20

th
Annual Saudi-Japan Symposium
Catalysts in Petroleum Refining & Petrochemicals
Dhahran, Saudi Arabia - December 2010

Catalytic Cracking of Paraffins on Zeolite Catalysts for the
Production of Light Olefins

Takayuki Komatsu
Department of Chemistry and Materials Science, Tokyo Institute of Technology
Tokyo 152-8550, Japan; komatsu@cms.titech.ac.jp
Abstract
Cracking of heptane and octane, typical components of naphtha, was carried out on
various proton-type zeolite catalysts. The selectivity to light olefins increased with
decreasing the pore diameter of zeolites. Among them, H-ferrierite showed the highest
olefin selectivity. Ca
2+
-exchange into H-ferrierite further increased the selectivity
especially at higher conversions and also improved the catalyst stability. The amount of
coke formed during the reaction decreased by the Ca
2+
-exchange. It is suggested that the
Ca cations located inside the pores hinder the diffusion of reactant, product and
intermediate molecules to retard hydride transfer between carbenium intermediate and
olefin product, a bi-molecular reaction to form paraffins and coke precursors. As a result,
the formation of paraffins and coke would be effectively suppressed, which may result in
the high selectivity and stability of Ca
2+
-exchanged ferrierite.

1. Introduction
Light olefins, such as ethylene, propylene and butenes, are produced mainly by the
thermal cracking of naphtha to supply these important raw materials for petrochemical
industry. In this process, a large amount of energy is consumed because the process is
usually operated at high temperatures around 1100 K. Moreover, it is difficult to control
the selectivity to obtain propylene in a high yield because the thermal cracking favors the
ethylene formation. The catalytic cracking, however, would require less energy and could
produce propylene with higher selectivity.
The catalytic cracking of light paraffins, such as pentane, hexane, heptane and octane,
has been studied on various zeolite catalysts as a test reaction of naphtha cracking to
clarify the performance of catalysts and the reaction mechanism
1
. Y-type zeolite is the
most extensively studied zeolite because it has been used commercially for FCC process.
Though the dealumination of Y zeolite gives USY zeolite with higher activity and stability
and varies the selectivity significantly
2-5
, the large space inside supercages would not be
favorable to obtain small molecules such as propylene. In addition, the large space will
accelerate the hydride transfer, one of the undesirable side reactions to produce paraffins
and hydrogen deficient species, a coke precursor, resulting in the decrease in olefin
selectivity and catalyst life.
ZSM-5 is one of the candidates for the production of light olefins through the naphtha
cracking. Wang et al.
6
carried out hexane cracking on H-ZSM-5(Si/Al=25) and found that
the addition of potassium (2 wt%) or boron (16 wt%) increased the selectivity to C2-C4
olefins into >50 C-% though the conversion was significantly decreased. Yoshimura et al.
7

have carried out the cracking of light naphtha and found that the addition of lanthanum (10
wt%) into H-ZSM-5(100) enhanced the selectivity to ethylene and propylene into 61 C-%
and that the further addition of phosphorus (2 wt%) improved the stability in the presence
of steam. Other studies on H-ZSM-5 catalysts include the NaOH treatment to form
mesopores
8
, the addition of gallium
9
, the spray-dry preparation with alumina
10
, and the
preparation of monolith catalyst by washcoat
11
.
Recently, other medium pore zeolites, ZSM-57(10- and 8-membered rings)
12
, ferrierite
(10- and 8-MRs

)
13
and ZSM-22(10-MR)
13
, and small pore zeolites, chabazite(8-MR),
ZK-5 (8-MR) and ZSM-58(8-MR)
14
, have been studied to obtain small olefin molecules.
However, the above zeolites do not have enough activity, selectivity and stability for the
production of light olefins instead of the commercial thermal cracking process.
In this study, we carried out the catalytic cracking of heptane
15
and octane on zeolites
with various pore structures to obtain the effective catalyst for the formation of light
olefins, especially propylene, in high selectivity at high conversion levels.

2. Experimental
Catalysts were prepared as follows. Two batches of Na,K-ferrierite with Si/Al atomic
ratio of 9.2 and 8.0, expressed as Na,K-ferrierite(9) and Na,K-ferrierite(8) hereafter, were
synthesized hydrothermally. ZSM-5(22), beta(14) and MCM-22(25) zeolites were also
synthesized hydrothermally to obtain their sodium-forms. Na-Y(2.7) was supplied by
Mizusawa Industrial Chemicals, Ltd. These zeolites were ion-exchanged with an aqueous
solution of ammonium nitrate at 343 K for three days, washed with pure water, dried in air
at 383 K, and calcined in air at 723 K to obtain each proton-form zeolite. The ion
exchange technique was also applied to the preparation of Ca
2+
and Ba
2+
-exchanged
zeolites using the aqueous solution of each acetate at 298-343 K. These exchanged zeolites
were dried and calcined in air at 723 K.
The cracking reactions were carried out with a fixed-bed flow reactor under
atmospheric pressure. A known amount of catalyst (0.2-1.5 g) was put into a tubular
reactor of 12 mm i.d. and activated in flowing helium at 773 K for 1 h as a pretreatment
before each run. n-Heptane or n-octane (Wako Pure Chemicals Ind.) was fed at 773 K by a
mechanical feeder with helium as a carrier gas. The flow rates of n-heptane and n-octane
were 2.7-16 mmol h
-1
with a constant helium/heptane(octane) molar ratio of 9. W/F
corresponded to 1.3-56 g h mol
-1
. Products were analyzed by gas chromatography
(Shimadzu, GC-14B) with an Alumina/KCl PLOT column.
The amount of coke on zeolite after 6.6 h of the cracking reaction was obtained by
thermogravimetry (TG) from 295 to 1073 K under flowing dry air. Cracking of
1,3,5-triisopropylbenzene (TIPB) was carried out at 623 K in a similar manner to the
heptane cracking. A mixture of TIPB and helium (1/30 molar ratio) was fed onto 0.3 g of
catalyst with W/F of 1.9 g h mol
-1
. Products were collected at 273 K and analyzed by gas
chromatography (Shimadzu, GC-8B) with a Silicone OV-101 column. Temperature
programmed desorption (TPD) of adsorbed ammonia was measured with a glass vacuum
system connected to a Canon-Anelva M-101QA-TDM quadrupole mass spectrometer. The
catalyst was set in a quartz reactor and evacuated at 723 K for 1 h as a pretreatment.
Ammonia (13 kPa) was introduced into the catalyst at 423 K for 10 min. After the catalyst
was evacuated at 423 K for 30 min, TPD was measured from room temperature in a
heating rate of 10 K min
-1
.

3. Results and Discussion
The cracking of n-heptane was first carried out on various proton-form zeolite
catalysts at the reaction temperature of 773 K. Conversion of n-heptane decreased with
time on stream except for H-ZSM-5, which showed almost constant conversion of 95% for
3 h on stream. The selectivity of catalysts changed with time on stream, because the
conversion affected the selectivity. The relation between conversion and selectivity is
shown in Fig. 1 for the results obtained on H-ZSM-5(22). As shown by the solid symbols,
the selectivity to each olefin, i.e. ethylene, propylene and butenes (trans-2-butene,
cis-2-butene, 1-butene and iso-butene) decreased with increasing conversion. In the case
of propylene, the selectivity decreased from 28 to 13 C-% when the conversion increased
from 46 to 92%. The selectivity to ethane and butane did not change significantly, whereas
that to propane increased steeply with conversion. Similar changes in selectivity with
conversion were observed for other proton-form zeolites.










40
30
20
10
0
20 40 60 80 100
Heptane conversion / %
S
e
l
e
c
t
i
v
i
t
y

/

C
-
%
Fig. 1. Change in selectivity to ethylene (),
propylene (), butenes (), ethane (),
propane () and butanes () with heptane
conversion on H-ZSM-5(22).
40
30
20
10
0
20 40 60 80 100
Heptane conversion / %
S
e
l
e
c
t
i
v
i
t
y

/

C
-
%
40
30
20
10
0
20 40 60 80 100
Heptane conversion / %
S
e
l
e
c
t
i
v
i
t
y

/

C
-
%
Fig. 1. Change in selectivity to ethylene (),
propylene (), butenes (), ethane (),
propane () and butanes () with heptane
conversion on H-ZSM-5(22).

















Then we compared the selectivity of various zeolites at a relatively higher conversion
of 80% to estimate the performance of zeolites under industrial conditions. The selectivity
values were obtained for various zeolites by interpolating the data obtained in a similar
manner to Fig. 1. The results for H-ferrierite(9), H-ZSM-5(22) H-MCM-22(25),
H-beta(14) and H-Y(2.7) are shown in Fig. 2. The size of pores or cages in these zeolites
roughly increased in this order. H-ferrierite having the smallest pores gave C1-C4
paraffins (C1-C4) and C2-C4 olefins (C2
=
-C4
=
) with comparable selectivity but did not
give iso-butane (iC4). The other products mainly contained aromatic hydrocarbons. As the
pore size increased, the selectivity to larger paraffins such as propane and butanes
increased and the formation of iso-butane dominated that of n-butane (nC4). Similar
results were reported for the cracking of n-decane on H-Y, H-erionite and H-ZSM-5 at the
conversions lower than 25%
16
. We calculated the total selectivity to olefins, S(olefin), as
shown in the right side of Fig. 2. The values indicate that ferrierite and ZSM-5, which
have 10-MR channels without larger cavities inside the pore, are favorable for the
formation of light olefins with higher yield. Higher olefin selectivity on H-ferrierite and
H-ZSM-5 than those on H-mordenite and H-USY were also reported for the products in
n-hexane cracking at 7-14% conversions
17
.
Scheme 1 shows the typical reaction mechanisms for paraffin cracking on acid
catalysts
18
. In the monomolecular mechanism (A), a paraffin molecule is protonated by a
Brnsted acid to form a carbonium ion (1). It is decomposed into a paraffin and a
carbenium ion (2), which gives an olefin and an acidic proton (3). In the bimolecular
0 20 40 60 80 100
Selectivity / C-%
H-ferrierite(9)
H-ZSM-5(22)
H-MCM-22(25)
H-beta(14)
H-Y(2.7)
S(olefin)
43 C-%
40 C-%
32 C-%
21 C-%
13 C-%
C1 C2 C2
=
C3 C3
=
nC4
C4
=
iC4
Olefin
Others
Fig. 2. Selectivity of proton-form zeolite catalysts in heptane cracking at 80%
conversion. C2
=
: ethylene, C3
=
: propylene, C4
=
: butenes, C1: methane, C2: ethane,
C3: propane, iC4: isobutane, nC4: butane, S(olefin): total selectivity to C2
=
-C4
=
.
0 20 40 60 80 100
Selectivity / C-%
H-ferrierite(9)
H-ZSM-5(22)
H-MCM-22(25)
H-beta(14)
H-Y(2.7)
S(olefin)
43 C-%
40 C-%
32 C-%
21 C-%
13 C-%
C1 C2 C2
=
C3 C3
=
nC4
C4
=
iC4
Olefin
Others
0 20 40 60 80 100
Selectivity / C-%
H-ferrierite(9)
H-ZSM-5(22)
H-MCM-22(25)
H-beta(14)
H-Y(2.7)
S(olefin)
43 C-%
40 C-%
32 C-%
21 C-%
13 C-%
C1 C2 C2
=
C3 C3
=
nC4
C4
=
iC4
Olefin
Others
Fig. 2. Selectivity of proton-form zeolite catalysts in heptane cracking at 80%
conversion. C2
=
: ethylene, C3
=
: propylene, C4
=
: butenes, C1: methane, C2: ethane,
C3: propane, iC4: isobutane, nC4: butane, S(olefin): total selectivity to C2
=
-C4
=
.
mechanism (B), a paraffin reacts with a carbenium ion to form a smaller paraffin and a
larger carbenium ion (4), which is AAAA




















decomposed into an olefin and a carbenium ion through the -scission (5). Only from
these reactions, the half of products must be olefins. On the other hand, an undesirable
side reaction, hydride transfer, usually occurs as shown in Scheme 2. The hydride transfer
from an olefin to a carbenium ion is catalyzed by acid sites at high conversion levels to
form a paraffin and a hydrogen deficient species, allylcarbenium ion (6)
19
. Such hydrogen
deficient species would be further transformed into aromatic hydrocarbons and coke
through the dehydrogenation and cyclization (7). Thus the hydride transfer decreases the
selectivity to olefins at high conversion levels, where the formation of aromatic
hydrocarbons was obviously observed on H-ZSM-5(22) and H-beta(14), as shown in Fig.
2. The results in Fig. 2 indicate that the hydride transfer from olefins to form paraffins
occurs more easily on zeolites with larger pores and cages. It was reported that the hydride
transfer is affected by pore sizes of zeolite because the bimolecular transition state is not
easily formed in small pores
20
.
In order to obtain zeolite catalysts with higher olefin selectivity, H-ferrierite(9), which
showed the highest total olefin selectivity, was exchanged with divalent cations. The
heptane cracking was carried out on Ca
2+
(39%)- and Ba
2+
(23%)-exchanged H-ferrierite(9).
(4)
(5)
+
+
H H
H
+
H
+
(1)
(2)
(3)
+
H
Scheme 1. Reaction mechanism for heptane cracking through the monomolecular (A)
and bimolecular (B) cracking.
(A) (B)
(4)
(5)
+
+
(4)
(5)
++
++
H H
H
+
H
+
(1)
(2)
(3)
+
H
H H
H
+
H H
H
+
H
+
H
+
(1)
(2)
(3)
+
H
+
H
Scheme 1. Reaction mechanism for heptane cracking through the monomolecular (A)
and bimolecular (B) cracking.
(A) (B)
(6)
(7)
+
+
coke
aromatics
Scheme 2. Hydride transfer to form paraffin, coke and aromatics.
(6)
(7)
+
+
coke
aromatics
(6)
(7)
++
++
coke
aromatics
Scheme 2. Hydride transfer to form paraffin, coke and aromatics.











Fig. 3 shows the selectivity of these catalysts at 70% conversion compared with that of
the parent H-ferrierite. Ca
2+
-exchange into H-ferrierite obviously increased the selectivity
to propylene and butenes, resulting in the increase in total olefin selectivity from 45 to 60
C-%. In Fig. 4, the selectivity of Ca(39%),H-ferrierite(9) is plotted against the conversion
as in the case of AA Fig. 1 for H-ZSM-5. In contrast to the result of H-ZSM-5 and
H-ferrierite (not shown), the selectivity to propylene gave almost constant value just below
30 C-%, even at the conversion higher than 80%. The selectivity to paraffins did not
increase significantly with increasing conversion. These results indicate that the hydride
transfer to consume olefins was effectively suppressed by the Ca
2+
-exchange into
H-ferrierite. As shown in Fig. 3, Ba
2+
-exchange also resulted in the high olefin selectivity
of 60 C-% though the Ba
2+
-exchange level, 23%, was lower than that in
Ca(39%),H-ferrierite. Alkaline earth ions exchanged into H-ferrierite would be effective
for the formation of light olefins with higher yields. We also examined the effect of
Ca
2+
-exchange into H-ZSM-5(22) and found that Ca(36%),H-ZSM-5 showed almost the
same selectivity as that of the parent H-ZSM-5. The alkaline earth ions must modify the
chemical or physical properties of H-ferrierite.
The effect of Ca
2+
-exchange into ferrierite was further examined on the stability of
activity. We carried out the cracking of n-octane, one of the components of naphtha, on
ferrierite(8) AAA








20 40 60 80 100
Heptane conversion / %
40
30
20
10
0
S
e
l
e
c
t
i
v
i
t
y

/

C
-
%
Fig. 4. Change in selectivity to ethylene (),
propylene (), butenes (), ethane (),
propane () and butanes () with heptane
conversion on Ca(39%),H-ferrierite(9).
20 40 60 80 100
Heptane conversion / %
40
30
20
10
0
S
e
l
e
c
t
i
v
i
t
y

/

C
-
%
20 40 60 80 100
Heptane conversion / %
40
30
20
10
0
S
e
l
e
c
t
i
v
i
t
y

/

C
-
%
Fig. 4. Change in selectivity to ethylene (),
propylene (), butenes (), ethane (),
propane () and butanes () with heptane
conversion on Ca(39%),H-ferrierite(9).
H-ferrierite(9)
Ca(39%),H-ferrierite(9)
Ba(23%),H-ferrierite(9)
0 20 40 60 80 100
Selectivity / C-%
S(olefin)
45 C-%
60 C-%
60 C-%
Olefin
C2
=
C3
=
C4
=
C2 C3
C1 nC4
Others
Fig. 3. Effect of cation-exchange into H-ferrierite on the selectivity in heptane cracking at
70% conversion.
H-ferrierite(9)
Ca(39%),H-ferrierite(9)
Ba(23%),H-ferrierite(9)
0 20 40 60 80 100
Selectivity / C-%
S(olefin)
45 C-%
60 C-%
60 C-%
Olefin
C2
=
C3
=
C4
=
C2 C3
C1 nC4
Others
Olefin
C2
=
C3
=
C4
=
C2 C3
C1 nC4
Others
Fig. 3. Effect of cation-exchange into H-ferrierite on the selectivity in heptane cracking at
70% conversion.












exchanged by Ca
2+
ions with various exchange levels. Fig. 5 shows the change in
conversion with time on stream at the reaction temperature of 823 K. H-ferrierite gave the
high initial conversion but the conversion decreased quickly with time on stream to reach
the value of thermal cracking at 6.6 h on stream. Ca(25%),H-ferrierite showed slightly
lower deactivation rate than that on H-ferrierite but the activity is hardly observed at 6.6 h.
On the other hand, Ca,H-ferrierite with Ca
2+
-exchange levels of 57% and 75% showed
much higher stability, that is, the decrease in conversion was effectively suppressed though
the initial conversion was slightly lower than that on H-ferrierite. The decrease in
conversion from the initial value to that at 6.6 h on stream was obtained for each catalyst
and plotted against the exchange level as shown in Fig. 6. It is clear that exchanged Ca
2+

ions significantly stabilize the activity of ferrierite and that 25% of Ca
2+
-exchange level is
not enough to generate this stabilizing effect.
We measured the amount of coke formed on ferrierite catalysts by TG after 6.6 h of the
reaction. As shown in Fig. 7, the amount of coke on H-ferrierite exceeded 10 wt%. The
amount of coke decreased with increasing the Ca
2+
-exchange level. Compared with Fig. 6,
it is concluded that the coke formation would be the major reason for the deactivation of
ferrierite and that the Ca
2+
-exchange retards the coke formation, resulting in the high
stability.








0 1 2 3 4 5 6 7
Time on stream / h
100
80
60
40
20
0
O
c
t
a
n
e

c
o
n
v
e
r
s
i
o
n

/

%
Fig. 5. Change in octane conversion with
time on stream on H-ferrierite(8) (), Ca
2+
-
exchanged H-ferrierite(8) with exchange
levels of 25% (), 57% (), and 75% ().
0 1 2 3 4 5 6 7
Time on stream / h
100
80
60
40
20
0
O
c
t
a
n
e

c
o
n
v
e
r
s
i
o
n

/

%
Fig. 5. Change in octane conversion with
time on stream on H-ferrierite(8) (), Ca
2+
-
exchanged H-ferrierite(8) with exchange
levels of 25% (), 57% (), and 75% ().
0 20 40 60 80 100
Ca
2+
-exchange level / %
60
50
40
30
20
10
0
D
e
c
r
e
a
s
e

i
n

c
o
n
v
e
r
s
i
o
n

/

%
Fig. 6. Effect of Ca
2+
-exchange level on the
decrease in octane conversion from initial
(TOS=0.5 h) to final (6.6 h) values on Ca,H-
ferrierite(8).
0 20 40 60 80 100
Ca
2+
-exchange level / %
60
50
40
30
20
10
0
D
e
c
r
e
a
s
e

i
n

c
o
n
v
e
r
s
i
o
n

/

%
Fig. 6. Effect of Ca
2+
-exchange level on the
decrease in octane conversion from initial
(TOS=0.5 h) to final (6.6 h) values on Ca,H-
ferrierite(8).










Fig. 8 shows the change in n-octane conversion with time on stream before and after
the regeneration of Ca(68%),H-ferrierite(8). The initial conversion was 59.1 % and the
conversion gradually decreased with time on stream. The regeneration was carried out
after 6.6 h of the reaction with flowing O
2
(20%)/He at 823 K for 1 h. After the
regeneration, the conversion was recovered to be 56.6%, which was 96% of the initial
value. It is indicated that the irreversible deactivation of the catalyst, such as the
dealumination or destruction of pore structure, would not occur during the reaction and
regeneration.
In order to know the reason why the Ca
2+
-exchange improved the selectivity and
stability, the role of acid sites on the external surface of ferrierite was examined through
the cracking of TIPB. The acid sites on the external surface would accelerate the hydride
transfer because these acid sites do not have so severe steric hindrance as those inside the
pores. The TIPB molecule is too large to enter the pore of ferrierite. Therefore, its cracking
must occur only on the external surface. At 623 K, Ca(39%),H-ferrierite(9) gave the
comparable conversion AAAA













0 2 4 6 8 10 12 14
Time on stream / h
100
80
60
40
20
0
O
c
t
a
n
e

c
o
n
v
e
r
s
i
o
n

/

%
Regeneration
O
2
/He=1/4
823 K, 1 h
Fig. 8. Regeneration of Ca(68%),H-ferrierite(8) during octane cracking at 823 K.
0 2 4 6 8 10 12 14
Time on stream / h
100
80
60
40
20
0
O
c
t
a
n
e

c
o
n
v
e
r
s
i
o
n

/

%
Regeneration
O
2
/He=1/4
823 K, 1 h
Fig. 8. Regeneration of Ca(68%),H-ferrierite(8) during octane cracking at 823 K.
A
m
o
u
n
t

o
f

c
o
k
e

/

w
t
%
0 20 40 60 80 100
Ca
2+
-exchange level / %
15
10
5
0
Fig. 7. Effect of Ca
2+
-exchange level on the
amount of coke formed on Ca,H-ferrierite(8)
during octane cracking for 6.6 h on stream.
A
m
o
u
n
t

o
f

c
o
k
e

/

w
t
%
0 20 40 60 80 100
Ca
2+
-exchange level / %
15
10
5
0
Fig. 7. Effect of Ca
2+
-exchange level on the
amount of coke formed on Ca,H-ferrierite(8)
during octane cracking for 6.6 h on stream.

(26%) of TIPB to the parent H-ferrierite(9) (29%). This indicates that Ca
2+
ions do not
weaken or poison the acid sites on the external surface.
The acid strength was then examined by NH
3
-TPD to know whether the
Ca
2+
-exchange modifies the acidity of H-ferrierite. H-ferrierite(8) showed a desorption
peak at 680 K, whereas Ca(89%),H-ferrierite(8) showed two peaks at 550 and 670 K. This
result indicates that the Ca
2+
-exchange weakens a part of strong acid sites (peak at
670-680 K) to form weak acid sites (550 K). The decrease in the strong acid sites may be
one reason for the promoting effect of Ca
2+
-exchange.
The effect of Ca
2+
-exchange was further examined by XRD. Rietveld analysis of the
measured XRD pattern gave an information about the position of Ca
2+
ions. The result
showed that about a half of Ca
2+
ions are located at the center of 8-MR pores near the
intersection of 10-MR and 8-MR channels. These Ca
2+
ions must hinder the diffusion of
molecules, such as propylene and carbenium ion through 8-MR channels, which would
suppress the bimolecular hydride transfer. This blocking effect may be the additional
reason for the promoting effect of Ca
2+
-exchange.

4. Conclusions
The catalytic cracking of naphtha components, n-heptane and n-octane, was carried out
on various zeolites to obtain light olefins, especially propylene. Zeolites with smaller
pores with 10-MR channels, ferrierite and ZSM-5, are suitable for the formation of olefins.
The Ca
2+
-exchange into H-ferrierite improves the selectivity to olefins as well as the
stability of conversion. The stable conversion is caused by the reduced amount of coke
formed during the cracking reaction. The Ca
2+
-exchange modifies the acidity and pore
structure of ferrierite to suppress the bimolecular hydride transfer for the selective
formation of light olefins.

A part of this work was supported by NEDO (New Energy and Industrial Technology
Development Organization).

5. References
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