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CHAPTER 5

TERT-BUTYLATION OF PHENOL WITH

TERT-BUTYL ALCOHOL

5.1 INTRODUCTION

Alkylation of phenol with tert-butyl alcohol (TBA) is an

industrially important reaction. The product, 4-tert-butylphenol (4-TBP), is
employed in the production of a variety of phenol–formaldehyde resins which
are applied as binders in surface coatings, lacquers and varnishes (Chandler et
al 1997). 2-tert-Butylphenol (2-TBP) is used as a raw material in the
production of antioxidants and agrochemicals (Mathew et al 2004). The other
product, 2,4-di-tert-butylphenol (2,4-DTBP), is an important feedstock for the
production of antioxidants, ultraviolet absorbers and heat stabilisers for
polymeric materials (Knop and Pilato 1985). Several catalysts have been
reported for tert-butylation of phenol which include Lewis acids such as AlCl3
and BF3, Brönsted acids such as H3PO4, H2SO4, HF, HClO4 (Carlton 1948),
cation exchange resins, mesoporous materials (Ushanandhini et al 2004 and
Sakthivel et al 2002), zeolites (Zhang et al 2002), supercritical and near
supercritical water (Chandler et al 1997 and Sato et al 2001) and ionic liquids
(Shen et al 2004).

The major drawbacks of homogeneous catalysts are their

hazardous nature and tedious work-up procedure involved in the separation of
catalyst from the reaction mixture after completion of the reaction. In order to
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overcome the drawbacks attempts have been made to use molecular sieves as
catalysts (Corma 1997, Zhang et al 1998). Zhang et al (2002) studied the
tert-butylation of phenol with TBA over zeolite HM. They reported that
strong acid sites are favourable for the formation of 2,4-DTBP whereas weak
and medium acid sites are advantageous for the formation of 4-TBP.

5.2 TERT-BUTYLATION OF PHENOL OVER MAPO-36 AND

Zn2+, Fe3+, La3+ AND Ce3+ ION-EXCHANGED MAPO-36

The vapour phase tert-butylation of phenol with tert-butyl alcohol

was investigated over MAPO-36 and Zn, Fe, La and CeMAPO-36. In order to
optimize the reaction conditions for the production of 4-TBP, the influence of
temperature, catalyst, feed ratio, WHSV and time on stream were studied. The
study of feed ratio (phenol:tert-butyl alcohol) has revealed inadequacy of 1:1
and 1:2 to effect alkylated products.

5.2.1 Effect of Temperature over CeMAPO-36

The effect of temperature on phenol conversion and products

selectivity was studied over CeMAPO-36 and the results are presented in
Table 5.1. The major products were found to be 2-tert-butylphenol (2-TBP),
4-tert-butylphenol (4-TBP) and 2,4-di-tert-butylphenol (2,4-DTBP). The
phenol conversion increased from 200 to 300 ºC and then decreased. The
decrease in the phenol conversion above 300 ºC is due to coke formation. The
formation of coke was confirmed physically. Such coke deposits were mainly
due to the formation of polyalkylated phenolics and polybutenes (Liu et al
1997). Alkylation of phenol occurred through dissociative chemisorption of
phenol on MO+ and the resulting phenolic proton is transferred to its nearby
bridging oxygen (Shanmugapriya et al 2004 and Vishnupriya et al 2008a).
tert-Butyl alcohol is chemisorbed on the protonic sites to form tert-butyl
cation which then undergoes electrophilic attack at o- or p- position of the
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adjacent chemisorbed phenol yielding 2-TBP or 4-TBP (Scheme 5.1). This is

the main route for the formation of 2-TBP and 4-TBP. Phenol can also be
chemisorbed on the Brönsted acid sites of the catalyst and there may be
tert-butyl cations close to it remaining as charge compensating cations. The
reaction between them leads to the formation of 2-TBP and 4-TBP as shown
in Scheme 5.2.

Table 5.1 Effect of temperature on phenol conversion and products

selectivity
Temperature Conversion Selectivity (%)
(°C) (%) 2-TBP 4-TBP 2,4-di-TBP Others
200 32.7 30 47 17 6
250 44.3 24 54 14 8
300 50.2 13 69 9 9
350 47.0 12 65 7 16
400 40.5 9 58 6 27
Reaction conditions: catalyst: CeMAPO-36; feed ratio: 1:1; WHSV: 2.80 h-1

It is indirectly evident that the formation of 4-TBP may occur by

the reaction between free phenol in the vapour phase and chemisorbed
tert-butyl cation. Mathew et al (2004) also reported the formation of 4-TBP
and 2,4-DTBP due to the attack of phenol by tert-butyl cation in the adsorbed
state as well as in the gaseous state. At lower temperatures phenol as well as
alcohol may be clustering around the protonic site which leads to slow
electrophilic reaction. The clusters are lost gradually with increase in
temperature, thus favouring enhanced free phenol concentration for
electrophilic attack at the p-position. Although o-position of phenol is not
sterically crowded for electrophilic reaction, substitution at the o-position is
slightly less due to repulsion between the positive charge on the tert-butyl
cation and the positive charge on the phenolic oxygen (Scheme 5.3).
 OH It is a free molecule inside
O the pores of MAPO-36

+
MO
+
MO H
O + OH
2- 2- O
Mg P Mg P
+

3+ 3+ 3+
M = La , Ce or Fe

O
OH
MO
+ +
MO
+
2- O 2- O
P P
Mg Mg + +
3+ 3+ 3+
3+ 3+ 3+
M = La , Ce or Fe
M = La , Ce or Fe

Scheme 5.1 tert-Butylation of phenol over MO + in M3+ ion-exchanged MAPO-36

97
 OH
OH OH OH
+ +
H H
+ + +
2- O 2- O
Mg P Mg P +
Minor

Major

Scheme 5.2 tert-Butylation of phenol over Brönsted acid sites in MAPO-36

..
HO +
.. HO Other structures
(-)

Scheme 5.3 Resonance structures of phenol

98
 99

Although selectivity to 4-TBP was expected to increase with increase

in temperature, decrease in the selectivity was observed at 350 and 400 ºC. The
decrease in the selectivity at higher temperatures is largely due to its conversion
to other products. The selectivity to 2,4-DTBP also decreased with increase in
temperature. This is also due to its conversion to other products, mainly
polyalkylated phenolics. 2,4-DTBP may be formed by the reaction between
chemisorbed phenol and closely adsorbed tert-butyl cations. Kurian and Sugunan
(2006) and Huang et al (2006) have reported requirement of strong acid sites for
the formation of 2,4-DTBP in the alkylation of phenol with tert-butyl alcohol.
However, di-alkylation depends only on the availability of tert-butyl cation for
the monoalkylated products. Hence, di-alkylated products could be formed even
with weak acid sites. Even after coke formation, the pores are large enough to
form other products with high selectivity at high temperatures.

5.2.2 Effect of Catalysts

The same reaction was also studied over calcined MAPO-36,

ZnMAPO-36, FeMAPO-36, LaMAPO-36 and CeMAPO-36 catalysts in order to
find out the better catalyst. The results are presented in Table 5.2. MAPO-36 is
found to be the least active catalyst. This observation clearly established that the
reaction is largely controlled by Lewis acid sites. Further, chemisorption of
phenol on the Lewis acid sites appeared to be more favourable than on the
Brönsted acid sites. Among the ion-exchanged MAPO-36, CeMAPO-36 is the
most active catalyst. Since CeO+ sites are more active than LaO+ sites, the former
is considered to assist better dissociative adsorption of phenol. Ce3+ (0.102 nm) is
smaller in size than La3+ (0.12 nm) due to lanthanide contraction. This is
suggested to be the cause for its higher Lewis acidity (Vishnupriya et al 2008).
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Table 5.2 Effect of catalyst on phenol conversion and products selectivity

Conversion Selectivity (%)

Catalyst
(%) 2-TBP 4-TBP 2,4-DTBP Others
MAPO-36 25.0 23 52 13 12
ZnMAPO-36 28.2 24 56 12 8
FeMAPO-36 33.0 18 60 12 10
LaMAPO-36 38.5 15 62 14 9
CeMAPO-36 50.2 13 69 9 9
Reaction conditions: temperature: 300 °C; feed ratio: 1:1; WHSV: 2.80 h -1

The selectivity to 4-TBP is higher than other products over all the
catalysts. But FeMAPO-36, LaMAPO-36 and CeMAPO-36 showed higher
4-TBP selectivity than ZnMAPO-36. The presence of both strong and weak acid
sites in ZnMAPO-36 is the cause for reduced selectivity to 4-TBP. Hence Fe, La
and CeMAPO-36 with more number of weak acid sites could be considered as
better catalysts than others (Vishnupriya et al 2008).

5.2.3 Effect of Feed Ratio over CeMAPO-36

The reaction was performed with 1:1, 1:2 and 1:3 feed ratios over
CeMAPO-36 at 300 ºC and the results are shown in Table 5.3. The conversion is
found to be higher at 1:2 than other feed ratios. The less conversion with 1:3 is
due to suppression of chemisorption of phenol in the presence of excess
tert-butyl alcohol. Such observation has already been reported in the literature
(Corma et al 1994). In addition, selectivity to 2-TBP, 2,4-DTBP and others are
suppressed to a large extent. This suggests that polyalkylated products could be
avoided by using feed containing less amount of tert-butyl alcohol. The effect of
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dilution of phenol may also exist even with the feed ratio 1:2. But there are
enough tert-butyl cations on the Brönsted acid sites which can attack free phenol
thus yielding 4-TBP as the major product. The formation of 2-TBP and
2,4-DTBP is due to chemisorption of phenol on the Lewis acid sites. Phenol may
be preferentially chemisorbed with 1:1 feed ratio which will enhance the
selectivity to 2-TBP, 2,4-DTBP and others. The less selectivity to 4-TBP also
supports this view. This study concludes that phenol can be selectively alkylated
at p-position with 1:2 feed ratio.

Table 5.3 Effect of feed ratio on phenol conversion and products selectivity

Phenol:tert-Butyl Conversion Selectivity (%)

alcohol (%) 2-TBP 4-TBP 2,4-DTBP Others
1:1 50.2 13 69 9 9
1:2 59.8 8 92 0 0
1:3 32.7 11 73 7 9
Reaction conditions: catalyst: CeMAPO-36; temperature: 300º C

5.2.4 Effect of WHSV on Phenol Conversion and Products Selectivity

The effect of WHSV on phenol conversion and products selectivity

was studied over CeMAPO-36 with a feed ratio 1:2. The effect of WHSV on
phenol conversion is depicted in Figure 5.1. The conversion decreased with
increase in WHSV due to rapid diffusion of reactants. The selectivity to 2-TBP
decreased while the selectivity to 4-TBP slightly increased with increase in
WHSV. Hence it is concluded that the selective formation of 4-TBP required
reaction between free phenol and tert-butyl cation on the catalyst surface.
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100

90

80

Conversion of phenol (%) 70

60

50

40

30

20

10

0
1 2 3 4 5 6
-1
WHSV (h )
Figure 5.1 Effect of WHSV on phenol conversion

5.2.5 Effect of Time on Stream

The effect of time on stream was studied for 6 h over CeMAPO-36 at

300 °C with 1:2 feed ratio and WHSV 2.81 h -1 and the results are depicted in
Figure 5.2. The conversion decreased gradually with increase in time on stream
and at the end of 6 h stream only 25 % conversion is observed. The selectivity to
2-TBP increased up to 4 h, remained steady between 4 th and 5th hours and
decreased thereafter, whereas the selectivity to 4-TBP decreased rapidly in the
initial period of time on stream. This is due to enhanced initial activity on the
Lewis acid sites followed by deactivation at the expense of rapid accumulation of
reaction products and intermediates (Mavrodinova et al 2004a). Thus the
deactivation of the catalyst at longer hours of time on stream may be due to
accumulation of reaction products on the active sites and blocking of Lewis acid
sites by coke (Vishnupriya et al 2008a). 2,4-DTBP selectivity increased with
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increase in time on stream due to conversion of monoalkylated products to

dialkylated products such as 2,4-DTBP.
120
Conversion of phenol
110
Selectivity of
100 2-TBP
4-TBP
Conversion and Selectivity (%)

90
2,4-Di-TBP
80
Other products
70

60

50

40

30

20

10

0
1 2 3 4 5 6

Time (h)
Figure 5.2 Effect of time on stream on phenol conversion and products
selectivity over CeMAPO-36

5.3 CONCLUSION

Vapour phase tert-butylation of phenol over MAPO-36 and Zn2+, Fe3+,

La3+ and Ce3+ ion-exchanged MAPO-36 revealed that CeMAPO-36 is more
active than other catalysts. The higher catalytic activity towards phenol
conversion and 4-TBP selectivity in CeMAPO-36 is due to the presence of
highly Lewis acidic CeO+ sites. High selectivity to 4-TBP is obtained with
considerable conversion of phenol at 300 °C with 1:2 feed ratio (phenol:tert-
butyl alcohol) and 2.81 h–1 WHSV. Thus the ion-exchange of MAPO-36 with
trivalent metal ion in general and rare earth metal ions in particular is a useful
modification in order to get catalytically significant material
(Vishnupriya et al 2008a).