Clays and Clay Minerals, Vol. 47, No. 4, 481 486, 1999.

EFFECT OF A C I D A C T I V A T I O N ON THE D E - T E R T - B U T Y L A T I O N
A C T I V I T Y OF S O M E J O R D A N I A N CLAYS

SABRI MAHMOUD AND SADIQ SALEH

Chemistry Department, Yarmouk University, Irbid, Jordan

Abstraet--Jordanian natural kaolin and bentonite show good catalytic activity towards debutylating 2-
tert-butylphenol, and varying debutylation vs. isomerization selectivity after acid activation. The resulting
catalytic activity of these samples is dependent on the acid employed for activation; the samples treated
with acetic acid showed relatively low conversions, whereas those treated with hydrochloric or phosphoric
acid were found to be very active. Treatments with strong acids such as HC1 have various effects on the
activity of the samples depending on the concentration of the acid. For example, treatment with 1 M HC1
gives the highest activity, whereas a treatment using 12 M HC1 produced the lowest activity. The debn-
tylation selectivity of the acid-activated samples is affected by the acid type and/or concentration. This
selectivity ranges from 20 to 60%, whereas that of water-treated samples is between 46-82%.
Key Words--Bentonite, Butylphenol, Catalyst, Clay, Debutylation, Kaolin, Kaolinite, Montmorillonite.

INTRODUCTION determine the suitability of these clays to be catalysts

Natural clays are increasingly used in industry as
catalysts or catalyst supports in many organic reactions
(Auer and Hofmann, 1993; Li and Jin, 1996; Ravi-
chandran et al., 1996, Upadhya et al., 1996; Chitnis
and Sharma, 1997; Clark et al., 1997). For example,
montmorillonite and kaolinite are two clays commonly
used in these reactions. The catalytic properties of
clays are affected by chemical composition, structure,
and pretreatment conditions (Auer and Hofmann,
1993; Ravichandran et at., 1996).
The catalytic properties can be improved by differ-
ent acid treatment and/or pillaring methods (Auer and
Hofmann, 1993; Ravichandran et al., 1996; Upadhya
et al., 1996; Chitnis and Sharma, 1997; Clark et al.,
1997). For example, the alkylation of many organic
compounds, including phenols, aromatics, and other
hydrocarbons, is catalyzed by acid-treated clays (Chit-
nis and Sharma, 1997). Also, acid treatment with HC1
has produced an overall increase in the surface acidity
and acidic sites of clays, which increases their catalytic
activity in the isomerization of cis- and t r a n s - 2 - b u -
tenes, and in the cracking of cumenes (Ravichandran
et al., 1996).
The tert-butyl group is used as a protector in the
synthesis of many organic products (Corma and Woj-
ciechowski, 1985), because this group may be easily
detached even at relatively low temperatures. Such a
reaction usually involves an acid catalyst, such as pil-
lared clay molecular sieves (Gao and Jiao, 1989) and
natural clays (Tkac et al., 1994; A1-No'aimei, 1997;
Komadel et al., 1997; Saleh and Mahmoud, 1998).
We investigated the stability and catalytic activity
of some Jordanian clays in a variety of reactions, such
as hydrogenation of acetylenes, hydrocracking of par-
affins, and debutylation of some substituted arenes
(A1-No'aimei, 1997; Saleh and Mahmoud, 1998), to
or catalyst supports. These clays proved to be good
debutylation catalysts and better than tested Bulgarian
and Turkish samples (Saleh and Mahmoud, 1998).
Here, we report the effect of acid treatment with
varying concentrations on the catalytic properties of
Jordanian bentonite and kaolin in the de-tert-butylation
of 2-tert-butylphenol. Such treatment includes the use
of weak and strong acids of different concentrations.
It is then possible to investigate the effect of acid type
and/or concentration on the strength and density of the
active acid sites on the clay surface. The debutylation
of 2-tert-butylphenol was chosen as the model reaction
because the tert-butyl group is ortho to the hydroxyl
group that activates positions 2, 4, and 6. Therefore,
in addition to catalytic activity, it is possible to study
the selectivity of these clays in producing various
mono- mad di-substituted tert-butylated isomers as a
result of transalkylation.
MA TERI A LS A N D M E T H O D S
Bentonite samples were collected from southeastern
A1-Azraq area, east of Jordan, whereas kaolin samples
were obtained from the northeastern region of Jordan.
All chemicals used were of reagent grade and were
not purified further before use. The chemical compo-
sition of the samples was determined by atomic ab-
sorption spectrometry (Pye Unicam SP9) after diges-
tion with HNO3, HC1, and HF (Table 1). All samples
were soaked overnight in acid solutions of HC1,
H3PO 4, or CH3COOH of proper concentrations (Table
1), then washed with distilled watel, and dried at
100~ for 2 d. The clays were then calcined at 450~
in flowing air (100 cm 3 rain ') in a fixed-bed flow
reactor for 4 h.

Copyright 9 1999, The Clay Minerals Society 481

482 Mahmoud and Saleh Clays and Clay Minerals

Table 1. Elemental analysis, BET surface area, surface acidity, and the concentration (ppm) of leached AP + of the activated
Jordanian bentonite and kaolin clay samples.
Clay composition (wt. %)J Bentonite 2
Kaolin 3
Bentonite 2 Kaolin 3 Activating acid l A P +] S.A. [H +] [AP*J

SiO2 52.9 60.6 Water 0 134 0.183 0

AI~O3 13.1 24.8 0.5 M HC1 5,9 229 0.823 5.7
Fe203 7.8 1.9 1.0 M HC1 6,4 242 0.800 6.2
MgO 5.3 0.2 2.0 M HC1 6,6 256 0.621 6.8
CaO 3.7 0.6 6.0 M HC1 9.1 269 0.415 8.2
Na20 0.8 0.4 12.0 M HCl 10.5 299 0.323 9.2
K20 1.8 1.6 1.0 M CH3COOH 1.4 163 0.456 1.4
TiO z 0.1 1.4 1.0 M H3PO 4 8.7 233 0.738 7.1
L.O.I. 4 13.1 8.5

Chemical composition of water-treated clay samples as determined by atomic absorption spectrometry.

2 --70% monmmrillonite; S.A.: surface area in m 2 g-l; [U+]: total surface acidity in mmol H + g-J, with Ho -< 4.8; [AP+]:
concentration of leached AI in ppm.
3 --90% kaolinite; S.A. -- 15 m 2 g-~, [H ~]: total surface acidity in mmol H + g-~ ~0.10, with Ho --< 4.8.
a Loss on ignition.

Catalytic reactions remaining -30% consists of non-clay minerals of

S a m p l e s (5.0 c m 3 e a c h ) of 2 - t e r t - b u t y l p h e n o l (Flu-
k a ) w e r e a d d e d w i t h a 1.0 g c a t a l y s t s a m p l e in a three-
n e c k r o u n d b o t t o m flask, e q u i p p e d w i t h a condenser,
a t h e r m o m e t e r , a n d a s e r u m c a p for s a m p l e r e m o v a l .
T h e flask was t h e n i m m e r s e d in a silicon oil b a t h a n d
the r e a c t i o n m i x t u r e w a s h e a t e d u n d e r reflux at 230~
S a m p l e s for analysis ( - 0 . 0 5 c m 3) were t a k e n f r o m the
r e a c t i o n m i x t u r e at 15 rain intervals, t h e n d i l u t e d w i t h
m e t h a n o l , a n d a n a l y z e d b y gas c h r o m a t o g r a p h y .
B E T analysis o f e a c h clay w a s m e a s u r e d b y nitro-
g e n a d s o r p t i o n u s i n g a glass a p p a r a t u s b u i l t a n d m o d -
ified for this p u r p o s e ( J o h n e a n d Severin, 1965). Also,
the B r o n s t e d surface acidity o f the s a m p l e s w a s deter-
m i n e d b y the a m i n e titration m e t h o d u s i n g several in-
dicators (Lucio, 1973).
Analysis
All r e a c t i o n s a m p l e s w e r e a n a l y z e d b y a P y e - U n i -
c a m gas c h r o m a t o g r a p h w i t h a F I D detector, a n d con-
n e c t e d to a n e l e c t r o n i c i n t e g r a t o r ( S p e c t r a - P h y s i c s ,
I n k - J e t ) i n t e r f a c e d to a computer. A n a l y s i s was per-
f o r m e d on a 1.5 m l o n g • 6 m m O.D. stainless steel
c o l u m n , p a c k e d w i t h 10% silicon E 3 0 a n d s u p p o r t e d
on silanized acid-washed diatomite "C" with a mesh
size o f 1 0 0 - 1 2 0 . H e l i u m carrier gas was p a s s e d at a
flow rate o f 45 c m 3 m i n -1. T h e injector, detector, a n d
o v e n t e m p e r a t u r e s were, 250, 300, a n d 150~ respec-
tively.
1H-NMR ( n u c l e a r m a g n e t i c r e s o n a n c e ) s p e c t r o s c o -
p y was u s e d to i d e n t i f y the i s o m e r i c f o r m s b y u s i n g
the c h e m i c a l shifts of the tert-butyl g r o u p in different
t e r t - b u t y l a t e d phenols.
RESULTS
C h e m i c a l a n a l y s i s s h o w e d that J o r d a n i a n b e n t o n i t e
c o n t a i n s - - 7 0 % m o n t m o r i l l o n i t e , w h i c h is the p r i n c i p a l
active c o m p o n e n t in this a c i d - c a t a l y z e d reaction. T h e
quartz, feldspar, a n d c a r b o n a t e s . M o n t m o r i l l o n i t e pos-
sesses b o t h B r o n s t e d a n d L e w i s acid sites, w h i c h are
r e s p o n s i b l e for its d e a l k y l a t i o n a n d t r a n s a l k y l a t i o n ac-
tivities ( G o n z a l e z et al., 1992). J o r d a n i a n k a o l i n c o n -
tains - 9 0 % k a o l i n i t e a n d - 1 0 % quartz. K a o l i n i t e is
catalytically active d u e to strong L e w i s acid sites (Be-
nesi, 1956). T h e s e clays also c o n t a i n s o m e o x i d e s o f
(periodic table) G I A , G I I A , a n d t r a n s i t i o n e l e m e n t s
(Table 1) that i n f l u e n c e t h e i r t h e r m a l stability a n d cat-
alytic properties (Tanabe, 1983).
Clay p r o p e r t i e s s u c h as surface area, s u r f a c e acidity,
a n d t h e r m a l stability v a r y w i t h c o m p o s i t i o n a n d / o r
structure. T h e s e properties are d e c i s i v e in e s t a b l i s h i n g
the catalytic b e h a v i o r o f t h e s e clays. F o r i n s t a n c e , the
B E T surface area of the w a t e r - t r e a t e d J o r d a n i a n b e n -
tonite is h i g h ( - - 1 3 4 m 2 g-~) a n d that treated w i t h 1.0
M HC1 is e v e n h i g h e r ( - 2 4 0 m 2 g z). B E T surface
area i n c r e a s e s w i t h the c o n c e n t r a t i o n o f the a c t i v a t i n g
acid. S u c h a n i n c r e a s e in surface area u p o n acid treat-
m e n t is d u e to a n i n c r e a s e in p o r o s i t y c a u s e d b y leach-
ing A1203 f r o m the clay m i n e r a l ( T k a c et al., 1994;
K o m a d e l et al., 1997). T h i s surface area b e c o m e s v e r y
h i g h at h i g h acid c o n c e n t r a t i o n s ( N e w m a n a n d B r o w n ,
1987) a n d p r o v i d e s a relatively s u i t a b l e surface for
a c i d - c a t a l y z e d reactions. J o r d a n i a n kaolin, s i m i l a r to
all kaolinitic clays, h a s a l o w B E T surface area ( - 1 5
m 2 g-l), b u t p o s s e s s e s strong L e w i s acid sites m a k i n g
it a suitable c a t a l y s t in a c i d - c a t a l y z e d reactions.
T a b l e 1 s h o w s surface acidity m e a s u r e m e n t s u s i n g
several i n d i c a t o r s at Ho --< 4.8 h a v e total B r o n s t e d -
surface acidity v a l u e s for b e n t o n i t e s a m p l e s ( 0 . 1 8 -
0.82) that are m u c h h i g h e r t h a n t h o s e o f k a o l i n s a m -
ples (--0.10). In the d e b u t y l a t i o n r e a c t i o n o f 2-tert-
b u t y l p h e n o l , all s a m p l e s g a v e the s a m e p r o d u c t s b u t
at d i f f e r e n t rates (Tables 2 a n d 3).
DISCUSSION
T h e p r e s e n c e o f constituent m e t a l o x i d e s in t h e clay
m i n e r a l d e c r e a s e s the B r o n s t e d surface acidity a n d
Vol. 47, No. 4, 1999 Effect of acid activation on some Jordanian clays 483

Table 2. De-tert-butylation activity of different activated Jordanian bentonite samples in the debutylation of 2-tert-butylphenol
at 230~ where C % conversion of 2-tert-butylphenol and S = debutylation selectivity. ~
HCI conc. (M) H3PO4 CH3COOH
Dist.
0.50 1.0 2.0 6.0 12.0 1.0 M 1.0 M water
Time
(h) C S C S C S C S C S C S C S C S

0.25 36 40 68 30 40 49 30 58 30 60 63 26 43 47 28 78
0.50 68 36 90 33 64 40 42 56 38 55 86 28 66 39 44 72
1.0 80 28 95 44 90 20 73 42 70 46 92 40 8l 33 62 64
1.5 87 24 96 52 93 18 82 40 83 39 95 44 88 30 70 62
2.0 90 22 97 58 95 20 86 35 84 34 96 43 91 28 77 55
Butyl. 2 -25% --8% --22% -22% --23% -11% --22% -20%

~Debutylation selectivity = (% phenol)/(% 4-tert-butylphenol) • 100%.

z Butyl. - average percentage of 2,4-di-tert-butylphenol at conversions ->50%.

thus affects the catalytic d e b u t y l a t i o n activity and se-
lectivity. Therefore, the studied clays w e r e p r e t r e a t e d
w i t h acids o f different strengths and various c o n c e n -
trations to i m p r o v e their surface acidity. F o r e x a m p l e ,
strong acids such as H2SO 4 or HC1 m a y g e n e r a t e n e w
surface acid sites quickly, but they m a y also cause
e x t e n s i v e leaching o f A1203 f r o m the clay mineral,
t h e r e b y leading to structure c o l l a p s e ( N e w m a n and
B r o w n , 1987; R u p e r t et aL, 1987; Lussier, 1991; M o -
k a y a and Jones, 1995). W e a k acids m a y p r e s e r v e the
clay structure, but are less e f f e c t i v e in g e n e r a t i n g sur-
face acid sites.
Tables 2 and 3 and Figures 1 and 2 s h o w the per-
c e n t a g e c o n v e r s i o n o f 2 - t e r t - b u t y l p h e n o l b y acid-treat-
ed b e n t o n i t e and kaolin s a m p l e s at d i f f e r e n t time in-
tervals. H i g h - p e r c e n t a g e c o n v e r s i o n s indicate high
catalytic activity o f the sample, and thus greater acid
activation. It appears that 1 M HC1 is the b e s t acid
solution for the activation o f b o t h s a m p l e s ; after 30
m i n o f reaction, 90 and 92% c o n v e r s i o n s w e r e ob-
tained for bentonite and kaolin, respectively. The ef-
f e c t i v e n e s s o f HC1 c l a y - a c t i v a t i o n m a y b e b e c a u s e
HC1 is a strong acid, w h i c h c o m p l e t e l y dissociates in
w a t e r to H + and C l - i o n s . A l s o , the p r o d u c e d metal
c h l o r i d e s due to this acid t r e a t m e n t are c o m p l e t e l y sol-
uble in water, and r e m o v e d by the p r e t r e a t m e n t pro-
cess. A l t h o u g h HC1 is a strong acid, it has not c a u s e d
significant deterioration o f the clay structure as indi-
cated b y the B E T surface area m e a s u r e m e n t data (Ta-
ble 1). O n the other hand, acetic acid is a w e a k acid
(pH -- 2.4 for 1 M ) and h e n c e is far less e f f e c t i v e at
activation o f the clays c o m p a r e d to HC1 o f the s a m e
c o n c e n t r a t i o n . A c o n v e r s i o n o f - - 6 6 % after 30 m i n
r e a c t i o n was o b s e r v e d for b o t h s a m p l e s w h e n treated
w i t h 1 M acetic acid. M o r e o v e r , p h o s p h o r i c acid w a s
m o r e e f f e c t i v e than acetic acid and was c o m p a r a b l e to
HC1. This m a y be attributed to the p h o s p h o r i c acid
b e i n g stronger (pH -- 1 for 1 M ) than acetic acid, but
it is still w e a k e r than HC1. Also, free p h o s p h a t e ions
(PO43-) f o r m i n s o l u b l e c o m p l e x e s with the l e a c h e d
metal ions, and h e n c e d e c r e a s e the clay m i n e r a l activ-
ity (Lussier, 1991).
It w a s also f o u n d that the 1 M HC1 is the b e s t so-
lution for this acid activation p r o c e s s , and as c o n c e n -
tration i n c r e a s e s a b o v e 1 M the activity o f t h e s e s a m -
ples d e c r e a s e s . Thus, the activity is directly related to
surface acidity. F o r e x a m p l e , the 12 M H C l - t r e a t e d
b e n t o n i t e s a m p l e has a l o w B r o n s t e d s u r f a c e acidity
(0.323) and c o n s e q u e n t l y , a l o w p e r c e n t a g e c o n v e r s i o n
(38%) after 30 m i n o f reaction. W h e r e a s , as g i v e n in
Tables 1 a n d 2, the b e n t o n i t e s a m p l e treated w i t h 1 M
HC1 has m u c h greater s u r f a c e acidity and p e r c e n t a g e

Table 3. De-tert-butylation activity of different activated Jordanian kaolin samples in the debutylation of 2-tert-butylphenol
at 230~ where C = % conversion of 2-tert-butylphenol and S = debutylation selectivity. ~
HC1 conc. (M) H3PO4 CH3COOH
Dist.
0.50 1.0 2.0 6.0 12.0 1.0 M 1.0 M water
Time
(h) C S C S C S C S C S C S C S C S

0.25 78 22 80 20 52 38 32 60 22 64 80 27 24 52 20 82
0.50 90 15 92 25 70 31 51 47 43 52 89 30 65 37 35 71
1.0 95 15 95 40 88 23 82 26 76 29 94 45 83 29 50 56
1.5 96 19 96 48 93 23 89 22 84 24 96 48 89 32 58 51
2.0 96 28 97 50 94 25 91 20 87 24 97 50 92 31 67 46
Butyl. 2 --15% --8% --20% --24% --26% --8% --20% --22%

1 Debutylation selectivity = (% phenol)/(% 4-tert-butylphenol) • 100%.

2 Butyl. = average percentage of 2,4-di-tert-butylphenol at conversions ->50%.
484 Mahmoud and Saleh Clays and Clay Minerals

80-

60-
.=

;J
I III1~" I -v-6~ u'cl
1 II/lr I -*-t=""c' =~ 4 0 -
- - I I - - 0.50 M HCI
- - O - - 1.0 M HCI
2 - - X - - 1 .o M CH3COOH
- - A - - 2 . 0 M HCI
- - V - - 6 . 0 M HCl
12.0 M HCI
20 - - + - - 1.0 M H3PO4
- - X - - 1.0 M CH3COOH
- - ~ - - Dist. Water
0.00 0.25 0.50 0.75 1.00 1.25 1.50 1.75 2.00 2.25
Time (hr)
Figure 1. De-tert-butylation activity of Jordanian bentonite 0 84
samples treated with different acid solutions. 0.00 0.25 0.50 0.75 1.00 1.25 1.50 1.75 2.00 2.25
Time (hr)

Figure 2. De-tert-butylation activity of Jordanian kaolin

conversion values (0.80 and 90%, respectively). Ex-
tensive leaching of the constituent oxides, especially
A1203 and Fe203, m a y have caused this effect. Evi-
dence of leached oxide minerals is found in the A P +
data of the filtrate of the acid-treated bentonite and
kaolin samples (Table 1). W h e n the concentration of
HC1 was increased f r o m 0.50 M to 12.0 M, A13+ con-
centration increased f r o m 5.9 and 5.7 p p m to 10.5 and
9.2 ppm, respectively. Moreover, the percentage con-
version for the 12.0 M HCl-treated samples was c o m -
paratively low at short reaction times, but at longer
times conversions for all samples b e c o m e m o r e simi-
lar. This suggests that the structures of these samples
were greatly affected by the high concentration of the
acid used. Such a change is consistent with changes
observed in the physical properties of the clays. Color
changed f r o m light yellowish b r o w n to dark brown,
and the B E T surface area o f the bentonite increased
f r o m --134 m 2 g 1 to --300 m 2 g 1 upon treatment with
12.0 M HC1. Such an increase in B E T surface area
caused by extensive loss of a l u m i n u m was not asso-
ciated with an increase, but with a decrease in catalytic
samples treated with different acid solutions.
carbocation (Greensfelder e t al., 1949). The partial re-
lease of isobutene was consistent with stoichiometric
calculations based on the collected v o l u m e s of this gas
over water, and is in agreement with other studies (Gill
et al., 1998). Second, the butylation of phenol 2 at the
para position to produce 4-tert-butylphenol 3. Third,
the butylation of 2-tert-butylphenol 1 to produce 2,4-
di-tert-butylphenol 4.
The ability to produce c o m p o u n d s 2, 3, and 4 de-
pends on the activity of the clay sample, as well as on
the type and relative population of the acid sites (Sher-
tukde e t al., 1993). M o r e active clay samples are ex-
+ILl+
O)
! 2_
OH

activity (Table 1).

The acid-activated samples b e h a v e d similarly with d +(c-=,)3C -~- + (2)
respect to the products f o r m e d and with respect to se-
lectivity in the conversion of 2-tert-butylphenol. Phe- 3

nol and 4-tert-butylphenol were the major products,

whereas 2,4-di-tert-butylphenol was obtained in minor
quantities. T h e s e products are a result of a reaction ~. (3)

that involves three possible pathways (Figure 3). First,

the debutylation of the substrate 1 occurs to produce 4

phenol 2 and isobutene, which partly b e c o m e s ad- Figure 3. Mechanism of the de-tert-butylation of 2-tert-bu-
sorbed on the clay acid sites, thereby forming tert- tylphenol by Jordanian bentonite and kaolin samples.
Vol. 47, No. 4, 1999 Effect of acid activation on some Jordanian clays
80
9 050 M HCI
9 10 M CH3COOH
9 60 M HC1
70 ~ 9 12 M HCI
? Dist.Water
.~
.~. 50
40
30,
20,
20 40 60 80 100
% Conversion
Figure 4. The effect of conversion on selectivity of some
Jordanian bentonite samples treated with different acid solu-
tions. (Data points from left to right are, respectively, at 0.25,
0.50, 1.0, 1.5, and 2.0 h)
pected to involve all reaction pathways to yield ini-
tially all products at relatively high concentrations.
However, as the percentage conversion increases,
m o r e debutylation products are obtained (i.e., the de-
butylation of 3 and 4) thus showing a higher debuty-
lation selectiv]]y. For example, the 1 M H C l - a c t i v a t e d
bentonite sample shows initial and final debutylation
selectivities of 30 and 58%, respectively, but only 8%
butylation selectivity (Table 2). Consequently, this
bentonite possessed initially low debutylation selectiv-
ity, but as the percentage conversion of 2-tert-butyl-
phenol increases, the concentration o f products 3 and
4 increases also. These products are then debutylated
to produce 2, resulting in increasing the debutylation
selectivity.
Contrary to the most active samples, the initially
high debutylation selectivity of the less active samples,
such as the water-treated samples and the samples
treated with 1 M acetic acid or with high concentra-
tions o f HC1, decreases with both time and percentage
conversion (Tables 2 and 3; Figure 4). Since the con-
centration of phenol and the concentration of the in-
termediate tert-carbocation increase with time, reac-
tions (2) and (3) b e c o m e highly competitive. This
leads to a l o w e r debutylation selectivity after 2 h of
reaction. During this time, the clay sample m a y h a v e
b e c o m e deactivated so that it cannot debutylate prod-
ucts 3 and 4. Thus, this variation in selectivity trend
is b e i i e v e d t-o be generally caused by the variation in
activity. The selectivity is a function of percentage
conversion, where at low conversions high debutyla-
485
tion selectivities were observed, and visa v e r s a (Figure
4). Such a decreasing debutylation selectivity, rela-
tively high butylation, and high isomerization selectiv-
ities are possibly due to low activity.
CONCLUSIONS
M i l d acid treatment is b e l i e v e d to increase the de-
butylation activity and selectivity of Jordanian benton-
ite and kaolin samples through the i m p r o v e m e n t of
their surface acidity. In contrast, treatment with strong
acids of high concentrations, e v e n though the B E T
surface area o f the clay increases, has an adverse effect
on the catalytic properties of the clays. Such effect is
caused by the extensive leaching of the metal oxides.
ACKNOWLEDGMENTS
The authors acknowledge the fnancial support generously
provided by the Deanship of Scientific Research and Gradu-
ate Studies at Yarmouk University and by the EEC.
REFERENCES
A1-No'aimei, M.Z. (1997) The effect of acid and thermal pre-
treatment on the catalytic activity of Jordanian bentonite.
M.S. thesis, Yarmouk Univ., Irbid, Jordan, 135 pp.
Auer, H. and Hofmann, H. (1993) Pillared clays: Character-
ization of acidity and catalytic properties and comparison
with some zeolites. Applied Catalysis A; General, 97, 23-
38.
Benesi, H.A. (1956) Acidity of catalyst surfaces I: Acid
strength from colors of adsorbed indicators. Journal o f the
American Chemical Society, 78, 5490-5494.
Chitnis, S.R. and Sharma, M. (1997) Industrial application of
acid-treated clays as catalysts. Reactive and Functional
Polymers, 32, 93-115.
Clark, J.H., Macquarrie, D.J., and Duncan, J. (1997) Hetero-
geneous catalysis in liquid phase transformations of im-
portance in the industrial preparations of fine chemicals.
Organic Process Research and Development, 1, 149-162.
Corma, A. and Wojciechowski, B.W. (1985) The chemistry
of catalytic cracking. Catalysis Reviews: Science and En-
gineering, 27, 29-150.
Gill, R., Petkovic, L.M., and Larsen, G. (1998) Interaction of
isobutene with the surface of different solid acids. Journal
o f Catalysis, 179, 56-63.
GaD, Z. and Jiao, J. (1989) Catalytic performance of pillared
interlayered clay molecular sieves with high thermal sta-
bility. Wuli Hauxue Xuebao, 5, 178-184.
Gonzalez, E, Pessquera, C., Benito, I., and Mendio, O.Z.
(1992) Synthesis and characterization of A1-Ga pillared
clays with high thermal and hydrothermal stability. Inor-
ganic Chemistry, 31, 727-731.
Greensfelder, B.S., Voge, H.H., and Good, G.M. (1949) Cat-
alytic cracking of pure hydrocarbons. Industrial and En-
gineering Chemistry, 38, 1033 1040.
Johne, R. and Severin, D. (1965) Die oberflachenmessung mit
dem areameter. Chemie-lngenieur-Technik, 37, 57-61.
Komadel, P., Janek, M., Madejova, J., Weeks, A., and Breen,
C. (1997) Acidity and catalytic activity of mildly acid-treat-
ed Mg-rich rnontmorillonite and hectorite. Journal o f The
Chemical Society Faraday Transactions, 93, 4207-4210.
Li, T.S. and Jin, T.S. (1996) Organic reactions catalyzed by
montmorillonite clays. Youji Huaxue, 16, 385-402.
LuciD, E (1973) Comparison of the methods for the deter-
mination of surface acidity of solid catalysts. Catalysis Re-
views: Science and Engineering, 8, 65-115.
486 Mahmoud and Saleh
Lussier, R.J. (1991) A novel clay-based catalytic material:
Preparation and properties. Journal of Catalysis, 129, 225-
237.
Mokaya, R. and Jones, W. (1995) Pillared clays and pillared
acid-activated clays: A comparative study of physical, acid-
ic and catalytic properties. Journal of Catalysis, 153, 7 6 -
85.
Newman, A.C.D. and Brown, G. (1987) The chemical con-
stitution of clays. In Chemistry of Clays and Clay Minerals',
A.C.D. Newman, ed., Longman, Birmingham, Alabama,
237-274.
Ravichandran, J., Lakshmanan, C.M., and Sivasankar, B.N.
(1996) Acid-activated montmorillonite and vermeculite
clays as dehydration and cracking catalysts. Reaction Ki-
netics and Catalysis Letters, 59, 301-308.
Rupert, J.R, Granquist, W.T., and Pinnavaia, T.J. (1987) Cat-
alytic properties of clay minerals. In Chemistry of Clays
and Clay Minerals, A.C.D. Newman, ed., Longman, Bir-
mingham, Alabama, 275-318.
Clays and Clay Minerals
Saleh, S.A. and Mahmoud, S.S. (1998) Catalytic debutylafion
of tert-butylphenols by some natural clays. Reaction Ki-
netics and Catalysis Letters', 64, 373-380.
Shertukde, EV., Hall, W.K., Dereppe, J.M., and Marcelin, G.
(1993) Acidity of H-Y Zeolites: Role of extralattice alu-
minum. Journal of Catalysis, 139, 468-481.
Tanabe, K. (1983) Solid acid and base catalysts. In Catalysis:
Science and Technology, J.R. Anderson, ed., Academie-
Verlag, Berlin, 231-273.
Tkac, I., Komadel, P., and Muller, D. (1994) Acid-treated
montmorillonites: A study by Si-29 and AI-27 MAS NMR.
Clay Minerals', 29, 11-19.
Upadhya, T.T., Daniel, T., Sudalai, A., Ravindraanthan, T., and
Sabu, K.R. (1996) Natural kaolinitic clay: A mild and ef-
ficient catalyst for the tetrahydropyranylation and trimeth-
ylsilylation of alcohols. Synthetic Communications, 26,
4539-4544.
(Received 30 March 1998; accepted 15 February 1999;
Ms. 98-038)