Friedel-Crafts Alkylation of Diphenyl Oxide with
1-Decene Over Sulfated Zirconia as Catalyst
Ganapati D. Yadav” and Buddhadeb Kundu
University Department of Chemical Technology (UDCT), University of Mumbai, Matunga, Mumbai/Bombay -
400 01 9, India
0
rganic process industry has of late realized the importance of
heterogeneous catalysis because of strict environmental laws.
Amongst different conversion processes, the use of liquid phase
acid catalysts is very common. In particular, Friedel-Crafts alkylation and
acylation reactions are traditionally conducted by employing different
homogeneous acid catalysts. These acids pose several problems such as
recovery and reuse of catalyst, poor selectivity, waste generation and
treatment, use of expensive acid-resistant material of construction,
process hazards, etc. Therefore, there is a continuous search for new solid
catalysts that can accomplish reactions under milder operating conditions
with minimal harm to the environment. Several heterogeneous catalysts
have been reported and among the non-zeolitic catalysts, sulfated
zirconia has a better scope for industrial applications (Tanabe et al., 1979;
Tanabe, 1981; Song and Sayari, 1996; Yadav and Nair, 2000). We have
evaluated the prowess of sulfated zirconia and clay-based non-zeolitic
catalysts for a number of reactions of industrial importance, such as
condensation (Kumbhar and Yadav, 1989), esterification (Kumbhar et al.,
1989; Yadav and Mehta, 1994; Yadav and Krishnan, 1998a; Thorat et al.,
1992), alkylation (Dixit and Yadav, 1996a, b; Yadav et al.; Yadav and
Thorat, 1996a, b; Yadav and Doshi, 1999a, b), etherification (Yadav and
Kirthivasan, 1995; Yadav and Bokade, 1995; Yadav and Krishnan,l998b;
Yadav and Kirthivasan, 1999), dehydration (Yadav and Kirthivasan, 1999;
Yadav and Kirthivasan, 1997), acylation (Yadav and Pujari, 1999a; Yadav
and Krishnan, 1999), isomerisation (Yadav and Satoskar, 1997; Yadav
and Nair, 1998), nitration (Yadav and Nair, 1999a) and acetalization
(Yadav and Pujari, 1999b) by using sulfated zirconia, clays, pillared clays,
ion exchange resins, supported heteroployacids, and zeolites. Among
these catalysts, sulfated zirconia has gained a considerable attention due
to its very high acidity under certain conditions (Yadav and Nair, 1999b)
and this catalyst can be modified or doped with other cations/anions,
even incorporating sieving behaviour, for specific reactions (Yadav and Nair,
1999b; Yadav and Pujari, 1999a).
One industrial reaction scheme is the alkylation of diphenyl oxide with
alcohols, alkyl halides, ethers and olefins. The reaction of diphenyl oxide
with hexadecene has been reported to be a second-order process with
an activation energy of 20.4 kcal/mol. An electrophilic substitution
mechanism has been proposed (Anpilogov et al., 1983). The alkylation
of diphenyl oxide with other compounds such as cyclohexene, styrene,
3-methyl cyclohexene, 1-phenylcyclohexene, 3-cyclohexyl cyclohexene
*Author to whom correspondence may be addressed. E-mail address:
gdy&dct.emet.in
The Canadian Journal of Chemical Englneerlng,Volurne 79, October 2001
Friedel-Crafts alkylation and acylation reactions,
using highly polluting homogeneous Lewis and
Bronsted acids, are ubiquitous in a variety of organic
process industries. In many cases very high conversions
and selectivities can be achieved with aluminum
chloride as catalyst and nitrobenzene as a solvent.
However, environmental concerns associated with
aluminum chloride-nitrobenzene or BF,-HF or mineral
acids catalysts have encouraged development of solid
acids, which not only intensify the rates of reactions
but also offer better product selectivity. Amongst these
catalysts, sulfated zirconia has gained a considerable
importance due to its super-acidity under certain
conditions. The alkylation of diphenyl oxide with
1-decene was studied over sulfated zirconia catalyst
and it leads to industrially important products. The
surface reaction between chemisorbed 1-decene
diphenyl oxide from the liquid phase, in the absence of
any mass transfer resistance, was found to be the rate
determining step with Eley-Rideal type of mechanism.
Les reactions d’alkylation et d‘acylation de Friedel-
Crafts, a I’aide d‘acides homogenes hautement polluants
de Lewis et Bronsted, se retrouvent dans plusieurs
industries de proc&d6 organiques. Dans bien des cas, des
conversions et des selectivit6s tr&s 6lev6es pewent etre
obtenuesavec du chlorure d’aluminium comme catalyseur
et du nitrobenzgne comme solvant. Toutefois, les consid-
erations environnementales assocites aux catalyseurs de
chlorure d‘aluminium-nitrobenzene, de BF,-HF ou
d’acides mineraux ont encourage le developpement
d’acides solides, qui non seulement intensifient les
vitesses de reaction mais offrent 6galement une meilleure
s4lectivit6 de produits. Parmi ces catalyseurs, le zirconium
sulfat6 a pris une importance considerableen raison de sa
super-acidite dans certaines conditions. L’alkylation de
I’oxyde de diphenye avec du 1-d&ne a 6te etudi6e sur
un catalyseur de zirconium sulfat6 et mene B des produits
industriellement importants. La reaction de surface entre
I’oxyde de dyphenile et le ldecene chimisorb6 de la
phase liquide, en I’absence de toute resistance au
transfert de matiere, s’avere &re I’btape determinant la
vitesse avec le type de mtkanisme de Eley-Rideal.
Keywords: sulfated zirconia, diphenyl oxide,
1-decene, a-olefins, kinetics, eley-rideal mechanism,
heterogeneous catalysis, Friedel-Crafts alkylation.
805
with homogeneous catalyst has been reported. The current
paper reports the use of sulfated zirconia as catalyst in the
alkylation of diphenyl oxide by 1 -decene. The kinetics and
mechanism are also elucidated.

Experimental
Chemicals
Zirconium oxychloride and diphenyl oxide were obtained from
M/s s.d. Fine Chemicals Pvt. Ltd., Mumbai, India. 1 -decene was
obtained from Herdillia Chemicals Ltd., Mumbai, India.

Catalyst
Sulfated zirconia was prepared by the method developed in this
laboratory (Kumbhar and Yadav, 1989; Kumbhar et al., 1989;
+ Q W:i3 t

Thorat et al., 1992). A known amount of zirconium oxychloride

was dissolved in deionized water and filtered. The filtrate was
then taken in a separating funnel and aqueous ammonia in

w
another separating funnel. Both of these were then added
simultaneously in a beaker at controlled flow rates maintaining
the pH of the solutions a t around 9 to 10 with constant stirring.
After the precipitation was complete, the precipitate was
digested for some time. The zirconium hydroxide thus obtained
was filtered and washed with deionized water until no ammonia
3 +
0
C X M H Y

and chloride ions were detected in the filtrate, which was verified
from the phenolphthalein and the silver nitrate tests, respectively.
The hydroxide was dried in an oven for 24 h at 393 K. The dried
cake was then crushed to obtain the desired particle size.
Sulfation of the hydrous zirconia was carried out by percolating
1 N H,SO, solution through it taken as 15 mL/g of solid hydrous
zirconia. The sulfated zirconium hydroxide was calcined in air at
923 K for 3 h in a quartz tube to yield the final catalyst. The
catalyst was characterized to find that its properties were in
agreement with those reported by our group (Kumbhar et al, 1989).

Experimental Figure 1. Scheme for the reaction between diphenyl oxide with 1-
The reactions were studied in a standard 100 mL Parr autoclave decene in presence of sulfated zirconia catalyst.
equipped with a 4-bladed turbine impeller. Typical experiments
were carried out by using 5 mol (0.034kg) of diphenyl oxide
and 1 mol (0.056 kg) of 1 -decene giving a mole ratio of 5:l.
The catalyst loading was 5 kg/m3 (0.195 g), at 423 K, at a speed
of agitation of 20 rps. Samples were collected periodically and
analyzed by gas chromatography. A 4 m x 0.03 m column
packed with 10% OW17 supported on chromosorb WHP was
used. A calibration curve was plotted, by using synthetic
mixture of pure components in order to quantify the data. The
final reaction mixture was also analyzed on a CC-MS.
A detailed kinetic study was also done by studying the effect
of various parameters such as speed of agitation, particle size,
catalyst loading, temperature of reaction and mole ratio of the
reactants. Reusability of the catalyst was also studied. All the
runs were conducted for 2 h.

Results and Discussions

The Friedel-Craftsalkylation of diphenyl oxide (B) with 1 -decene
(A) in presence of sulfated zirconia catalyst (S-Zr0.J leads to the
formation of an isomeric mixture of diphenyl oxide-decanes.
This was confirmed by CC-MS, IR and NMR. The reaction
products and mechanism of the reaction are shown in Figure 1
and Figure 2, respectively. In the presence of S-ZrO, catalyst
0
1 -decene is protonated and four carbocations are formed which
then combine with diphenyl oxide in the ortho and para
positions of the benzene ring to produce a mixture of diphenyl Figure 2. Mechaism for the reaction between diphenyl oxide with
1-decene in presence of sulfated zirconia catalyst.

806 The Qnadlan Journal of Chemical Engineering, Volume 79, October 2001
oxide-decanes. A maximum of eight products were detected in
the reaction mixture. The products were identified as isomeric
mixtures of four different diphenyl oxide-decanes. A 88.5%
conversion of 1 -decene was obtained in 2 h and the selectivity
of 2-, 3-, 4-, and 5-diphenyl oxide-decanes were 40%, 23%,
19%, and 18%, respectively. The effect of various parameters
were studied under otherwise similar conditions a t a standard
temperature of 423 K.
This is a typical solid-liquid slurry reaction involving the
transfer of 1-decene (A) and diphenyl oxide (B) to the catalyst
wherein the reactants are transferred to the surface of the
catalyst particle, followed by intra-particle diffusion in the pore
space, and adsorption, surface reaction and desorption. The
influence of both external solid-liquid mass transfer and
intra-particle resistance must be ascertained before a true
kinetic model can be developed. Thus experimental and
theoretical analyses were done.
Since diphenyl oxide (B) was used in large excess over 1-
decene (A), there was a chance of control by the transfer of A
from the bulk liquid phase to the external surface of the catalyst
particle. The effect of speed of agitation was studied over the
range of 8.34 to 25 rps, at a catalyst loading of 5 kg/m3 liquid
phase with an average particle size of 90 pm. Figure 3 shows the
conversion of 1-decene a t different time intervals. The conversions
are found to remain practically the same at speeds beyond 20 rps,
thereby indicating absence of solid-liquid mass transfer resistance.
Surface reaction control is further supported by the effect of
particle size of the catalyst on the rate. To predict the solid-liquid
mass transfer coefficients for A and 6,ksLa and ksl-, the diffusivities
of A in bulk 6 and 6 in bulk A were calculated by using Wilke-Chang
0 I 2 3 4 5 8 7
Time I. loJ, s
e 8 . 3 4 ~m 1 3 . 3 4 ~ A20rps X 2 5 r p s
Figure 3. Effect of speed of agitation. Catalyst loading: 5 kg/m3;
catalyst: sulfated zirconia; temperature: 423 K; DPO: 1-decene (molar)
= 5:l.
The Canadian Journal of Chemical Englneerlng,Volume 79, October 2001
equation for which the various required parameters were
determined from the group contribution method.
The diffusivity values a t 423 K were: DAB(423 K) = 9.366 x
10-10 m2/s, D, (423 K) = 9.1 71 x 10-lo m2/s. The solid-liquid
mass transfer coefficients were calculated by assuming the
Sherwood number of 2. Thus k5,, = 2.08 x m/s and
k,,, = 2.038 x 1O-s m/s.
For the particle size (d,,) of 90 pin, the surface area of
particles (a,) per unit liquid volume was calculated by assuming
spherical particles for the particular catalyst loading w
(kg/m3). So a, = 6w/(p,, d,,) = 62.54 m2/m3.
Substituting these values in an expression for the adsorbed
rate, assuming mass transfer controls, 1/[k,,,a,,(A,)] = 7.495 x
102 m3.kmol-1.s and l/[k,,,aP(6J] = 1.53 x lo2m3.kmol-1.sand
1/(robs)= 1 /[k,,w (A0)(6,J]= 3.362 x 1 O2 m3.kmol-l.s.
Since the reciprocal of the observed rate is larger than the
reciprocal of the minimum mass transfer rate a significant
external resistance to mass transfer was absent and overall rate
could either be controlled by intra-particle resistance or the
surface reaction within the pores. Further experiments were
done a t or above 20 rps.
The contribution of intra-particle diffusional resistance was
ascertained by studying the reaction for different particle sizes
by keeping the same solid loading. It is apparent from Figure 4
that the particle sizes below 90 pm has no effect on the conversion
of 1-decene. This in turn signifies that intra-particle mass
transfer resistance is insignificant below catalyst particle sizes of
90 pm and the surface reaction is rate controlling. The application
of the Wietz-Prater criterion confirmed that below 90 pm
particle size there was no intra-particle diffusion limitation.
lo
0
8
0 2 4 6 8
mme l o 3 ,
+ 212-W)pm rn 90-105 pm A 75-90 pm
Figure 4. Effect of particle size. Temperature: 423 K; DPO: 1-decene
(molar) = 5 1 ; speed of agitation: 20 rps; catalyst loading: 5 kg/m3;
catalyst: sulfated zirconia.
807
 -I
mt

O Y
0 1 2 3 4 5 8 7 8 0 1 2 3 4 5 8 7 8
Time x lo3, I
Time x 103,r
+ 2 kgm3 5 kg/m3 A 7.5 kg/m3
DPO: 1 -L)ecene (molar) = 3: 1 5 : 1 A 10: 1

Figure 5. Effect of catalyst loading. Speed of agitation: 20 rps; catalyst:

sulfated zirconia; temperature: 423 K; DPO: 1 -decene (molar) = 51. Figure 7. Effect of mole ratio. Speed of agitation: 20 rps; catalyst
loading: 5 kg/m3; catalyst: sulfated zirconia; temperature: 423 K.

30

25

Y)
nE 20

E
3., 15
.-
c
0
r
X
.- 10
P

0 1 2 3 4 5 8 7 8
0 T i m xlO', I
0 0.2 0.4 06 08
w x lo', kglm' + 413 O K 423 O K A 433 O K

Figure 6.Plot of initial rate of reaction (rJ against catalyst loading (w). Figure 8. Effect of temperature. Speed of agitation: 20 rps; DPO: 1-decene
DPO: 1-decene (molar) = 5:l; temperature: 423 K; speed of agitation: (molar) = 5:l; catalyst: sulfated zirconia; catalyst loading = 5 kg/m3.
20 rps; catalyst: sulfated zirconia.

808 The Canadian Journal of Chemical Engineering, Volume 79, October 2001
 The effect of catalyst loading was studied by varying the
catalyst loading from 2 kg/m3 to 7.5 kg/m3. The plots of
conversion as a function of time and the initial rate of reaction
as a function of catalyst loading are shown in Figures 5 and 6
respectively. It is found that the rate of reaction increases
linearly with the catalyst loading. This is a consequence of
absence of both external and internal mass transfer resistance.
The effect of mole ratio of the reactants was studied for different
mole ratios of diphenyl oxide to 1-decene. Figure 7 shows the
plots of conversion of 1-decene as a function of time at three
different mole ratios. It can be seen from the plots that as the
mole ratio is increased, the conversion of 1-decene also increases.
The effect of temperature on proceedings of the reaction was
investigated for three different temperatures. Figure 8 shows the
plot of percent conversion of 1-decene with time a t temperatures
of 41 3 K, 423 K, and 433 K. The rate of reaction increasesas the
temperature increases.
added to make up for losses in order to ascertain any loss in
activity. Thus, on the basis of the unit mass of catalyst taken
the loss in the activity was 15.4% and 17% after first reuse
and second reuse, respectively. This activity loss could be due
to blockage of pores of the catalyst by some products of the
reaction, which might not have been washed out properly by
acetone, or it could be experimental error because of the
batch size.
Discussion
The initial rate data was analyzed on the basis of Langmuir-
Hinshelwood-Hougen-Watson (LHHW) or Eley-Rideal
mechanisms. It was found that an Eley-Rideal mechanism with
chemisorption of 1-decene alone which reacts with the
diphenyl oxide from the pore space with weak adsorption of the
products. Adsorbtion of Diphenyl oxide only poisons the sites.
The overall rate was given by:

Reusability of Catalyst
The deactivation of the catalyst was assessed for this alkylation
reaction.
Figure 9 shows the effect of catalyst deactivation on the
percent conversion of 1-decene. After the initial reaction, the
catalyst was filtered, washed with acetone and reused. It was
found that the conversion after first reuse of catalyst was 55%
of the freshly prepared one. For the second reuse the
conversion was 62% of the first reuse. It was observed that
there was considerable attrition of particles and about 35%
of total fine particles were lost during first washing with the
solvent and filtering. Since the particles were quite small
(75 to 90 pm), such fine particles were not completely
retained on the laboratory filter papers. On subsequent use,
the loss of catalyst was about 25%. No fresh catalyst was
where k, represents the combined forward rate of constant for
reaction for all isomers. If the initial rates of reaction (rJ are
measured, then Equation (1) can be transformed into:
c w 1
BO=-+- 1
(2)
roi ~RKACAO k~
Figure 10 plots {C,,w /roj against (1/CAo) yielding a straight
line with a slope of (k,KA)-l and an intercept of (l/k,) from
which both the reaction rate constant k, and adsorption equilib-
rium constant KA can be established. Equation fits the data well.
Assuming the surface reaction between chemisorbed 1-decene

2.5
#r
fa 2
5
9-
15

3
..r
3 ’
B
Y
05

0 1 2 3 4 5 6 7 8
0
Tme x 18 0 5 10 15 20
( l/clro)xloJ, 119) I kgmok
+ Fresh m lst Resue A 2 nd Reuse

Figure 10. Plot to establish equilibrium constant and rate constant.

FIgure 9. Reusability of catalyst. Catalyst: Sulfated zirconia; speed of Catalyst: sulfated zirconia; catalyst loading: 5 kg/rn3; speed of
agitation: 20 rps; DPO 1-decene (molar) = 5:l; temperature: 423 K. agitation: 20 rps; temperature: 423 K.

The Canadian Journal of Chemical Englneerlng,Volume 79, October 2001 809

(AS) and diphenyl oxide (B) from the liquid phase is rate
determining, k, and KA are 3.3 x m3.kg-1s1, and 0.285
m3/kmol, respectively. KA indicates that for C, < 0.35 kmoVm3, 35
the denominator of Equation (1) can be approximated as unity
within experimental error. Thus the concentrations of A were so
chosen that KAC, < < 1, then Equation (1) gives the following: 3

2.5

This situation may also exist a t high temperature, since a t high

3
-
C
2 -

temperature it is expected that the adsorption equilibrium

constants are low. Moreover, a t high temperature, A is expected 15
to be weakly adsorbed on the catalyst surface.
Since C,, >> C, then the change in concentration of B with 1
respect to time can be neglected to give a pseudo-first order
kinetics. On integration, with C, constant Equation (3) leads to:

(4) 05
01
2.3
I 2.32 2.34 2 3 2.M 2.4 2.42 2.44
(5) ii T x lo3(@K 1-l
Thus, plots of -In(l-X,) vs. time were made for this reaction
Figure 12 Arrhenious plot for alkylation of DPO with 1-decene. Catalyst
at various temperatures (Figure 11). It can be seen that all of
loading: 5 kg/m3; catalyst: sulfated zirconia; DPO: 1-decene (molar) =
these plots show straight lines passing through the origin. Their 5:l; speed of agitation: 20 rps.
linearity confirms the pseudo-first order behaviour of the
reaction.
From the slopes of these plots the rate constants (kSR)at 41 3 K,
423 K and 434 K are found to be 5.1 1 x 10-9, 11.31 x 10-9 and

17.55 x 10-9 m6.kmol-1.g-1.s-1, respectively. These values are

reasonable because k,, is a product of k, and K,; and k,
increases with temperature whereas KA decreases.
Again a t a fixed catalyst loading w, the Arrhenius plot was
3 made of In(k,, ) against 1/ T (Figure 12). From the slope of this
plot the value of apparent activation energy was found to be

- 2.5
20.5 kcal/mol confirming that the reaction rate is controlled by
intrinsic kinetics a t the surface of catalyst pores.

r2
-
W

e
Conclusion
The effects of different parameters on rates of alkylation of
diphenyl oxide with 1-decene catalysed by sulfated zirconia
1.5
were studied systematically to establish the kinetics of the
reaction. The rate determining step was found to be the
1 surface reaction between chemisorbed 1-decene and
diphenyl oxide from the liquid phase within pores according
0.5 to Eley-Rideal mechanism.
Under certain conditions the adsorption equilibrium and
rate constant could be found. At lower concentrations of 1 -
0
dodecene, it is observed that the reaction is first order in 1-
0 2 4 6 8
decene.
Time x lo', 8 The influence of temperature showed typical apparent
activation energy for this reaction as 20.5 kcal/mol.
* 4 1 3 " K m423')K A433'K Acknowledgements
B.K. acknowledges the award of a JuniorResearch Fellowship by
the University Grants Commission, New Delhi. C.D.Y. acknowledges
Figure 11. Kinetic plots for various temperatures. Catalyst loading: 5 kg/m3; research funding by DST, Covt. of India and the Darbari Seth
catalyst: sulfated zirconia; DPO: 1-decene (molar) = 5:l; speed of
Professorship Endowment.
agitation: 20 rps.

810 The Canadian Journal of Chemical Engineering, Volume 79, October 2001
Nomenclature
A reactant species A, 1-decene
AS chemisorbed species A
solid-liquid interfacial area, m2/m3of liquid phase
3 reactant species B, diphenyl oxide
concentration of A, (kmol/m3)
CA
'AO initial concentration of A in bulk liquid phase, (kmol/m3)
concentration of A at solid (catalyst) surface, (kmol/m3)
CAI
CB concentration of B, (kmol/m3)
initial concentration of B in bulk liquid phase, (kmol/m3)
CEO
diffusion coefficient of A in B, (m2/s)
DAB
DBA diffusion coefficient of B in A, (m2/s)
d diameter of catalyst particle, (pn)
4
kR
adsorption equilibrium constant for A, (m3/kmol)
modified surface reaction rate constant, (rn3.g-l.s-l)
second order rate constant, kRK, (rn6.kmol-l.g-ld)
kSR
solid-liquid mass transfer cofficient for A, (m/s)
k5L-A
solid-liquid mass transfer cofficient for B, (m/s)
k5L-B
M mole ratio of C,dCA,
rate of mass transfer of A, ( k m ~ l . m - ~ d )
RA
observed (overall) rate of reaction per unit liquid volume,
'obs
(km~l.rn-~d)
initial rate of reaction, ( k m ~ l . m - ~ d )
'oi
W catalyst loading, kg/m3 of liquid phase
fractional conversion of A
XA
Greek Symbol
density of catalyst particle, (kg/m3)
PP
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Manuscript received March 15, 2000; revised manuscript received
April 23, 2001; accepted for publication July 10, 2001.
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