Applied Clay Science 101 (2014) 229236

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Applied Clay Science

journal homepage: www.elsevier.com/locate/clay

Research paper

Study of surface acidbase properties of natural clays and zeolites by the

conversion of 2-methylbut-3-yn-2-ol
Lyudmila Novikova a,, Frank Roessner b, Larisa Belchinskaya a, Murad AlSawalha c, Victoriya Krupskaya d
a

Voronezh State Academy of Forestry and Technologies, 8 Timiryazeva str., Voronezh 394087, Russian Federation
Institute of Chemistry, Industrial Chemistry 2, Carl von Ossietzky University of Oldenburg, Oldenburg D-26111, Germany
Department of Chemical and Process Engineering Technology, Jubail Industrial College, PO Box 10099, Jubail Industrial City 31961, KSA
d
Institute of Geology of Ore Deposits, Petrography, Mineralogy and Geochemistry Russian Academy of Science, 35 Staromonetniy per., Moscow 119017, Russian Federation
b
c

a r t i c l e

i n f o

Article history:
Received 28 June 2014
Received in revised form 28 July 2014
Accepted 8 August 2014
Available online 29 August 2014
Keywords:
Montmorillonite
Kaolinite
Palygorskite
Zeolites
Surface acidbase properties
Conversion of 2-methylbut-3-yn-2-ol

a b s t r a c t
Surface acidbase properties of natural clays and non-clay minerals from Jordanian (J) and Russian (R) deposits
as well as H-ZSM-5 were studied applying catalytic reaction of 2-methylbut-3-yn-2-ol (MBOH) conversion.
Products of both acidic and basic pathways of the reaction were formed involving surface acid/basic sites of
clay minerals. Specic conversions of MBOH decreased in the following order: kaolinite-R N hydromicaR N bentonite-J N red-kaolinite-J = palygorskite-R = H-ZSM-5 N zeolite-J N white-kaolinite-J N diatomite-J,
which fairly correlated with TPD-NH3 acidity assessment for a majority of samples. However, a contribution of
basic sites to the reaction should be taken into account, especially for hydromica-R and kaolinite-R.
The strength of acid sites of natural aluminosilicates was compared based on surface acidity and reaction product
yields. After 116 min of MBOH conversion, the strength of acid sites changed in the following order: kaoliniteR N palygorskite-R N bentonite-J N red- kaolinite-J N white-kaolinite-J N zeolite-J N diatomite-J N H-ZSM-5.
At an early (17 min) stage of the reaction, the strength of active sites for natural zeolite-J and H-ZSM-5 were comparable, while the latter underwent signicant deactivation due to its microporous structure.
The rise of activation temperature from 500 C to 700 C for montmorillonite containing sample increased the
conversion of MBOH due to the formation of stronger or additional number of basic sites as a result of mineral
dehydroxylation. Natural clay samples with a higher content of montmorillonite (3080%) altered the acid
base properties of the surface and observed higher ability to convert MBOH over acid and basic pathways.
2014 Elsevier B.V. All rights reserved.

1. Introduction
Natural clay minerals are cheap and simultaneously valuable materials widely applied in manifold processes of gas and liquid treatment,
chemical industry, as well as fabrication of various advanced composite
materials (Adams and McCabe, 2006; Gil et al., 2010; Sinha Ray and
Bousmina, 2005; Trombetta et al., 2000). Materials based on natural
aluminosilicates, i.e., sorbents, llers of polymeric compositions, are environmentally safer, have an improved performance and can be re-used
as additives in building or other industries to avoid regeneration step
(Belchinskaya, 2002; Belchinskaya and Anisimov, 2012).
The main feature of clay minerals is their layered structure formed
by tetrahedral TO4 (T = Si4 +, Al3 +, Fe3 +) and octahedral MeO6
(Me = Al3+; Fe3 +; Mg2+; Fe2+) sheets. The alternating connections
of tetrahedral (T) and octahedral (O) sheets generate different groups

Corresponding author at: 8 Timiryazeva str., 394087 Voronezh, Russian Federation.

Tel.: +7 473 2537659; fax: +7 473 2537651.
E-mail addresses: novikov-la@yandex.ru (L. Novikova),
frank.roessner@uni-oldenburg.de (F. Roessner), chem@vglta.vrn.ru (L. Belchinskaya),
murad_s@jic.edu.sa (M. AlSawalha), krupskaya@ruclay.com (V. Krupskaya).

http://dx.doi.org/10.1016/j.clay.2014.08.005
0169-1317/ 2014 Elsevier B.V. All rights reserved.

of clay minerals, e.g., 1:1 mineral group (kaolinite group) with alternating
T-O-sheets, 2:1 group (smectite group) with T-O-T layers, etc. Besides,
bers of palygorskite and sepiolite (hormite group) are riddled with
zeolite-like channels formed by SiO4 ribbons joint by discontinuous
O-sheets (Galan, 1996). Isomorphic substitutions of Si 4 + for Al3 +
in T-sheets and Al3+ for Fe2+, Mg2+ in O-sheets induce a negative charge
of the layers compensated by exchangeable cations, which nevertheless
block micropores in raw clays and natural zeolites (clinoptilolite,
chabazite) along with water molecules or mineral accompanying impurities (Inglezakis and Zorpas, 2012). The stacks of 920 layers (Le Forestier
et al., 2010) form mineral particles having irregular form and being never
true crystals (Bergaya and Lagaly, 2013). Weak contacts between particles constitute aggregates and assemblages with a complex structure of
mesopores (Kuila and Prasad, 2013; Wang et al., 2014). These pores
with a diameter of 25 nm are the main domains of surface active sites
responsible for adsorption and catalytic activity of minerals in a natural
state.
Commonly, the surface active sites of aluminosilicates are characterized in terms of Broensted and Lewis acidity/basicity comprising
exchangeable cations, coordinatively unsaturated ions Al3 +, Mg2 +,
Fe3+, acid/basic hydroxyl groups and oxygen anions of aluminosilicates

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L. Novikova et al. / Applied Clay Science 101 (2014) 229236

CH3
H3C

CH

OH
2-methylbut-3-yn-2-ol
MBOH
Acid

Coordinatively unsaturated
CH3
CH3
C

H2C

H3C

CH

C
H3C

CH

H3C
H3C

CH3
OH
2-hydroxy-2-methyl-3-butanone
HMB

3-methyl-3-buten-1-yne
MBYNE
H3C

Basic

O
3-methyl-2-buten-1-al
Prenal

acetone

H3C
C

HC

CH

CH3

H2C

3-methyl-3-buten-2-one
MIPK

acetylene

Fig. 1. Scheme of the MBOH conversion over different active sites of a catalyst.

(Schoonheydt and Johnston, 2006). Surface acidbase properties

strongly depend on the chemical composition and the structure of
aluminosilicates and can be varied applying different treatments,
e. g., mechanical (Balogh and Laszlo, 1993), thermal (Pushpaletha et al.,
2005), chemical treatment (Fari et al., 2010; He et al., 2013; Komadel,
2003) or, recently, the magnetic eld exposure (Belchinskaya et al.,
2009).
Various physicochemical methods are applied to estimate the type
and quantity of active sites, for instance, FTIR studies of pyridine adsorption (Blanco et al., 1988; Sun Kou et al., 2000), thermal programmed
desorption (TPD) of NH3, CO2 or pyridine (Ertl et al., 1997; Matsuhashi
et al., 1994; Okada et al., 2006; Topsoe et al., 1981), NMR-method
(Hunger, 2008), titration with various probe molecules (Tanabe et al.,
1990) and thermoanalytical methods (Ravichandran and Sivasankar,
1997; Ruiz et al., 2002). Other tools for the characterization of the
acid-basic properties of solids, which have been used extensively
over recent decades, are catalytic test reactions, i.e., n-hexane or isopropanol conversion, but-1-ene isomerisation (Ono and Baba, 1997;

Pines and Stalick, 1977; Trombetta et al., 2000), etc. Applying test
reactions under conditions close to that of real catalytic processes one
can evaluate the type of active sites catalyzing the reaction (Brnsted/
Lewis sites and base sites), the concentration and the strengths of active
sites. Nevertheless, it is required from a test reaction to proceed along
one pathway and to have no side products. Moreover, the large size of
the probe molecule can cause diffusion limitations of the reaction,
especially for microporous materials. However, interparticle porosity
available in clay catalysts makes it less possible.
For characterization of clay minerals, a number of test reactions were
applied including dehydration of 1-butanol, cracking of cumene
(Ravichandran et al., 1996) and benzene benzylation (Pushpaletha
et al., 2005). It was proved that severe acid activation of bentonites
and vermiculite caused an increase in substrate conversions and in the
number of Lewis and Brnsted sites.
Recently, a powerful test reaction of 2-methylbut-3-yn-2-ol
(MBOH) conversion (Lauron-Pernot, 2006; Lauron-Pernot et al., 1991)
has been successfully applied for unambiguous differentiation between

Table 1
Chemical and phase composition of the investigated aluminosilicates samples.
Sample

Phase composition

Chemical composition (mass%)

Al2O3

Fe2O3

FeO

MgO

CaO

Na2O

K2O

TiO2

Zeolite, Tell Rmah, Jordan, (Zeol-J)

Bentonite, Al-Azraq, Jordan (Bent-J)
White kaolinite, Al-Azraq, Jordan (W-Kaol-J)
Red kaolinite, Batn el Ghoul, Jordan (R-Kaol-J)
Diatomite, Al-Azraq, Jordan (Diat-J)
Palygorskite, Cherkassy, Russia (Pal-R)

(Majorphillipsite, chabazite, faujasite)

Smectite 10%, illite, feldspar, quartz
(Minorquartz, mica, feldspar, gypsum)
(Minorquartz, mica, feldspar, gypsum)
Traces of kaolinite, illite, quartz
Plg-R ~50%, quartz, zeolite, mica, feldspar

42.0
55.7
48.0
47.6
72.0
53.2

12.8
20.1
36.3
24.9
11.8
9.8

12.1
1.5
1.0
6.1
5.8
7.7

0.6

10.1
3.5
0.3
1.0
1.5
7.9

8.5
2.1
0.1
0.5
7.2
3.6

0.8
2.4
1.8
2.3
0
K2O

0
2.5
0
0.7
0
0

Kaolinite-R, Voronezh, Russia (Kaol-R)

Hydromica-R, Voronezh, Russia (Hdm-R)

Kaolinite ~60%, hydromica ~30%, montmorillonite ~10%

Hydromica ~3035%, clinoptilolite ~5%, kaolin
~5%, quartz, micatraces

50.5
48.5

18.2
11.2

6.8
0.9

0.3

1.8
1.1

1.9
9.8

4.0
0.1
0.1
0.8
0
Na2O +
0.9
0.3
4.1

SiO2

0
0

L. Novikova et al. / Applied Clay Science 101 (2014) 229236

231

Table 2
Phase composition of montmorillonite containing aluminosilicates samples.
Sample

Phase composition

Mt30-R, Montmorillonite (Russia, Velikoarkhangelskoe deposit, Voronezh region)

Mt60-R, Montmorillonite (Russia, Uspenskoe deposit, Voronezh region)
Mt80-R, Montmorillonite (Russia, Voronezh region)

Montmorillonite 30%, kaolinite 35%, hydromica 35%, quartztraces

Montmorillonite 60%, kaolinite 10%, hydromica, quartz, feldspartraces
Montmorillonite 80%, zeolite 15%, hydromica 5%

acidic, basic and amphoteric surface sites (Fig. 1) of various materials.

Later on, it was suggested to substitute the term amphoteric sites by
the coordinatively unsaturated sites (AlSawalha and Roessner, 2008).
Noteworthy, the conversion of MBOH had no diffusion limitations
over zeolites (Huang and Kaliaguine, 1993), hydrotalcites (Meyer and
Hoelderich, 1999) and magnesium oxide catalysts (Chizallet et al.,
2006; Kutrowski et al., 2004). However, there are only few applications
of this test reaction to natural clays and clay minerals (AlSawalha et al.,
2011; Novikova et al., 2006).
In present work, the reaction of MBOH conversion was applied for
comparison of surface acidbase properties and catalytic activity of
natural aluminosilicates varied in their structure for further application
as adsorbents of toxic compounds from the air, aqueous solutions and
composite materials.

2. Experimental
2.1. Materials
Samples of natural aluminosilicates containing zeolite, bentonite,
palygorskite, kaolinite and diatomite were collected from the National
Resource Authority, Jordan and several Russian deposits. The chosen
samples belonged to different groups of clay minerals and zeolites according to their structure, i.e., layered or framework (zeolite) structure.
The chemical compositions of Jordanian clay samples (Table 1) were
determined by X-ray Fluorescence (XRF) method (Abu Salah et al.,
2002; Al-Ghouti et al., 2003; Nawasreh et al., 2006), whereas that for
the aluminosilicates from Russian deposits was derived from chemical
analysis.
Besides, several samples with varied content of montmorillonite
were studied as well. The phase compositions of montmorillonite
containing samples are listed in Table 2.

Fig. 2. MBOH conversion over Jordanian zeolite and clay minerals at 120 C: 1 Zeol-J, 2
Bent-J, 3 R-Kaol-J, 4 Diat-J, 5 W-Kaol-J.

The aluminosilicates samples were studied in natural form without

any preliminary purication being thermally activated before the reaction. They were crushed and sieved into a 200- to 315-m fraction. Samples of synthetic zeolite H-ZSM-5 (SiO2/Al2O3 = 45) were used as
reference catalyst.
2.2. Conditions for MBOH conversion
The reaction of MBOH conversion (95 vol.% MBOH and 5 vol.%
toluene) was carried out in a xed-bed, automated bench unit
(Kutrowski et al., 2004), using toluene as an internal standard. Both
MBOH and toluene were obtained from Fluka with purity of 99% and
used without further purication. The mixture was cooled to 13 C in
a storage vessel. Applying a static nitrogen pressure of 202.65 kPa, a
constant ow of the mixture (0.02 mL/min) passed through a capillary
into the evaporator. A sample charge of 0.2 g was activated in air ow at
500 C for 4 h in a tubular stainless steel reactor. This temperature was
chosen experimentally in order to compare different catalysts under the
same conditions (Kutrowski et al., 2004; Okada et al., 2006). Afterwards the reactor was ushed by N2 ow for 4 h and nally was cooled
down till the temperature of reaction t = 120 C. The reaction products
were analyzed on a Hewlett-Packard Model 5890 series II gas chromatograph connected online to the reactor outlet and equipped with a capillary column (Optima Wax, Macherey-Nagel). The conversion of MBOH
(XMBOH in mol%) and the yield of products (YP in mol%) were calculated
taking into account that in case of O-containing compounds the
response factors should be corrected by the number of C-atoms as
shown by Decker et al. (2013).
2.3. Temperature programmed desorption of ammonia
The TPD of ammonia was carried out in a quartz reactor on the
device made by Raczek Analyse Technik GmbH, Hannover, Germany.

Fig. 3. MBOH conversion over Russian clay minerals and zeolite H-ZSM-5 at 120 C: 1
Pal-R, 2 Kaol-R, 3 Hdm-R; 4 H-ZSM-5.

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L. Novikova et al. / Applied Clay Science 101 (2014) 229236

Table 3
Specic surface area, SBET, surface acidity and MBOH conversion for investigated natural aluminosilicates.
Sample

SBET, m2/g

Acidity mol/g

Acidity/SBET, mol/m2

XMBOH, % (t.o.s. = 116 min)

XMBOH/SBET, %/(m2/g) (t.o.s. = 116 min)

Zeol-J
Bent-J
R-Kaol-J
W-Kaol-J
Diat-J
Pal-R
Kaol-R
Hdm-R
H-ZSM-5

96a
70a
45a
41a
39a
146b
27b
24b
370b

130.0a
59.4a
56.9a
14.1a
29.0
73.0
48.0

240.0

1.3
0.8
1.3
0.3
0.7
0.5
1.8

0.6

56.0
54.7
31.9
22.3
11.5
96.7
61.3
36.3
26.6

0.6
0.8
0.7
0.5
0.3
0.7
2.3
1.5
0.7

AlSawalha et al., 2011; bNovikova et al., 2006.

Adsorption of ammonia from a mixture with argon (5% NH3) was

carried out at 70 C at a ow rate of 50 mL/min for 30 min. Physically
adsorbed ammonia was desorbed at 130 C for 15 h under control of
thermo conductivity detector (TCD-signal). Chemically adsorbed
NH3 was desorbed by heating of an adsorbent in a stream of He at
130 C850 C with a heating rate 20/min. For the integral quantitative determination of ammonia, the gas ow was passed through hydrochloric acid solution and titrated with NaOH.
2.4. BET-nitrogen adsorption
The specic surface areas of the samples Mt30-R, Mt60-R and Mt80-R
were measured on a Quantachrome Autosorb-1 instrument. Before the
experiments, samples were evacuated at 300 C for 30 min. The specic
surface area was calculated using the BET method.
3. Results and discussion
3.1. MBOH conversion over natural clay minerals
The catalytic activity versus time on stream for the investigated clay
minerals from the Jordanian and Russian deposits are presented in
Figs. 2 and 3.
It follows from Figs. 2 and 3 that two groups of aluminosilicate samples displayed divers behaviors in MBOH conversion. The samples of
aluminosilicates originated from Jordan revealed relatively constant
(Zeol-J and Diat-J) or even increasing on time (Bent-J, R-Kaol-J and
W-Kaol-J) catalytic activity during MBOH conversion. The values
of MBOH conversion over Jordanian clay samples varied in a range
of 1758% (t.o.s. = 116 min) and decreased in the following order:
Zeol-J N Bent-J N R-Kaol-J N W-Kaol-J N Diat-J.
On the contrary, H-ZSM-5 and clay minerals from Russian deposits
displayed a signicantly higher rate of MBOH conversion despite
being deactivated in a notable way after the initial stages of reaction.

The highest conversion of MBOH in the beginning and after 116 min
on t.o.s. was observed for Pal-R (96.7%) and the lowest for Hdm-R
(36.3%) and H-ZSM-5 (26.5%). In order to explain such behavior of
natural clay samples in MBOH conversion one should address to
Table 3, summarizing surface characteristics of the samples as well
as the specic conversions of MBOH (XMBOH/SBET) is necessary for
the assessment of the catalytic activity of the unit area of the aluminosilicate surface.
It follows from Table 3 that a clear correlation between the MBOH
conversions (Figs. 2 and 3) and the respective changes in the SBET of aluminosilicates can be found only within the separate group of Jordanian
samples Zeot-J N Bent-J N R-Kaol-J N W-Kaol-J N Diat-J and the samples
from Russian deposits Pal-R N Kaol-R N Hdm-R. The catalytic ability of
aluminosilicates decreased in the same order as SBET changed.
Moreover, these tendencies fairly agree with the amount of desorbed
ammonia (surface acidity) of the samples except for W-Kaol-J; Diat-J
and H-ZSM-5. The acidity per unit area of the samples varied in the following sequence:
KaolR N Zeol J
RKaolJ N BentJ N Diat J N HZSM5 N PalR N WKaol J;

allowing comparison of the strength or the concentration of surface

sites. However, this sequence does not coincide with the row of
XMBOH/SBET values, as follows:
KaolR N HdmR N Bent J N HZSM5 PalR
RKaolJ N Zeol J N WKaol J N DiatJ;

as the contribution of both acid and basic sites should be taken into
account for clay minerals. The contribution of surface basicity to
MBOH conversion is conrmed hereinafter.
The reasons for catalyst deactivation during MBOH conversion could
be strong adsorption of secondary products and irreversible surface

Table 4
Yields of reaction products in MBOH conversion over natural aluminosilicates (t.o.s. = 116 min).
Catalyst

Zeol-J
Bent-J
R-Kaol-J
W-Kaol-J
Diat-J
Pal-R
Kaol-R
Hdm-R
H-ZSM-5 (t.o.s. = 116 min)
H-ZSM-5 (t.o.s. = 17 min)

Yields of reaction products, mol%

Acid sites (Ya.s.)

Basic sites (Yb.s.)

MBYNE

Prenal

Acetone

Acetylene

42.5
33.9
17.9
10.0
1.4
55.8
37.9
15.1
23.8
73.1

1.1
0.0
5.2
0.0
1.2
1.6
1.7
0.8
2.8
0.0

6.5
15.2
4.5
11.2
4.5
18.0
9.9
9.4
0.0
0.0

5.9
5.6
4.2
1.1
4.4
21.3
11.8
11.1
0.0
0.0

As, mol%/(m2/g)

Bs, mol%/(m2/g)

Ra/b, mol/mol

Am, mol%/(mmol/g)

0.4
0.5
0.5
0.2
0.1
0.4
1.5
0.7
0.1
0.2

0.1
0.2
0.1
0.3
0.1
0.1
0.4
0.4

6.7
2.2
5.1
0.9
0.6
3.2
4.0
1.9

336
571
407
346
186
786
825

111
304

Asyield of products formed on acid sites normalized to SBET, mol%/(m2/g); Bsyield of products formed on basic sites normalized to SBET, mol%/(m2/g); Ra/b = As/Bs, mol/mol; Amyield
of products formed on acidic sites normalized to surface acidity, Am = Ya.s./Ca.s., mol%/(mmol/g), Ca.s. - surface acidity (TPD-NH3), mmol/g.

L. Novikova et al. / Applied Clay Science 101 (2014) 229236

XMBOH, %
100
80
60
40
20
0
0

50

100

Kaol-R-500

150
Kaol-R-700

200

250

Time on stream, min

Fig. 4. MBOH conversion over Kaol-R activated at 500 and 700 C, respectively: 1 Kaol-R500; 2 Kaol-R-700.

modication (Lauron-Pernot, 2006). The FTIR-spectra proved the formation of polyaromatic compounds and coke on the surface of H-ZSM-5 due
to acid catalyzed polymerization of MBOH. The microporosity of zeolite
and the natural admixtures of quartz and micas in raw clay samples
strengthen this effect. Moreover, stronger active sites of catalyst, in this
case, the catalysts with a higher acidity per unit area, are expected to undergo earlier and faster deactivation that was observed for Kaol-R, HZSM-5 and Hdm-R (Fig. 3).
The highest catalytic activity of Pal-R among the studied samples is
explained by its unique needle-like structure (Galan, 1996), providing
a high surface area and accessibility of active sites for substrate molecules. However, the surface sites of palygorskite (Pal) are mainly represented by silanol groups (Galan, 1996) having weak acid properties.
It is essential to note that high activation temperatures of clay catalysts not only causes the loss of hygroscopic, zeolitic and crystal waters
and CO2 from decomposition of carbonates/hydrocarbonates but also
partially destroys their structure. For example, folding of the channel
structure for Pal starts above 300 forming the Pal anhydride (Chen
et al., 2006), keeping its layered-band morphology up to 800 C.
Furthermore, thermal treatment at 550 C leads to maximal values of
surface area and total pore volume of Pal followed by subsequent
decrease in surface characteristics while heating at 750 C (Frini-Srasra
and Srasra, 2008). According to Bayram et al. (2007), reversible folding
of the nanochannels of Pal takes place by heating up to 400 C, whereas
at 500 C and 600 C, an irreversible folding of structure occurs.
In the case of Bent-J, despite the calcinations at 500 C, there was still
a possibility of reversible hydration of the mineral (Sarikaya et al., 2000)
by water molecules from the dehydration of MBOH at 120 C. It is
supposed that swelling of the clay mineral caused by its rehydration
resulted in its structural rearrangements and made internal acidic sites
more accessible (AlSawalha et al., 2011). The calcination of kaolinite, a
1:1 clay mineral, results in its transformation to partially amorphous

233

phase of metakaolinite, in which acidity/basicity is varied by regimes of

heating, providing material an ability to act as a super acid under certain
condition (Macedo et al., 1994).
Yields of products formed on acidic and basic sites during MBOH
conversion are summarized in Table 4. For a comparison of the catalytic
activity of different aluminosilicates, the yields of products were normalized by the values of SBET and, on the other hand, by the number
of acid sites determined by amount of desorbed ammonia. Note that according to the reaction mechanism (Lauron-Pernot et al., 1991), MBOH
is converted to MBYNE and prenal on acid sites whereas acetone and
acetylene are formed as a result of cleavage of the MBOH molecule on
basic sites. Hence, for the qualitative assessment of surface acidity,
both the yields of MBYNE and prenal have to be considered. On the
other hand, acetylene and acetone are stoichiometrically coupled, only
the yield of one compound (here acetone) has to be considered for
the calculation of specic activity of basic centers.
It follows from Table 4 that typical products of MBOH conversion
over the clay minerals studied were MBYNE, prenal, acetone and acetylene. The formation of MBYNE and prenal illustrated the presence of the
acid surface sites, while the formation of acetone and acetylene was a
characteristic of basic centers. The presence of both acid and basic
sites is characteristic for the surface of clay minerals and was considered
in detail in literature (Avena, 2006; Azzouz et al., 2004; Kaya, 2004).
The ratio Ra/b between the acid and basic products differs with the
type of clay sample. Yields of MBYNE and prenal exceed yield of acetylene and acetone during the MBOH conversion over majority of samples. This fact shows, apparently, that the number or/and strength of
the acid centers on the surface of the given clay minerals exceed the
number/strength of basic centers.
The values of As and Bs were introduced mainly for a qualitative
comparison of the activity of acid and basic sites of different aluminosilicates. They do not represent any physical background but allow characterizing an ability of the unit area of surface to promote the acid (As) or
the basic (Bs) pathway of the reaction. As follows from Table 4, the
highest acidity per unit area was observed for Kaol-R. For the other
aluminosilicates samples, the acidity of unit surface area varied in the
order: Kaol-R N Hdm-R N Bent-J = R-Kaol-J N Zeol-J = Pal-R N WKaol-J N H-ZSM-5 = Diat-J. This is in agreement with the conrmed
fact of an extremely high acidity of thermally treated Kaol, the acidic
surface of which at 0% moisture is equivalent in acidity to a solution of
90% sulfuric acid (Solomon and Murray, 1972). Additionally, Liu et al.
(2013) applied the rst principles molecular dynamics (FPMD) and
showed that acid surface groups of Kaol had pKas of 6.9 and 5.7 and
those of Mt had pKas of 7.0 and 8.3, respectively. For each mineral, the
calculated pKas were consistent with the results from the titration
curves, indicating that Si-OH and Al-OH2OH groups are the major
acidic sites on the edges of minerals particles.
Regarding the surface sites of other clay minerals, it was conrmed
by Voronchak et al. (2012) that 48% of surface sites of Pal were weak
acid sites whereas that for Bent was only 21%.
According to values of Am (Table 4), the strength of acid sites
available after 116 min of the MBOH conversion distributed among
the studied samples in the following way: Kaol-R N Pal-R N Bent-J N RKaol-J N W-Kaol-J N Zeol-J N Diat-J N H-ZSM-5.

Table 5
Yields of reaction products in MBOH conversion for Kaol-R, activated at 500 C and 700 C (t.o.s. = 116 min).
Catalyst

Kaol-R-500
Kaol-R-700

Yields of reaction products, mol%

Acid sites (Ya.s.)

Basic sites (Yb.s.)

MBYNE

Prenal

Acetone

Acetylene

37.9
41.1

1.7
1.8

9.9
14.1

11.8
16.7

As, mol%/(m2/g)

Bs, mol%/(m2/g)

Ra/b, mol/mol

XMBOH/SBET, %/(m2/g)

1.5
1.6

0.4
0.5

3.7
3.2

1.8
2.1

Asyield of products formed on acid sites normalized to SBET, mol%/(m2/g); Bsyield of products formed on basic sites normalized to SBET, mol%/(m2/g); Ra/b = As/Bs, mol/mol.

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L. Novikova et al. / Applied Clay Science 101 (2014) 229236

3.2. Inuence of the temperature of catalyst activation on MBOH conversion

Changes of MBOH conversions (Fig. 4) over natural kaolinite activated
at 500 C (Kaol-R-500) and 700 C (Kaol-R-700) conrmed an increase in
MBOH conversion at higher activation temperatures.
The yields of acidic products (Table 5) remained practically constant,
whereas the yield of acetone and acetylene formed via the basic reaction
pathway increased. The decrease of Ra/b testies to an alteration of
surface acidity/basicity by thermal treatment leading to the formation
of either stronger surface sites (Liu et al., 2011) or additional numbers
of basic sites due to mineral dehydroxylation at t 700 C (HellerKallai, 2006; Sarikaya et al., 2000). As a result, the higher XMBOH/SBET
for Kaol-R-700 is the evidence of the enhanced activity of its unit area
of surface.

3.3. Inuence of the montmorillonite content on catalytic properties of clay

minerals

Fig. 5. MBOH conversion over clay minerals with different content of montmorillonite:
1 Mt10-R; 2 Mt30-R; 3 Mt60-R; 4 Mt80-R.

The evidence of a strong and fast deactivation of H-ZSM-5 follows

from its values of Am at an early (17 min) and late (116 min) stages of
reaction (Table 4). At the same time, it is obvious that the strength of active sites for natural Zeol and H-ZSM-5 is comparable, while the latter
undergoes signicant deactivation due to its microporous structure.
Along with the acid products of MBOH conversion, one should consider the formation of noticeable amounts of basic products proving,
essentially, the contribution of basic centers to the general population
of surface centers. The values of Yb.s. were higher than those of Ya.s. for
Diat-J and W-Kaol-J. The normalized yields of basic products were also
high for Kaol-R and Hdm-R despite its high values of As. As shown by
AlSawalha and Roessner (2008), the energy of activation for the basic
pathway was slightly higher than for the acidic one (EA = 79.4 kJ/mol
and EA = 45.8 kJ/mol, respectively) as calculated for the conversion of
MBOH on silica-alumina and hydrotalcite. The reaction mechanism
considered in detail by the same authors indicated that the SiOH groups
were the acidic centers and the oxygen anions OO- were the basic
centers on the surface of the catalyst. As expected from the structure
of zeolite H-ZSM-5 and from its high value of SiO2/Al2O3 ratio, equal
to 45, only products of the acidic pathway were formed. In case of clay
minerals, the Broensted acid sites are mainly represented by the
water molecules polarized by interlayer cations during an activation
procedure.
The lowest conversion and product yields were observed for Diat-J,
probably due to its low acidity (AlSawalha et al., 2011) as a result of
partial condensation of surface silanols to siloxane groups during the
thermal treatment (Fubini et al., 1995).

Natural clay samples with different proportions of montmorillonite

were tested in the MBOH conversion reaction in order to compare
their catalytic ability. The time changes of experimental conversions of
MBOH are represented in Fig. 5.
It is seen from Fig. 5 that an increase in Mt content caused a higher
conversion of MBOH on the active centers of the samples. The activity
of samples containing 3080% of Mt was rather high providing almost
the same values of conversion for all samples during 50 min of the reaction. The Mt10-R underwent earlier and signicant deactivation that
could be explained by its lower number of transport pores in comparison with other samples having higher Mt content (Novikova et al.,
2005).
The conversion of MBOH ran via both acidic and basic pathways
forming MBYNE, acetylene and acetone as main products. Yields of
products formed on acid sites were 2.67.7 times higher as for basic
sites (Table 6), conrming the dominating surface acidity. The normalized yields As and Bs for Mt10-R, Mt30-R, Mt60-R and Mt80-R were calculated using values of SBET, which came to 28, 36, 62 and 83 m2/g
correspondingly, as followed from the BET nitrogen adsorption
measurements. The sample of Kaol-R was considered here as Mt10-R
as it contained 10% of montmorillonite.
The changes of Ra/b values in the order Mt30-R N Mt10-R N Mt80R N Mt60-R testify to different ratios between surface acidity and basicity of the samples, obviously, due to their complex phase compositions
including, in some cases, comparable amounts of Mt, Kaol and Hdm
(Table 2). A decrease of XMBOH/SBET values for Mt60-R and Mt80-R
indicated the reduced activity of surface sites, here mainly due to the
acid sites, according to Ra/b and As.
The contribution of basic site to the conversion of MBOH was also
remarkable. The higher was the content of Mt and respective SBET of
the sample, the higher was the yield of products formed on basic sites
as they were easier accessible, though the basicity per unit surface
area slightly decreased from Mt10-R to Mt80-R according to Bs values.

Table 6
Yields of reaction products in MBOH conversion for natural aluminosilicates with varied montmorillonite content (t.o.s. = 116 min).
Catalyst

Yields of reaction products, mol%

Acid sites (Ya.s.)

Mt10-R
Mt30-R
Mt60-R
Mt80-R

As, mol%/(m2/g)

Bs, mol%/(m2/g)

Ra/b, mol/mol

XMBOH/SBET, %/(m2/g)

1.5
2.0
0.8
0.6

0.4
0.3
0.3
0.2

3.7
6.7
2.7
3.0

2.2
2.6
1.5
1.2

Basic sites (Yb.s.)

MBYNE

Prenal

Acetone

Acetylene

37.9
70.1
51.2
52.4

1.7
2.5
1.8
1.4

9.9
9.4
18.4
20.6

11.8
10.8
21.4
23.5

Asyield of products formed on acid sites normalized to SBET, mol%/(m2/g); Bsyield of products formed on basic sites normalized to SBET, mol%/(m2/g); Ra/b = As/Bs, mol/mol.

L. Novikova et al. / Applied Clay Science 101 (2014) 229236

4. Conclusions
Applying the reaction of MBOH conversion, it was possible to assess
and compare the acidbase properties of natural aluminosilicate
samples from various deposits. The variety of phase compositions determined the catalytic activity and the respective surface acidity or basicity
of samples. As it was shown, MBOH can be converted both on acidic and
basic active surface sites of natural aluminosilicates from Jordanian and
Russian deposits. The highest catalytic activity was found for Pal-R and
the lowest for Diat-J. The yields of acidic products exceeded the yields
of basic products for most of the samples proving the higher acidity of
surface. The yield of reaction products formed on acid sites normalized
by surface area of samples varied in the order: Kaol-R N R-Kaol-J =BentJ N Zeol-J = Pal-R N W-Kaol-J N H-ZSM-5 = Diat-J, which was different
from the one for acidity values obtained from TPD-NH3 measurements:
Kaol-R N Zeol-J = R-Kaol-J N Bent-J N Diat-J N H-ZSM-5 N Pal-R N WKaol-J. Comparable values of products yields formed on basic and acid
sites were observed for W-Kaol-J and Diat-J.
The Jordanian clay minerals revealed the constant conversion of
MBOH throughout the reaction process, whereas the Kaol-R and Hdm-R
underwent signicant deactivation straight from the initial stages of reaction. Rising the temperature of catalyst activation from 500 C to 700 C
led to a higher conversion of MBOH over basic sites.
Acknowledgments
L.N. and M.A. gratefully acknowledge the German Academic
Exchange Service (DAAD) and the Russian Ministry of Education and
Science for the visiting grants within the framework programme
Michael Lomonosov.
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