Applied Catalysis, 14 (1991) 37-52 31

Elsevier Science Publishers B.V., Amsterdam

Deactivation of zeolites in n-hexane cracking

Norihisa Mori, Satoru Nishiyama, Shigeru Tsuruya* and Mitsuo Masai

Department of Chemical Engineering, Faculty of Engineering, Kobe University, Nada,
Kobe 657(Japan), tel. (+81-78)8811212 (ext. 5240), fax. (+81-78)8023564

(Received 4 October 1990, revised manuscript received 8 January 1991)

Abstract

The deactivation process of the H-type zeolites (H-mordenite, H-Y zeolite, and H-ZSM-5) in n-
hexane cracking was studied using a pulse method in which the emphasis was put on the clarification
of the initial stage of the deactivation of these H-type zeolites. The adsorption behaviors of n-hexane
and ammonia on fresh and used zeolites were compared in order to elucidate the relationship between
the micropore structure of the zeolites and the deactivation by the carbonaceous deposits (coke). The
main deactivation of the H-mordenite (HM) zeolite was found to be caused by pore blockage of the
deposited coke. The H-Y zeolite (HY) was suggested to be deactivated by the proton coverage of the
coke. No deactivation of the H-ZSM-5 (HZ) was observed under the present pulse conditions. These
deactivation behaviors of the H-type zeolites were found to be consistent with the results obtained by a
gravimetric flow method. The initial activity, defined as the conversion at the first pulse, could be
correlated with the strong acidity, irrespective of the micropore structure of the zeolites used. The cor-
relation of both the initial aromatic and coke yields with the strong acidity was discussed in connection
with the micropore structure of the H-type zeolites.

Keywords: acidity, coke, cracking, deactivation, n-hexane, pulse method, zeolites.

INTRODUCTION

Solid acid, particularly zeolite, has been known as an excellent catalyst for
the cracking of hydrocarbons as well as for isomerization reactions [11,and
has become a major commercial catalyst, finding applications in a number of
industrial processes. However, due to the presence of relatively strong acid
sites in the zeolites, a quite rapid decay in activity is observed during the con-
version of organic compounds through the concomitant formation of undesir-
able carbonaceous by-products, referred to as “coke”. Coke deposition which
poisons the acid sites and/or blocks the catalyst pores is the main reason for
catalyst deactivation in gas-phase organic reactions. A major step in the for-
mation of carbonaceous residues is the reaction and conversion of alkylaro-
matics by cyclization, dehydrogenation, further alkylation, etc., leading to po-
lyalkylaromatics and polyaromatics which are coke precursors. The coke
deposits can eventually lower the catalytic activity by site poisoning and/or by

0166-9834/91/$03.50 0 1991 Elsevier Science Publishers B.V.

38

pore blocking which prevents the access of the reactants to the active sites [ 21.
Although most of the studies on catalyst coking have so far been devoted to
the kinetics of coke formation and catalyst deactivation, recent studies on the
detailed mechanism of zeolite deactivation caused by the deposited coke and
on the nature of coke isolated through solvent extraction have been reported
by comparing the changes in its activity and of its adsorption properties as
functions of the amounts of the composition of the coke [ 3-61. It is important
to understand the scheme of deactivation and to limit the rate of deactivation,
from a technological and an economical point of view, no matter what the
catalytic system is.
Usually, studies on the deactivation of oxide catalysts like zeolite have been
performed using a flow reactor [ 7,8]. In this paper, to study in detail the initial
stage of the deactivation, a pulse method was applied to the deactivation pro-
cess of n-hexane cracking over the zeolites, HY, H-mordenite (HM), and H-
ZSM-5 (HZ), each having a different pore structure and acidic properties, in
addition to the flow gravimetric method. The sorption capacities of n-hexane
and ammonia on these zeolites before and after the pulse reactions were related
to the correlation between the deactivation behavior and the pore structures.
We attempt to understand the importance of the initial stage of the catalyst
deactivation based on the consideration that the main part of the deactivation
process will be governed by the initial stage. The initial mode of the catalyst
deactivation is thus considered to mainly affect the subsequent steps in the
deactivation process.

EXPERIMENTAL

Y and X type zeolites were supplied by Union Carbide (SK-40, Si/Al atomic
ratio = 2.5 ) and Toso (NaX, Si/Al atomic ratio = 1.5)) respectively. Mordenite
was purchased from Norton (Zeolon, Si/Al atomic ratio = 7.2). NaZSM-5 zeo-
lite (Si/Al atomic ratio=43) was synthesized according to the procedure in
Mobil patents [ 9,101. Before use, all the zeolites were converted into the pro-
tonated forms via NH4 ion exchange (1 N NHINOB or NH&l aqueous solution
at 373 K) followed by further calcination in air at 773 K for 5 h. The resultant
H-formed zeolites possessed the following degrees of proton ion exchange; 99.6%
for HY, 93.9% for HX, and 99.7% for HZ.

n-Hexane transformation

A pulse reactor (10 mm I.D., stainless) connected to a gas chromatograph

was used under the following conditions: amount of catalyst, 0.5 g; helium flow-
rate, 20 cm3 min-‘; temperature, 573-773 K; pulse size, 4~1; and total pressure,
1 atm. Before the reaction, the catalyst was calcinated at 773 K for 2 h in a
flowing mixture of oxygen and nitrogen (oxygen-to-nitrogen ratio = 1: 4). The
 39

reaction products were analyzed with an on-line gas chromatograph fitted with
a thermal conductivity detector (Shimazu GC-4A) using a column of a Pora-
pak Q (2 rn~ 3 mm, carrier helium of 20 cm3 min-’ flow-rate); the column
temperature was programmed from 345-513 K at a heating rate of 20 K min-‘.
The main products were the cracking products consisting of Cz, C3, Cd, and C,
aliphatics and aromatics (benzene, toluene, and trace of xylene) compounds.
The nearly 100% recovery of the supplied n-hexane was confirmed in this pulse
reactor system without catalyst (blank test). The material balance of n-hex-
ane, the yield of coke, the conversion of n-hexane, and the selectivity were
defined as follows:
Material balance of n-hexane (% ) =

Total moles of products and unreacted n-hexane (based on carbon number)

Moles of n-hexane fed (based on carbon number)

Yield of coke (% ) = 100 -Material balance of n-hexane (2)

Moles of unreacted n-hexane x loo

Coversion of n-hexane (% ) = l- (3)
Moles of n-hexane fed

Moles of each product x loo

Selectivity (% ) = (4)
Total moles of products

It must be noted that “coke” is defined as unrecovered materials deposited in

the zeolite as suggested from eqns. 1 and 2.

BET surface area measurements

Before BET measurements, the HY, HZ, and HM were degassed at 773,773
and 873 K, respectively, for 1 h under ca. l*lO-* Torr. The BET surface area
of these zeolites (0.05 g) were measured at 77 K using a conventional low
pressure adsorption apparatus.

Adsorptions of n-hexane and ammonia, and temperature-programmed

desorption (TPD) of ammonia

Adsorption and TPD measurements were carried out using conventional

low-pressure static-type gas adsorption equipment. It consisted of an adsorp-
tion chamber containing the zeolite sample (0.05 g) and an ionization gauge.
Before the introduction of adsorbed gases, the zeolite samples were evacuated
at 773 K (HY, HZ) and 873 K (HM) for 1 h under ca. l*lO-* Torr. The
adsorption of n-hexane and ammonia were performed by exposing the samples
to 1.33*103 Pa n-hexane and 1.33~10~Pa ammonia, respectively, at room tem-
40

perature. The TPD of ammonia was performed by monitoring the desorbing

ammonia using an ionization gauge after the adsorption of ammonia on the
zeolite by exposing the sample to 1.33~10~Pa ammonia at room temperature.

Thermal gravimetric (TG) measurement of the formed coke by the flow method

A Shimazu MTB-50 thermal gravimetric micro-balance was used to study

the formation of coke accumulation. Activation and coking treatments were
performed in situ in the TG system. Zeolite (0.05 g) was used in all cases.
Following activation in air (100 cm3/min) at 773 K for 2 h, a n-hexane-nitro-
gen gas mixture (nitrogen-to-n-hexane mole ratio, 26; P,.c, = 3.8*103 Pa,
P NS=9.8* lo* Pa) was passed isothermally over the catalyst sample at 773 K
( W/J’= 11 gcat min/mol). Coke formation was directly and continuously mon-
itored by following the increase in sample weight with time.

X-ray diffraction measurement of coke

X-ray diffraction measurements of the unextractable coke-like material in

each zeolite, after the extraction of coked HM and HY catalysts with methyl-
ene chloride, were performed using a Rigaku Denki diffractometer, Model 2171
B (Cu Ka radiation; 28 range of 20-30” ).

RESULTS

Acid properties of H-zeolites used as catalysts

The TPD of ammonia from the HM, HZ, HY, and HX zeolites used as cat-
alysts for the n-hexane cracking are shown in Fig. 1. Both peaks in the range
of the high and low temperatures were observed in the TPD from the HM and
HZ zeolites. The TPD spectra from the HX and HY did not clearly show the
peaks in the high temperature range, though the peak at low temperature was
observed. Since the ammonium desorption peaks at higher temperature cor-
respond to strong acid in the zeolite, the amount of the strong acid was, for
convenience, defined as the area of the ammonia desorption peaks for temper-
atures greater than 573 K. The amounts of total and strong acidities in the H-
type zeolites are summarized in Table 1. The order of the amount of strong
acidities was HM > HZ > HY > HX, which is in agreement with the results re-
ported by Hidalgo et al. [ 111. Fig. 2 illustrates that the TPD of ammonia from
the H-NaM zeolites varied with the degree of the ion exchange of protons.
Table 2 summarizes the variation in the amount of strong acidity with the
degree of the proton ion-exchange, in addition to the total amounts of acidity
in the zeolites. It is evident that the increase in the degree of the ion exchange
 41

I I I I I L
373 L73 573 673 773 8: 73
Temp ( K)

Fig. 1. TPD spectra of ammonia from H-type zeolites.

TABLE 1

Acidities of the H-type zeolites used in this study

Zeolite Total acidity” Strong acidity*

(mmol/g,,J (mmol/g,,,)

HM 2.59 0.82
HZ 1.49 0.49
HY 0.97 0.16
HX 0.48 0.07

“Based on the total area of the TPD spectra of ammonia.

*See text.

of protons of the H-NaM made the amount of the strong acidity increase, which
is consistent with the amount obtained for the H-KM zeolites [ 111.

n-Hexane cracking by the pulse method

Fig. 3 illustrates the variation in the n-hexane conversion over the HM, HZ,
and HY zeolites. At pulse numbers up to approximately ten, the conversion
over the HM was constantly maintained at a high level, but this markedly
decreased upon a further increase in the pulse number. The degree of the deac-
 kmp( K)
Fig. 2. TPD spectraofammonia from H-NaM zeolites: (a) NaM [H(O)-NaM]; (b) H(17)-NaM;
(c) H (50) -NaM; and (d) HM [H (100) -NaM]. The number in parentheses shows the degree of
the ion exchange of H+.

TABLE 2

Acidities of H-NaM zeolites

Degree of the H+ ion exchanged Total acidity” Strong acidity*

(%) (mmol/g,,,) (mmol/g,,, )

100 (HM) 2.59 0.82

50 [H(50)-NaM] 2.46 0.64
23 [H(23)-NaM] 2.36 0.21
17 [H(17)-NaM] 2.22 0.08
0 (NaM) 2.01 0

“Based on the total area of the TPD spectra of ammonia.

*See text.

tivation at pulse numbers above ca. ten tended to increase with the reaction
temperature. A high reaction temperature provided higher activity and also
higher initial deactivation of the HY. The activities of the HY decreased more
slowly than those of the HM. The activity of the HZ also increased with an
 43

100

0
P

r 50
.P
%
e
8

0
0 IO 20 30 LO 50
FUse wmber

Fig. 3. The relationship between n-hexane conversion vs. pulse number: A =HM, 573 K; 0 = HM,
673 K; 0 = HM, 773 K; CB= HY, 673 K; •I = HY, 773 K; 0 = HZ, 673 K; and ?? = HZ, 773 K.

0 -~-.-&--.-w-~~-
I I I I I 1
0 10 20 30 40 50
Puke number

Fig. 4. The relationship between coke yield vs. pulse number: A = HM, 573 K; 0 = HM, 673 K;
0 = HM, 773 K; CD= HY, 673 K; 0 = HY, 773 K; 0 = HZ, 673 K; and ?? = HZ, 773 K.

increase in the reaction temperature. The conversion over the HZ only slightly
decreased even at 50 pulse numbers at higher reaction temperatures. Fig. 4
indicates the coke yield (eqn. 2) obtained by the pulse method as a function of
pulse number. The coke yield over the HM at the reaction temperature of 773
K had a high value, but tended to markedly decrease above ca. ten pulse num-
bers. The sharp decrease in coke yield over the HM at 773 K seems to be iden-
tical with the one for the conversion over the HM illustrated in Fig. 3. The
coke yield over the HY at 773 K tended to decrease with increasing pulse num-
bers. The degree of the decrease in coke yield with the increase in the pulse
number were more mild than over the HM previously described, once again in
agreement with the variation in the conversion over the HY at 773 K (Fig. 3).
In contrast to the HM and HY zeolites, little coke was produced using the HZ
catalyst even at 773 K in the range of pulse numbers studied here.
The variations in product composition of n-hexane conversion over the HM,
44

(b)

Puke number F&e number

Fig. 5. The variation in product selectivity vs. pulse number. Reaction temperature, 773 K; (a)
HM; (b) HY; and (c) HZ.

HY, and HZ at 773 K are shown as a function of pulse number (Fig. 5). Prod-
ucts did not change very much during the pulse reaction of up to 50 pulse
numbers. It is of particular interest to note that over the HZ, no change in
product composition was observed during the pulse reaction as shown in Fig.
5c. The n-hexane conversion over the HZ was found to have higher aromatic
yields than over HM or HY.

Thermogravimetric study of the coke formed using the flow reaction system

The deposition of coke from the n-hexane conversion over the HZ, HY, and
HM zeolites using a flow reaction system have been followed by isothermal
gravimetry (Fig. 6). The initial rate of coking, per unit mass of catalyst, is
clearly increasing in the order: HZ < HY < HM [ 121. The saturation of coke
deposition was observed over the HM at earlier times on stream as compared
to HY or HZ. This behavior of coke deposition on the HM, HY, and HZ zeolites
using the flow reaction system were similar to those observed when using the
pulse method (Fig. 4).
 45

Time ( h )

Fig. 6. The relationship between deposited coke vs. reaction time in n-hexane conversion over H-
type zeolites using a flow reaction system. Reaction temperature, 773 K; W/F= 11 g,., min/mol.

TABLE 3

BET areas and sorption properties of the fresh and used zeolites

Parentheses indicate the relative values based on the fresh ones

BET area n-Hexane sorption Ammonia sorption

(m’/g) amount amount
(mmol/g) (mmol/g)

HM HY HZ HM HY HZ HM HY HZ

Fresh 325 192 405 0.40 0.38 1.11 4.14 2.38 2.58
(1.00) (1.00) (1.00) (1.00) (1.00) (1.00) (1.00) (1.00) (1.00)
Used” 673 Kb 292 161 405 0.15 0.29 1.14 3.88 1.95 2.59
773 K” 250
(0.90) 145
(0.84) 404
(1.00) (0.38)
0.01 (0.78)
0.25 (1.03)
1.15 (0.94)
3.72 (0.82)
1.73 $9;)

(0.77) (0.76) (1.00) (0.02) (0.67) (1.04) (0.90) (0.73) (1:OO)

“After 50 pulse numbers.

bReaction temperature of n-hexane cracking. The coke content increased with the reaction
temperature (see text).

Adsorption of n-hexane and ammonia on fresh and used zeolites

In order to obtain a clue to understand the location and/or the state of coke
deposition, the adsorptions of n-hexane and ammonia on fresh and used zeo-
lites were tried, in addition to the measurement of the BET surface areas of
these zeolites. For used zeolites, we chose the zeolites after 50 pulse numbers
at 673 and 773 K. Table 3 summarizes the results of BET surface areas and the
amounts of adsorption of n-hexane and ammonia. The relative values of used
(coke deposited) zeolite based on fresh zeolite are also shown in the parenthe-
ses of Table 3. The zeolites used at 773 K are considered to deposit more than
46

those at 673 K, as evidenced from the results of the coke deposition under the
pulse method in Fig. 4. On the HM, the adsorption amount of n-hexane con-
siderably decreased with an increase in coke deposition (fresh HM > HM used
at 673 K > HM used at 773 K), on the other hand, the degrees of decrease in
the adsorption amount of ammonia with coke deposition were found to be much
smaller than those of n-hexane. In contrast to the adsorption behavior of the
HM, both the adsorption amounts of the hexane and ammonia on the HY
decreased in an almost similar order with increasing deposition of coke. No
decrease in the adsorption amount of n-hexane and/or ammonia on the HZ,
regardless of its history of use, was observed, in addition to the observation of
constant BET surface area.

Catalytic properties of fresh zeolites and their strong acidities

In order to study the relationship between the catalytic activity of fresh zeo-
lites and acidity, we have focused the conversion at the first pulse number over
each zeolite, which was defined here as an initial activity of the fresh zeolite.
Fig. 7 illustrates the dependence of the initial activities of HM, HY, HX, and
HZ, in addition to various H-NaM zeolites, on the strong acidities, which were
obtained from the TPD spectra of ammonia as defined in Figs. 1 and 2. In a
series of H-NaM zeolites, which have the same pore structure and pore size,
the initial activity was intended to increase with an increase in strong acidity.
The initial activities of the H-type zeolites with different structural features
like the HY and HZ were also plotted as a function of strong acidity. It is of
interest to note that the dependence of the initial activity of the H-type zeolite
in n-hexane cracking on the strong acidity is expressed through a smooth curve,
regardless of the difference in micro pore structure and/or pore size of these
zeolites studied here. The process of coke formation has been reported [ 131 to
include the steps of alkanes+aromatics+polyaromatics, and is easier from
aromatic hydrocarbons than from paraffinic hydrocarbons. To elucidate the

100

0
U 0.5 1.0
Strong aciditycm mollg 1

Fig. ‘7. The relationship between initial conversion vs. strong acidity. Reaction temperature, 773
K;O=H(X)N~M;I-J=HZ;O=HY;O=HX;A=N~Y;~~~V=N~Z.
 41

initial step of coke formation, both the initial yields of coke and aromatic com-
pounds were plotted as a function of strong acidity (Fig. 8). The initial yields
of coke and aromatic compounds here refer to the ones at first pulse number
as initial activity, respectively, as have been defined previously. Fig. 8a illus-
trates the variation in the initial yields of aromatics and coke with strong acid-
ity in the H-NaM zeolites. The initial yield of coke on the H-NaM was found
to have a strong correlation with the initial one for aromatics. The dependence
of the initial yields of aromatics and coke with strong acidity was observed for
the HX, HY, HZ, and HM zeolites, which have different pore structure and
pore size (Fig. 8b). In contrast to the results (Fig. 8a) for a series of H-NaM
zeolites, a parallelism between the variations in the initial yields of aromatics
and in the initial yield of coke as a function of the amount of strong acid was
not observed, though the total yields of the summarized aromatics and coke
tended to increase with an increase in strong acidity, just as has been observed
over a series of H-NaMs in Fig. 8a. On HZ, which has an appreciable amount
of strong acidity, no coke was detected in spite of the considerable high value
of the initial yield of aromatics. On the other hand, on the HM, which has the

I 0.5 1.c , 0.5 1.0

Strong acidity(mmol lg ) Strong acidity(mmol/g)

Fig. 8. The relationship between initial yield vs. strong acidity. (a) H(X) -NaM catalysts; A = ini-
tial aromatic yield; 0 = initial coke yield; c] = initial total (aromatic + coke) yield. (b) H-type
zeolite catalysts (HX, HY, HZ, HM); A = initial aromatic yield; 0 = initial coke yield; 0 = initial
total (aromatic + coke yield).
48

26 4

HV

HM

Fig. 9. XRD spectra of the unextractable coke-like material in the zeolite.

largest amount of strong acidity among the zeolites studied here, the initial
yield of coke was found to be quite high in comparison with that of aromatics.

X-ray diffraction (XRD) spectra of coke

To characterize the carbonaceous product formed in the zeolites, a technique

consisting of treating the coked zeolites at room temperature with a solution
of 47% hydrofluoric acid in order to dissolve the zeolite and to liberate the inner
coke, was followed by the X-ray diffraction (XRD) measurement of the car-
bon-like residues in the HY and HM with the results shown in Fig. 9. The
diffraction peak at 28= 26.37’ has been reported to be assigned to the graphite
(002 ) face [ 71, thus ordered graphite. It is evident that graphitization proceeds
faster in the HY than in the HM. The degree of graphitization of the inner
coke was found to be higher in the HY zeolite than in the HM. These results
seem to reflect the difference in the pore structure of both zeolites. It was dif-
ficult to measure the XRD spectrum of the carbonaceous product in the HZ
since little coke-like residue remained in the HZ after the cracking of the n-
hexane by a flow reactor under the present reaction conditions.

DISCUSSION

The variation in the activity of n-hexane cracking with the pulse number
was found to depend on the H-type zeolite used as a catalyst. Although the
 49

activity over the HM remained almost unchanged up to ca. ten pulse numbers,
the deactivation for n-hexane transformation was found to abruptly proceed
at more than ten pulse numbers. This behavior tended to be strengthened with
an increase in reaction temperature. A considerable amount of the accumula-
tion of the coke on the HM through the pulse method during the n-hexane
cracking was observed during the initial stage as illustrated in Fig. 4. From the
variations in both the activity and the coke accumulation on the HM zeolite
during the initial stage of n-hexane cracking, the mode and site of the coke
deposits on the HM will be discussed in connection with the structural feature
of the HM. Thus, on the HM zeolite, which has a large pore size structure, but
is considered as a pseudo mono-dimensional structure (a two-dimensional
channel network of which one channel is not easily accessible), the modes of
the deactivation are best interpreted as being due to the blockage of its pseudo
mono-dimensional channel by the coke produced, the blockage of the entrance
of the channel by the coke will cause a rapid deactivation during the initial
stage, as observed in Fig. 3. This prediction seems to be furthermore supported
by the data in Table 3. Although the amount of n-hexane adsorption abruptly
decreased when using the HM at 773 K and comparing it with that on the fresh
HM, only a small amount of ammonia adsorbed on the HM used at 773 K
decreased when compared to the value adsorbed on the fresh HM, which was
similar to the behavior between the variation in the BET surfaces of the fresh
and the coked HM zeolites. The blockage of the entrance of the channels might
almost perfectly inhibit the entry of n-hexane molecules into the channel, but
the acid sites, which are active ones for n-hexane cracking and are present in
the channel of the HM, remain intact. On these sites ammonia will be able to
be adsorbed, regardless of the presence and/or absence of coke. Magnoux et al.
[ 41 have indicated that in the coke-free or low coke HM zeolite, the circulation
of nitrogen molecules occurs in all directions, whereas that of n-hexane is mono-
dimensional; at low coke contents, nitrogen can pass through the narrow chan-
nels and attain the volume which has become inaccessible to n-hexane. The
difference of the adsorption behavior between ammonia and n-hexane on the
HM (Table 3 ) can be easily understood if small basic ammonia molecules have
a similar behavior to that of nitrogen molecules.
The catalytic activity of n-hexane cracking over the HY zeolite was found
to gradually decrease from the initial stage of the cracking with an increase in
the pulse numbers. This deactivation behavior of the HY may be interpreted
in connection with the behavior of the adsorption of n-hexane and ammonia
in order to elucidate the deactivation scheme by coke. Both the variations in
the adsorption amounts of n-hexane and ammonia over the HY zeolite were
found to be similar to each other (Table 3), in contrast to the HM zeolite
previously described. A Y-type zeolite has been known to have a three dimen-
sional pore structure with a comparatively large size. The n-hexane molecule
can access the acid sites in the three dimensional cage and the coke deposits
50

on the acid sites will begin with the start of the cracking reaction. The cause
of the deactivation over the HY zeolite could be considered as being due to the
coating ma& by depositing the carboneous material on the active sites, though
the deactivation process through pore blockage by coke can not be denied. This
consideration concerning the deactivation over the HY may be interpreted as
resulting from the fact that the decays of both the adsorption amounts of n-
hexane and ammonia on the HY zeolites, in the order of the fresh HY, the HY
used at 673 K, and the HY used at 773 K (Table 3 ), showed a similar behavior
to each other. No deactivation and coke accumulation in n-hexane cracking
over the HZ were observed (Figs. 3,4) under the present pulse reaction con-
dition and this was also confirmed from the results that no decrease in the
adsorption amounts of n-hexane and ammonia on the HZ zeolites used at 673
and 773 K in the pulse reaction of the n-hexane cracking was observed (Table
3). The profile of the coke accumulation with reaction time in the n-hexane
cracking over each H-type zeolite under a flow reaction system (Fig. 6)) which
had a similar behavior to the ones previously reported [ 121, seems to be con-
sistent with the results for the deactivation behavior of each H-type zeolite
obtained through the pulse technique previously mentioned.
From the point of view of catalytic deactivation, the pulse reaction method
has an advantage over the corresponding flow reaction system in that some
features of the initial stage of the zeolites can be directly observed. It is of
interest to focus on the dependence of the initial activity in the n-hexane crack-
ing over all the H-type zeolites studied here, which was defined as the conver-
sion at the first pulse, on the acidity of the each fresh zeolites, rather than the
steady state value obtained by the usual flow method. The plots of the initial
activity and the strong acidity defined here (see results section) were found to
be represented as an identical curve, irrespective of the zeolites used with dif-
ferent structures and the degree of proton exchange of the mordenite zeolite.
This result suggests that the initial activity in n-hexane cracking over the H-
type zeolites are primarily governed by the strong acidity, irrespective of the
difference in the pore ‘structures of the H-type zeolites used.
Both the initial yields of benzene and coke in n-hexane cracking over the H-
NaM zeolites have been found to increase in a similar manner with the increase
in the strong acidities (Fig. 8a). However, the dependence of both the yield of
benzene and coke on the strong acidity indicated a different behavior when the
zeolites with different pore structures were compared (Fig. 8b ). The aromatic
yield increased in the order of HX, HY, HZ, which is the same order as the
strong acidity in these zeolites. However, the aromatic yield over the HM con-
siderably decreased in spite of the high strong acidity. The yield of coke over
the HZ is abruptly low, while having a significantly high yield of aromatic
compound as already described. Inversely, the HM has a high yield of coke and
a low yield of aromatics. These results from Fig. 8 suggests that the strong acid
sites are important for the production of aromatic compounds which are con-
 51

sidered to be precursors of the coke, if the pore structures of the zeolites are
similar to each other (Fig. 8a). Since the aromatics formed in the HZ zeolite
can be easily removed from the pores during the initial stage of the reaction
before they are converted to coke and/or its precursors, the high aromatic and
low coke initial yields are considered to be obtained over the HZ catalyst. Be-
cause of its quasi-mono-dimensional pore structure in the HM, the aromatics
formed at the initial stage of n-hexane cracking in the HM zeolite may have a
longer residence time in the pores leading to the formation of coke and/or its
precursors during the initial stage of the reaction, in contrast to the case of the
HZ zeolite. The difference in the initial yields of coke and aromatics between
the HM and HZ zeolite may, in addition to the pore structure, also be attrib-
uted to the density of their acidic sites [ 121, a higher acid density zeolite such
as the HM giving a condensation reaction field which favors the formation of
coke and/or its precursor.

CONCLUSIONS

From the results of n-hexane cracking over the H-type zeolites (HM, HY,
and HZ) using a pulse method, the deactivation of the HM zeolite was found
to be due to pore blockage by the deposited coke. It was thought that the HY
zeolite was deactivated by the proton coverage, which is considered to be an
active site, with the coke. No deactivation of the HZ zeolite was observed in
the present pulse condition. These deactivation behaviors of the H-type zeo-
lites were consistent with the adsorption behaviors of n-hexane and ammonia
on the fresh and used zeolites. The initial activity, defined as the conversion
at the first pulse, could be correlated with the strong acidity of the H-type
zeolites. The initial yields of the aromatics and coke were found to depend on
both the strong acidity and the micropore structure of the zeolites.

ACKNOWLEDGEMENT

We gratefully thank Mr. Kenji Nomura for his technical assistance during
this work.

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