1 (related to presence of
kaolinite phase) for KM and K5M samples were very

low and they disappeared for K1M. The SiOSi

stretching parallel band at 1029 cm 1 (Fig. 2b)
disappeared with the treatment and the band at higher
frequency corresponding to SiOSi stretching perpendicular (1075 cm 1) appeared simultaneously broadened. The loss in crystalline order through breaking and
bending of chemical bonds produced a final solid with
high resembling silica gel (Temuujin et al., 2004;
Nguetnkam et al., 2005; Wypych et al., 2005).

Fig. 3. Gas adsorption vs. BET surface.

Fig. 4. Normalised gas retention vs. BET surface.

3.2. Retention of gases and discussion

The untreated samples showed low retention gases
except in general for CO2, C2H2 and SO2 gases (Table
4). After thermal-acid modifications on kaolins, the
retention of all gases analysed (N2, O2, CO, CH4, CO2,
C2H2 and SO2) improved; nevertheless, the retention
values for N2, O2, CO, CH4 gases were lower (0.039
0.131mmol/g) than CO2, C2H2 and SO2 which increased
in the range of 0.4371.242 mmol/g, depending on the
sample and gases used by XRD. The amounts of
retention were in the order CO2 b C2H2 SO2.
The BET surface increased after treatment and some
correlation was found with adsorption of gases as shown
in Fig. 3 in which the adsorption of CO2, C2H2 and SO2

C. Volzone, J. Ortiga / Applied Clay Science 32 (2006) 8793

91

gases are plotted against BET surface areas. Similar

behaviour was also found by using modified smectitic
clay (Venaruzzo et al., 2002; Volzone and Ortiga, 2004)
and kaolinite amorphous derivative (Volzone et al.,
1999; Melnitchenko et al., 2000).
The normalised gas retention vs. BET surface plot
(Fig. 4) indicates that the increase of the adsorption per
surface area (mol per m2) is not proportional to the
surface area for low BET surface value, which
corresponded to raw materials (K, K1 and K5). At
higher value of BET surface, corresponding to modified
clays, the normalised plot indicated some proportion
with the contribution of surface area. Then, the starting
materials showed different behaviours with respect to
the modified clays. Fig. 4 also shows that the SO2
normalised retention was higher than CO2 and C2H2
gases.
By plotting CO2 gas adsorption as a function of Si
content of the adsorbents (Fig. 5), it was found that the
adsorption by each raw sample increased with the
increase of Si content originated after treatments.
Similar correlation was found for C2H2 and SO2
gases. K, K1 and K5 samples increased in the different
forms. To clarify this situation, the Si contribution from
different mineralogical phases of each sample was
plotted vs. adsorption as shown in Fig. 6. The Si of
amorphous/free silica of the modified clays influenced
the gas adsorption, but not the Si from quartz, illite or
kaolinite phases. At low gas adsorption, where the
amorphous silica was not present, the increase that was
found dependent of illite clay as shown in Fig. 7. The
same behaviour was found for SO2 and C2H2 gases.
Then, the illite phase is better for gas adsorption than the
kaolinite phase present in starting clay material (Tables
2 and 4). Fig. 8 shows that the contribution to free

surface is mainly due to two factors: illite for raw

materials and amorphous/free silica for treated clay
materials. It is probable that the interlayer spacing of
illite (10 ) which is higher than kaolinite (7 )
influence in adsorption gas molecules. Besides, the
presence of potassium of the illite may favour the
retention of the gases similarly as it was found when
potassium cation was present in interlayer position of
the smectites (Volzone and Ortiga, 2004). Fig. 1 and
Table 2 show that the K1 clay contents more proportion
of illite phase than K5 clay and the former retained more
amount of gas as shown in Table 4. On the other hand,
after thermal-acid treatment on materials, the content of
the kaolinite phase originated more amorphous silica,
which was responsible for a better gas retention because
the illite phase remained practically unalterable after
treatment. The retention of gases by amorphous silica,
which was originated by modified kaolinite phase, was

Fig. 5. Increase of CO2 gas adsorption by each sample vs. Si content.

Fig. 7. Contribution of mineral phase in percent vs. gas adsorption.

Fig. 6. Percentage of Si from different phases vs. gas adsorption.

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C. Volzone, J. Ortiga / Applied Clay Science 32 (2006) 8793

kaolinitic materials. On the other hand, the increase in

both surface areas (external and internal), with high
contribution of external surface, and the higher
amorphous silica content of the sample after thermalacid clays, due mainly to kaolinite phase, were the main
cause for the improvement on adsorption gases
measured at 25 C and 0.1 MPa.
The capacities of adsorption N2, O2, CO, CH4 CO2,
C2H2 and SO2 gases increased in the modified kaolinitic
clays. The retention values for N2, O2, CO, CH4 gases
were lower (0.0390.131mmol/g) than CO2, C2H2 and
SO2 (0.4371.242 mmol/g). The prepared modified
kaolinitic clays could be proposed as potential solids for
separation of gas mixtures.
Fig. 8. Contribution of clay and silica to external surface vs. gas
adsorption.

higher than retention by the starting sample with illite

phase.
The different retention values of the each molecule
gases could be attributed to the influence of the physicochemical properties of the adsorbates (critical size,
polarizability, etc.) as reported Yang and Baksh (1991).
CO2 gas adsorptions by modified kaolinitic clays in
this study (0.602 mmol/g, KM; 0.534 mmol/g, K1M and
0.437 mmol/g, K5M) were higher than by Al-, Zr-, Cr- and
Ti-pillared clays (0.210, 0.185, 0.100 and 0.141 mmol/g)
and modified Al-PILCs (0.300 mmol/g) (Volzone et al.,
1998) Nevertheless, the values were similar to those of
adsorption by smectites treated with organic compounds
(0.480 mmol/g) and acid-treated smectites as it was
reported (Venaruzzo et al., 2002; Volzone et al., 2002).
SO2 gas adsorptions by thermal-acid treated clays
described in this paper (0.9141.242 mmol/g) were
similar to acid-treated montmorillonite (1.231 mmol/g),
which was reported by Venaruzzo et al. (2002).
The levels of adsorption for CH4 and CO were
similar to those reported previously for montmorillonites (Volzone et al., 1998; Volzone and Ortiga, 2004).
The modified kaolinite clays by thermal-acid treatment (Table 4) could be proposed as a potential material
for SO2, CO2 or C2H2 separation from N2, O2, CO, or
CH4 because the equilibrium gas retention ratio values
were higher than 3.00 (Yang and Baksh, 1991).
4. Conclusions
The mineralogical composition of the natural kaolin
plays an important role in adsorption gases by raw and
after treated kaolins. The presence of illite phase in raw
kaolin was the main cause for gas retention by raw

Acknowledgments
We thank to CONICET (PIP02100) for financial
support.
References
Delon, J.F., Lietard, O., Cases, J.M., Ivon, J., 1986. Determination of
porosity of layer materials using slit-shaped and bevelled pores.
Clay Minerals 21, 361375.
Farmer, V.C., 1974. The infrared spectra of minerals. Mineralogical
Society, Monograph, vol. 4. Mineralogical Society, London.
Kapoor, A., Yang, R.T., 1989. Kinetic separation of methanecarbon
dioxide mixture by adsorption on molecular sieve carbon.
Chemical Engineering Science 44, 17231733.
Melnitchenko, S., Thompson, J.G., Volzone, C., Ortiga, J., 2000.
Selective gas adsorption by metal exchanged amorphous kaolinite
derivative. Applied Clay Science 17, 3553.
Nguetnkam, J.P., Kamga, R., Villiras, F., Ekodeck, G.E., Razafitianamaharavo, A., Yvon, J., 2005. Assessment of the surface areas of
silica and clay in acid-leached clay materials using concepts of
adsorption on heterogeneous surfaces. Journal of Colloid and
Interface Science 289 (1), 104115.
Radovic, L.R., Rodrguez-Reinoso, F., 1997. Carbon materials in
catalysis. In: Thrower, P.A. (Ed.), Chemistry and Physics of
Carbon, vol. 25. Dekker, New York, pp. 243358.
Temuujin, J., Jadambaa, T.S., Burmaa, G., Erdenechimeg, S.H.,
Amarsanaa, MacKenzie, K.J.D., 2004. Characterisation of acid
activated montmorillonite clay from Tuulant (Mongolia). Ceramics
International 30 (2), 251255.
Venaruzzo, J.L., Volzone, C., Rueda, M.L., Ortiga, J., 2002. Modified
bentonitic clay minerals for CO, CO2 and SO2 adsorption.
Microporous and Mesoporous Materials 56, 7380.
Volzone, C., 2004. Removal of metals by natural and modified clays.
In: Wypych, F., Satyanarayana, K.G. (Eds), Clay Surfaces:
Fundamentals and Aplications. Academic Press, Elsevier, The
Netherlands, vol 1, pp. 290-320.
Volzone, C., Ortiga, J., 1998. O2, CH4 and CO2 gas adsorption by acid
di- and tri-octahedral smectites. International Workshop of
Activated Clays, 68 December, La Plata, Argentina, pp. 4554.
Volzone, C., Ortiga, J., 2000. Retention gas O2, CH4 and CO2 by acid
smectites with and without thermal treatment. Journal Material
Science 35, 52915294.

C. Volzone, J. Ortiga / Applied Clay Science 32 (2006) 8793

Volzone, C., Ortiga, J., 2004. Influence of the exchangeable cations of
montmorillonite on gas adsorptions. Process Safety and Environmental Protection 82 (B2), 170174.
Volzone, C., Garrido, L.B., Ortiga, J., Pereira, E., 1998. Sntesis de
arcillas pilareadas para su utilizacin como adsorbentes. In:
Rodrguez-Reinoso, F., Andreu, P. (Eds.), Desarrollo de adsorbentes para la separacin de gases, Programa Iberoamericano de
Ciencia y Tecnologa (CYTED) Subprograma V. Catlisis y
Adsorbentes, Proyecto V.3 CYTED-Madrid, Espaa, pp. 97119.
Volzone, C., Thompson, J.G., Melnitchenko, A., Ortiga, J., Palethorpe,
R.S., 1999. Selective gas adsorption by amorphous clay mineral
derivative. Clays and Clay Minerals 47, 647657.
Volzone, C., Rinaldi, J.O., Ortiga, J., 2002. N2 and CO2 adsorptions by
TMA- and HDP-montmorillonite. Materials Research 5, 475479.
Volzone, C., Rinaldi, J.O., Ortiga, J., in press. Retention of gases by
hexadecyltrimethylammonium-montmorillonite clays, Journal Environmental Management. (corrected proof, Available online 22
September 2005).

93

Worral, W.E., 1982. Ceramic Raw Materials, 2nd Edition. Pergamon

Press, Great Britain.
Wypych, F., Adad, L.B., Mattoso, N., Marangon, A.A.S., Schreiner,
W.H., 2005. Synthesis and characterization of disordered layered
silica obtained by selective leaching of octahedral sheets from
chrysotile and phlogopite structures. Journal of Colloid and
Interface Science 283 (1), 107112.
Yang, R.T., 1987. Gas Separation of Adsorption Processes. Butterworth Publisher, Boston.
Yang, R.T., Baksh, M.S.A., 1991. Pillared clays as a new class of
sorbents for gas separation. AIChE Journal 37, 679686.
Yang, R.T., Cheng, L.S., 1995. Pillared clays and ion-exchanged
pillared clays as gas adsorbents and catalysts for selective
catalytic reduction of NO. In: Pinnavaia, T.J., Thorpe, M.F.
(Eds.), Access in Nanoporous Materials. Plenum Press, New
York, pp. 7392.