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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
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.
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
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%
thus affects the catalytic d e b u t y l a t i o n activity and se- cess. A l t h o u g h HC1 is a strong acid, it has not c a u s e d
lectivity. Therefore, the studied clays w e r e p r e t r e a t e d significant deterioration o f the clay structure as indi-
w i t h acids o f different strengths and various c o n c e n - cated b y the B E T surface area m e a s u r e m e n t data (Ta-
trations to i m p r o v e their surface acidity. F o r e x a m p l e , ble 1). O n the other hand, acetic acid is a w e a k acid
strong acids such as H2SO 4 or HC1 m a y g e n e r a t e n e w (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
surface acid sites quickly, but they m a y also cause activation o f the clays c o m p a r e d to HC1 o f the s a m e
e x t e n s i v e leaching o f A1203 f r o m the clay mineral, 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
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 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
B r o w n , 1987; R u p e r t et aL, 1987; Lussier, 1991; M o - 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
k a y a and Jones, 1995). W e a k acids m a y p r e s e r v e the 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
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- HC1. This m a y be attributed to the p h o s p h o r i c acid
face acid sites. b e i n g stronger (pH -- 1 for 1 M ) than acetic acid, but
Tables 2 and 3 and Figures 1 and 2 s h o w the per- it is still w e a k e r than HC1. Also, free p h o s p h a t e ions
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- (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
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- 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-
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 ity (Lussier, 1991).
catalytic activity o f the sample, and thus greater acid It w a s also f o u n d that the 1 M HC1 is the b e s t so-
activation. It appears that 1 M HC1 is the b e s t acid lution for this acid activation p r o c e s s , and as c o n c e n -
solution for the activation o f b o t h s a m p l e s ; after 30 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 -
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- ples d e c r e a s e s . Thus, the activity is directly related to
tained for bentonite and kaolin, respectively. The ef- 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
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 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
HC1 is a strong acid, w h i c h c o m p l e t e l y dissociates in (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
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 (38%) after 30 m i n o f reaction. W h e r e a s , as g i v e n in
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- 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
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- 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%
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)
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 485
30,
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.
20,
20 40 60 80 100
% Conversion
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