Indian Journal of Chemical Technology

Vol. 3, November 2001, pp. 469-472

Isopropylation of naphthalene over large pore zeolites
lshwarya Mathew, Smita Sabneb, S Mayadevib*, SA Pardhyb & S Sivasankerb
Department of Applied Chemistry, Cochin University of Science and Technology, Cochin 682 022, India
b National Chemical Laboratory, Pune 411 008, India
Received 22 November 2000; revised 31 May 2001; accepted 8 June 2001
Isopropylation of naphthalene with isopropanol (IPA) proceeds at 200C over the large pore zeolites HY, H-
Mordenite and REY in the presence of N
2
. Over conversion is more in N
2
than when cyclohexane is used as solvent or
in absence of N
2
. Conversions and selectivities to diisopropyl naphthalenes fall in the sequence > REY > HM > HY, but
2,6: 2,7 ratio is greatest with HM. With conversion is maximum at 200C, and increasing the IPA : naphthalene ratio
leads to deactivation of the catalyst.
Isopropylation of naphthalene to produce 2,6-diiso-
propylnaphthalene (2,6-DIPN) is a commercially
important reaction. 2,6-DIPN is an important inter-
mediate for making advanced new polymer materials.
Isopropylation of naphthalene has been studied in
both the liquid I-J and gas
4

5
phases over zeolite
catalysts, with the aim of achieving high yield of 2,6-
DIPN. Different alkylating agents, such as propene
6
,
isopropanoe and isopropyl bromide
1
have been used
for this reaction over zeolite catalysts. Song and
Kirbl reported that the 2,6-/2,7-DIPN ratio was
dependent on the alkylating agent used. They
obtained a 2,6-/2,7-ratio between 2 and 3 using
isopropanoUpropene, whereas an earlier study
7
reported 2,6- and 2,7- in equal proportions when
isopropyl bromide was used. High
isopropylnaphthalene; 2-isopropylnaphthalene) selec-
tivity was observed for isopropylation of naphthalene
when HM (H-Mordenite) was used as the catalyst. It
has been shown by several research groups
1

8
that
2,6-DIPN can be obtained with high selectivities over
HM by alkylation of naphthalene with propene and 2-
propanol. The preferential formation of 2,6-DIPN
within the HM framework may be due to the
difference in diffusion kinetics between the
dialkylnaphthalenes
9
Song and co-workers
10
-
12
explained the improvement in selectivity on
dealumination of mordenite to be due to reduced
contribution of external acid sites and reduction of
*For correspondence (Fax: +91-(0)20-589 3041.
E-mail : maya@che.ncl.res.in)
unit cell dimensions
13
'
14
Poisoning of external acid
sites by silylation
7
, by adsorption of water
13
, and by
deposition of cerium oxide
13
, was found to enhance
the selectivity of HM for 2,6-DIPN formation.
Though considerable literature is available on the
isopropylation of naphthalene over zeolite catalysts,
studies using isopropyl alcohol or bromide as
alkylating agents have been carried out in the
presence of an organic solvent
1

12
The study of
alkylation in the absence of organic solvents is of
interest as it reduces the load on down stream
separation. The present work has been undertaken to
study the isopropylation of naphthalene on different
zeolites in the absence of organic solvent. Activity of
different zeolites has been compared for the
isopropylation reaction and the selectivity for 2,6-
DIPN. The influences of reaction parameters on the
isopropylation reaction have also been studied.
Experimental Procedure
The of zeolites beta Y and
mordenite (M) were obtained from PQ Corp., USA.
The zeolites were converted into the H-forrn by
calcination at 450C for 4h. The calcined powders
were pressed into pellets, crushed and sieved to obtain
particles of size, 0.8 - 2 mm. A commercial sample of
REY (15% RE
2
0
3
) was also used in the studies. The
sized zeolite particles were activated at 450C for 4h
before use. XRD patterns of the zeolites matched well
with their standard patterns. Compositional analyses
of the zeolites were done by chemical methods.
470
INDIAN J. CHEM. TECHNOL., NOVEMBER 2001
Isopropylation experiments were carried out in
batch mode in a 300 mL stainless steel Parr autoclave.
The catalyst (lg) enclosed in a stainless steel wire
mesh was attached to the stirrer blades to ensure good
contact with reacting fluids . The reactor was loaded
with the required amount of naphthalene and
isopropylalcohol (IPA), and filled with nitrogen to the
required pressure. After carrying out the reaction for
the desired time, the reactor and its contents were
cooled, the product mixture dissolved in diethyl ether,
and analyzed by GC (Perkin-Elmer Auto System XL;
column: Ultra 2 (cross linked 5 % PHME siloxane),
film thickness: 0.52 Jlm, length: 25 m; i.d.: 0.32 mm)
with FID detector.
Results and Discussion
The isopropylation of naphthalene was carried out
over HY, REY and HM. The studies were also
carried out at different process conditions (tempera-
ture between 175 and 225C, pressures (with N
2
) of
15 to 90 bars, IPA/naphthalene mol ratios of 1 to 3
and different periods of time ( 1.5 - 9h)) in the case of

Isopropylation of naphthalene produces first the a-
and (1- and 2-IPN). The two
isomers undergo further alkylation to produce the
dialkylnaphthalenes. The isopropanol rapidly dehy-
drates into propene, which is the major alkylating
agent. The various isopropylnaphthalenes that are
formed in the reaction are shown in Scheme I.
Interconversions between the various isomers through
isomerization have not been shown in the scheme.
Comparison of activities of zeolites
The results of the isopropylation of naphthalene
with IPA at simi lar reaction conditions are presented
in Table 2. The zeolites may be arranged in the
following orders based on their performance w.r.t.
naphthalene conversion, diisopropylnaphthalene
(DIPN) selectivity and 2,6-/2,7-DIPN ratio.
> REY > HM > HY (conversion; DIPN selectivity)
HM > > HY > REY (2,6-/2,7-DIPN)
Naphthalene conversion is the highest for and
REY followed by HM. The lower conversion over
HY is probably due to its possessing weaker acidity as

00 / 1.4- DrPN 1.5-DIPN 1.8-DIPN
y I-lPN
1.2-DIPN 1.3-DIPN 1.6-DIPN 1.7-D!PN
2- IPN ' _pg{W'
2,3- DIPN 2.6-DIPN 2.7-DIPN
Scheme 1
Table I --Composition and surface area of the zeolites
Zeolite

HM
HY
REY
Zeolite Si/AI Unit cell composition
SsET
(m2/g)

15.49 HJ_s Na<O.OOI [AI J.sSiro. 1 0 128] .nH20 650
HM 11.07 H3_9Na<Ooo1 [AIJ_9Si44096] .nH20 560
HY 2.39 H2s.JNllo.2[Al 28.sSi6s.20tn l -nH20 880
REY 2.43 RE7.7HsNao.2[Al28.Si6sOtnl-nH20 720
Table 2--Comparison of activity of zeolites in isopropylation of naphthalene
Conv. Product yields(%) DIPN
(%) MlPN
1
DIPN
2
Others
3
selectivity

(%)
63.4 37.2 18.3 8.0 28.8
43.6 32.8 8.2 2.5 18.8
22.1 19.1 2.0 1.1 9.0
62.4 41.6 15.4 5.4 24.7
Selectivity ratios

2,6-/
2,7-
0.7 0.9
2.6 3.3
0.5 0.6
0. 5 0.5
Reaction conditions: temperature, 200C; pressure, 90 bars (with N
2
); Naphthalene, 0.02mol; lPA, 0.04mol; catalyst weight, I g.
1
: MIPN=monoi sopropylnaphthalene;
2
: DIPN=diisopropylnaphthalene;
3
: mostly poly alkylated products and oligomers of propylene
MATHEW eta/.: ISOPROPYLATION OF NAPHTHALENE
471
a result of its high AI content. Due to the presence of
RE-ions, REY possesses stronger acidity than HY.
The high conversion observed over can be
attributed to a combination of two factors; the 3-D
channel system made up of twelve-membered rings
enabling rapid diffusion of the reactant and product
molecules and the strong acidity arising from its large
Si/AI ratio. Even though one would expect HM to
possess strong acid sites as in its activity is lower
due to its unidimensional pores (pore dimensions:

- - Naphthalene Conversion
- - MIPN Yield
lO
60

<fl.
50
40
--------
30
0
6 8 10
Time (h)
Fig. !-Influence of duration of run on conversion and product
distribution. (Reaction conditions: temperature, 200C; pressure,
90 bars (with N
2
); naphthalene, 0.02mol; IPA, 0.04mol; catalyst
weight, lg)
0.75 x 0.55nm; HM, 0.67 x 7.1nm) and consequent
diffusion limitations.
DIPN selectivity follows the same trend as
conversion. One would expect DIPN selectivity to be
a function of catalyst activity, the concentration of
MIPN in the reaction mixture and the zeolite pore
dimensions. It appears that all the above effects are
responsible for the observed trend in DIPN
selectivity. As expected, among the large pore zeolites
(HM, and HY), 2,6-/2,7- ratio is highest for HM
due to its unidimensional pore system.
Influence of process parameters
The influence of temperature, naphthalene/IPA
mole ratio, N
2
partial pressure are presented in Table
3 and the influence of duration of run (contact time) is
presented in Fig. 1. The experiments (except the last
three in Table 3) were carried out over
On increasing the reaction duration from 1.5 to 6h,
conversion increased from 57.4 to 68.5% (Fig. 1).
There was not much change on increasing the reaction
time further to 9 h, indicating that equilibrium
conversion is attained in about 6h. Similar trends are
also observed for DIPN yield.
When the temperature was increased from 175 to
200C, naphthalene conversion increased from 34.0 to
63.4%. On further increasing the temperature to
225C, conversion decreased to 56.5%. Apparently,
thermodynamic equilibrium is attained at both 200
and 225C. The ratio increases continuously with
increase in temperature again due to thermodynamic
reasons; the isomer is thermodynamically more
Table 3---lnfluence of reaction parameters on isopropylation of naphthalene over Hf3
1
Parameter Conv. Product yields(%) Selectivity Selectivity
Temp Press. IPA/Naph (%) MIPN DIPN Others for DIPN Ratios
(bar) (mol ratio) (a+f3) [3/a 2,6-/2,7-
175 90 2 34.0 25.7 3.2 1.0 14.3 0.65 1.1
200 90 2 63.4 37.2 18.3 8.0 28.8 0.74 0.9
225 90 2 56.5 29.8 17.4 9.2 30.9 1.57 1.0
200 90 I 51.9 33.8 13.7 4.4 26.5 1.86 1.0
200 90 3 51.6 33.8 12. 1 5.8 23.4 0.70 1.5
200 15 2 58.7 32.2 18.3 6.2 31.1 0.94 0.9
200 46 2 55.8 34.1 15.3 6.4 27.4 0.72 1.0
200 90 2 43.6 32.8 8.2 2.5 18.8 2.60 3.3
200
2
2 35.4 26.8 5.9 2.7 16.7 2.53 3.1
200
3
2 11 .5 8.7 0.8 2.0 7.2 1.91 3.1
1
: Catalyst wt. , lg; N
2
used for pressurization; last 3 experiments carried out over HM;
2
: no solvent or N
2
used;
3
: cyclohexane (50ml)
used as solvent; see table 2 for other abbreviations.
472
INDIAN J. CHEM. TECHNOL., NOVEMBER 2001
stable than the a isomer at higher temperatures.
Selectivity for DIPN also increases with temperature,
the increase being more (14.2 to 28.8) between 175
and 200C and less (28.8 to 30.9) between 200 and
225C.
The influence of the relative concentrations of IPA
and naphthalene on the reaction was studied by
varying the IPA to naphthalene mole ratio from 1 to 3.
As the mole ratio is increased from I to 2, there is an
increase in conversion from 52 to 63%. There is also a
corresponding increase in the formation of
dialkylates. However, on increasing the mole ratio
from 2 to 3, there is deterioration in the performance
of the catalyst, as can be seen from the decrease in the
conversion and selectivity values. This may be
because, at higher concentrations of IPA, the effect of
propene oligomerisation and cracking leading to coke
deposition on the catalyst becomes significant. This
results in a decrease in the activity of the catalyst and
hence lower conversion and selectivity values.
Besides, the larger amount of water formed from IPA
(at higer IPA content) might al so be poisoning the
catalyst more.
Much of the reported work on naphthalene
alkylation using IPA have been carried out in an
organic solvent. The use of large organic molecules as
solvents in reactions involving zeolites is likely to
create difficulties due to competitive adsorption of the
solvent and counter diffusion problems. In this study,
the reactions have been carried out in the absence of
an organic solvent, but in nitrogen medium. To
examine the influence of using a solvent, a reaction
was carried out in using cyclohexane as solvent and
another in the absence of any added material. The
results of these experiments and that done in N
2
are
presented in Table 3. The conversion and selectivity
values are low when the reaction is carried out neat
(only with IPA and naphthalene) or when cyclo-
hexane is used as the reaction medium. Moreau et al.
1
had earlier reported a lower conversion (-20%) under
similar conditions using cyclohexane as solvent
1

Conclusion
A comparison of the activity of HY, REY, ~ and
HM in the isopropylation of naphthalene with isopro-
panol shows that ~ is the most active. REY is more
active compared to its H-form. Though conversion
over HM is lower than over H() and REY, DIPN
selectivity is highest over this zeolite due to its shape
selective nature. The reaction is rapid over ~ and
near equilibrium conversion and product yields are
reached in three hours at 200C. Highest conversion
of naphthalene is observed when stoichiometric
amount of IPA (IPNnaphthalene mole ratio=2) is
used. A comparison of the reaction in cyclohexane, N
2
and without any medium shows that the reaction
proceeds better in N
2
with higher activi ty and
selectivity.
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