Applied Catalysis A: General 288 (2005) 149–157

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Catalytic cracking of n-octane over alkali-treated MFI zeolites

Je Sik Jung, Ji Won Park, Gon Seo *
Department of Applied Chemical Engineering and The Institute for Catalysis Research,
Chonnam National University, Gwangju 500-757, Republic of Korea
Received 23 December 2004; received in revised form 13 April 2005; accepted 22 April 2005
Available online 31 May 2005

Abstract

The catalytic cracking of n-octane over alkali-treated MFI zeolites was studied to investigate the catalytic roles of acidity and pore
structure in the catalytic cracking of naphtha. The alkali treatment on the MFI zeolite induced the dissolution of silica and alumina, resulting in
the loss of strong acid sites and the formation of mesopores. The low acidity and short residence time induced the reduction of cracking
activity, lowering the conversion and enhancing the selectivity for primary cracking products. The alkali treatment, therefore, shows the
cracking path of n-octane in zeolite pores. The acidity was the predominant factor in determining the conversion level and product
composition, so a high conversion and a high yield of alkene were obtained over the MFI zeolite with a large amount of strong acid sites.
Mesopores formed during the alkali treatment suppressed the production of longer alkanes such as hexane and heptane by reducing further
oligomerization. The alkali treatment was not effective in enhancing overall alkene selectivity, but the selectivity for propene was high over
alkali-treated zeolites, due to the rapid elution of primary cracking products.
# 2005 Elsevier B.V. All rights reserved.

Keywords: Catalytic cracking; n-Octane; MFI zeolite; Alkali treatment

1. Introduction primary cracking step of so-called protolytic cracking [4].

The thermal cracking of naphtha is one of the most
important processes in petrochemical industry, producing
raw materials such as ethane and propene. The cracking at
high temperatures, however, requires a huge amount of heat,
and thus, catalytic cracking at lower temperatures by
applying catalysts has been steadily studied [1]. The
reduction of carbon dioxide emissions is also a strong
driving force for the low temperature cracking. Although
several catalysts have been tested, their rapid deactivation
and insufficient olefin yield delay the commercial operation
of the catalytic cracking [2].
Solid acids are well-known catalysts that promote the
cracking of alkane by accelerating the cleavage of C–C
bonds [3]. Carbonium ions formed on Bronsted acid sites are
widely accepted as being the active intermediates in the
* Corresponding author. Tel.: +82 62 530 1876; fax: +82 62 530 1899.
E-mail address: gseo@chonnam.ac.kr (G. Seo).
They are cracked consecutively to alkane and alkene
molecules. Various reactions among primary cracked
products, such as cracking, oligomerization, isomerization,
hydride transfer and cyclization, bring about very complex
reaction products composed of lower alkanes and alkenes.
Since the first desired point of catalytic cracking is the
low temperature operation to save energy and to reduce the
emission of carbon dioxide, the employed catalysts must
have strong acid sites to produce a large amount of active
carbonium ions even at low temperature. The second point is
the selectivity for alkene, especially ethene and propene.
The high selectivity for propene increases the economic
feasibility of the catalytic cracking of naphtha, because the
production routes of propene are not varied compared with
those for ethene. The selectivity for propene is generally
dependent on the extent of the reaction: the selectivity for
propene is usually high at low conversion, while that for
ethene becomes higher with increasing conversion [5]. As a
result, the pore structure and particle size of catalysts, which

0926-860X/$ – see front matter # 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcata.2005.04.047
150 J.S. Jung et al. / Applied Catalysis A: General 288 (2005) 149–157
determine the reaction path and the residence time of the
catalytic cracking, are important factors in determining
product composition.
Zeolites show very different conversions in the catalytic
cracking of n-octane according to their acidities and pore
shapes [6]. The strong acid sites of MOR and MFI zeolites are
responsible for their high initial conversion. On the contrary,
the rapid deactivation on MOR zeolite and negligible
deactivation on MFI zeolite are due to the differences in
the rates of carbon deposit, as determined by their pore
structures. The product compositions obtained over various
zeolites, however, are very similar, regardless of their species
and acidity. The sufficient residence of cracked products in
zeolite particles results in the achievement of re equilibrium
among alkanes and alkenes. Further reactions of cracked
products in zeolite pores, therefore, must be suppressed in
order to enhance the selectivity for primary cracking products
of the catalytic cracking by introducing mesopores and
reducing the number of strong acid sites, while the conversion
of n-octane must be decreased.
MFI zeolites have been widely used in the petrochemical
industry as catalysts. Their strong acidity is suitable for the
cracking, alkylation and isomerization of hydrocarbons [7].
Furthermore, their specific sinusoidal pores suppress the
formation of high molecular oligomers, the precursor of
carbon deposit, resulting in a long catalyst life. The particle
size of zeolites, which determines the residence time of
cracked products in zeolite particles, also affects product
distribution.
Since silica and alumina, the components of the zeolite
framework, are dissolved in alkaline solution, the alkali
treatment of zeolites induces a significant change in their
acidity and pore structure [8]. In addition, the dissolution of
alumina removes aluminium atoms in its framework,
resulting in the loss of strong acid sites. Weak alkali
solutions dissolve a small amount of silica and alumina,
producing mesopores by enlarging the micropores of zeolite.
The treatment of zeolites with strong alkali solutions,
however, destroys their crystal structure, converting them to
amorphous materials with macropores and extremely small
acid sites.
The lowering of acid site concentration and the increase in
pore diameter of MFI zeolite by alkali treatment contribute to
reducing the extent of further reactions, resulting in a
significant change of product composition. The rapid elution
of reactants and cracked products from pores also reduces the
residence time considerably, preserving the primary products.
In this study, we treated MFI zeolite with alkali solutions of
various concentrations, and employed alkali-treated MFI
zeolites as catalysts in the catalytic cracking of n-octane, a
typical component of naphtha. The zeolites showed a wide
variety of product compositions according to the concentra-
tions of the alkali solutions used for treatments. The physico-
chemical properties of the zeolites were examined to confirm
the changes in acidity and pore structure with the alkali
treatment. The catalytic activity and selectivity for alkene
over these catalysts were discussed to verify the effects of
acidity and pore structure on the product composition in the
catalytic cracking of n-octane.
2. Experimental
2.1. Synthesis and alkali treatment of MFI zeolite
A MFI zeolite was synthesized by a hydrothermal reaction,
followed by the procedure described in literature [9]. A
synthetic mixture with the composition of 8K2O
Al2O3

50SiO2
2160H2O was prepared from colloidal silica (silica
content 40 wt%, Aldrich), aluminum hydroxide (64 wt%,
Fluka) and potassium hydroxide (81 wt%, Duksan). The
mixture was heated in an autoclave without stirring under
autogeneous pressure at 190 8C for 2 days, then washed with
deionized water. The ammonium nitrate (98 wt%, Duksan)
solution of 0.1N was used for the cation exchanging of
synthesized K-form MFI zeolite. The zeolite was treated with
the exchange solution at room temperature for 2 days. After
washing with deionized water and filtering, the cake was dried
in an oven of 110 8C. H-form MFI zeolite was obtained by
calcining it at 550 8C for 6 h.
Sodium hydroxide (98 wt%, Daejung) solutions with
various concentrations ranging from 0.1–1.0N were
employed for the alkali treatment of the MFI zeolite. The
suspension of the MFI zeolite in alkali solution was heated at
60 8C for 6 h. Alkali-treated zeolites were washed with
deionized water to remove remained alkali material. Since
the alkali-treated MFI zeolites had sodium ions as cations,
their cations were changed to protons following the cation
exchange procedure described above. The number in the
parentheses after ‘‘MFI’’ denotes the concentration of the
NaOH solution used at the alkali treatment.
2.2. Catalyst characterization
X-ray diffraction patterns of the alkali-treated MFI
zeolites were recorded on an X-ray diffractometer (Regaku
D/MAX Ultima III) with Cu Ka rays at 40 kV and 40 mA.
The scan rate was 38/min for the range of 58–508.
The morphology change of MFI zeolites with the alkali-
treatment was examined by using a SEM (JEOL JSM 5400).
The Si/Al molar ratios of the alkali-treated zeolites were
calculated from the contents of silica and alumina determined
by an EDX unit (NORAN Z-MAX 3000) attached on the
SEM.
The 29Si MAS Solid NMR spectra were measured on a
BRUKER AVANCE 500 spectrometer operating at a
spinning rate of 10.0 kHz at a 29Si frequency of
99.351 kHz with a p/2 rad pulse length of 8 ms. The long
recycles of 30–60 s were used to avoid relaxation effects in
the signal intensities. Typically, 3000 pulse transients were
accumulated, and the 29Si chemical shifts were referenced to
TMS. The 27Al MAS NMR spectra were recorded on the
 J.S. Jung et al. / Applied Catalysis A: General 288 (2005) 149–157 151

same spectrometer operating at a 27Al frequency of

130.325 kHz and a spinning rate of 10.0 kHz with a p/
2 rad pulse length of 5 ms and a recycle delay of 1 s. The
spectra were obtained with an acquisition of ca. 2000 pulse
transients. The 27Al chemical shifts were reported relative to
Al(H2O)63+ solution.
Adsorption and desorption isotherms of nitrogen on the
alkali-treated MFI zeolites were obtained at 77 K by using a
nanopore analyzer (KICT-3000). Zeolite samples were
evacuated at 150 8C for 1 h prior to the exposure of them to
nitrogen gas. Their surface areas were calculated by
applying the BET equation and pore size distributions were
obtained by the analysis based on the BJH method.
The variation of acidity of the MFI zeolites with the alkali
treatment was investigated from their TPD profiles of
ammonia. The zeolite samples of 0.1 g charged in a quartz
tube (o.d. = 1/4 in.) were activated in a helium flow of
30 ml min1 at 550 8C for 1 h, and then cooled to 150 8C.
Ammonia was supplied to dehydrated zeolite samples as
pulses until they were saturated. After purging with the
helium flow of 100 ml min1 for 1 h to remove physically
adsorbed ammonia, the temperature of the samples was
raised to 900 8C at a rate of 10 8C min1. Desorbed
ammonia was detected by using a thermal conductivity Fig. 1. XRD patterns of alkali-treated MFI zeolites.
detector.
A gravimetric adsorption system equipped with a quartz
balance was employed to obtain the uptake curves of o- 3. Results and discussion
xylene. The zeolite samples of 0.15 g loaded in a quartz
basket were evacuated at 300 8C for 24 h. The o-xylene 3.1. Physico-chemical properties of alkali-treated MFI
(99%, Yaukuri) vapor of 31 kPa was supplied to the zeolites
evacuated zeolite samples at 120 8C. The uptake curves of o-
xylene were recorded from the increase in the mass of the Since alkali solutions dissolve silica and alumina of the
samples during its adsorption. zeolite framework, the alkali treatment of the MFI zeolite
induces a significant change in its shape and pore structure
2.3. Catalytic cracking of n-octane [10]. Fig. 1 shows X-ray diffraction patterns of the alkali-
treated MFI zeolites. Characteristic diffraction peaks
The catalytic cracking of n-octane over the alkali-treated attributed to MFI zeolite still remained even on the
MFI zeolites was carried out on a conventional flow reactor. MFI(0.5) zeolite. The MFI(1.0) zeolite, however, did not
A zeolite catalyst of 0.15 g was charged at the center of show any characteristic diffraction peaks, indicating the
stainless steel reactor tube (o.d. = 1/2 in.) and activated in a complete loss of its structure.
helium flow of 50 ml min1 at 500 8C for 2 h. After the Table 1 shows the recovery yields and Si/Al molar ratios
reactor temperature was adjusted to the desired value, n- of the alkali-treated MFI zeolites. As the concentration of
octane vapor diluted in the helium flow was fed. n-Octane the NaOH solution increases, the increased solubilities of
was vaporized in a bubbler heated by a constant temperature silica and alumina lowered their recovery yields. The
circulator (KOMA, KR-08) maintained at 59.9 8C. The decrease in the Si/Al molar ratio with increasing alkali
partial pressure of n-octane was kept at 10 kPa. A six-port concentration revealed a relatively higher solubility of
valve took sample pulses from the product stream and alumina in alkali solution compared to that of silica.
injected them to a directly connected gas chromatograph
(Donam DS6200) equipped with a Porapak Q column Table 1
(1.8 mm  2 m) and a FID detector. The conversion of n- Si/Al molar ratios and recovery yields of alkali-treated MFI zeolites
octane was defined as the fraction of n-octane consumed and Catalyst Recovery yield (%) Si/Al molar ratio
the selectivity for a given species was defined as the fraction MFI(orig.) – 14.6
of n-octane consumed to produce the species per total MFI(0.1) 85 14.3
consumed n-octane. The olefin yield was calculated by MFI(0.3) 69 12.5
multiplying the sum of the selectivities for every alkene MFI(0.5) 65 12.1
produced with the conversion. MFI(1.0) 43 7.8
152 J.S. Jung et al. / Applied Catalysis A: General 288 (2005) 149–157

Fig. 2. SEM photos of alkali-treated MFI zeolites.

The alkali treatment causes a significant change on the
surface of the MFI zeolite. As shown in Fig. 2, many small
holes with diameters of about 10 nm were formed on the
surface of the MFI(0.5) zeolite. The formation of nano-sized
holes was very clear on the MFI(1.0) zeolite. Although the
crystal structure of the MFI(1.0) zeolite was completely
destroyed (Fig. 1), its particle shape was still maintained.
This means that the alkali solution dissolved silica and
alumina of the inside of zeolite particles first.
The alkali treatment of MFI zeolite also induces
considerable change in the coordination of silicon and
aluminium atoms which composed the zeolite framework.
Fig. 3 shows MAS NMR spectra of 29Si and 27Al in the
alkali-treated MFI zeolites. Most of the silicon and
aluminium atoms of the MFI(orig.) zeolite were tetra-
hedrally coordinated, confirming its high crystallinity. The
alkali treatment caused considerable decreases in the peaks
of both 29Si and 29Al, indicating that the loss of zeolite
framework. Small peaks of 29Si and 29Al of the MFI(1.0)
zeolite clearly showed that most of silicon and aluminium
atoms lost their regularly coordinated state after treatment
with strong alkali solutions.

29 27
Fig. 3. MAS NMR spectra of alkali-treated MFI zeolites: (A) Si MAS and (B) Al MAS.
 J.S. Jung et al. / Applied Catalysis A: General 288 (2005) 149–157 153

Fig. 4. N2 adsorption isotherms of alkali-treated MFI zeolites.

The loss of silica and alumina by alkali treatment induces a
significant change in the pore structure of MFI zeolite. The
adsorption isotherm of nitrogen on the MFI(orig.) zeolite was
a typical Langmuir one, as shown in Fig. 4. On the contrary,
those of MFI(0.5) and MFI(1.0) zeolites showed hysteresis,
indicating the presence of mesopores. A partial dissolution of
silica and alumina causes the enlargement of micropores,
resulting in the formation of mesopores on the alkali-treated
MFI zeolites. The adsorption amount of nitrogen at low
pressure corresponding to micropores was considerably
decreased on the MFI(1.0) zeolite, while the large hysteresis
showed the formation of meso- and macropores.
Table 2 lists the changes in the surface area and pore
volume of the alkali-treated MFI zeolites according to the
concentrations of employed alkali solution. The treatment of
the MFI zeolite(orig.) with 0.1N NaOH solution did not
cause any significant changes in its surface area or pore
volume. The large surface area and pore volume due to the
presence of mesopores of the MFI(0.3) zeolite indicated a
partial collapse of micropores. The significant increase in
the mesopore surface area of the MFI(0.5) zeolite
accompanied by the decrease in micropore volume showed
clearly the formation of mesopores by the dissolution of
micropores. The strong NaOH solution of 1.0N completely
destroyed the zeolite micropores and resulted in a negligible
amount of micropore volume.
The formation of mesopores accelerates the diffusion
rates of hydrocarbon molecules in the MFI zeolite. Fig. 5
shows the uptake curves of o-xylene on the alkali-treated
MFI zeolites at 120 8C. About 300 min was required for the
saturation of o-xylene on the MFI(orig.) zeolite. The
saturation of o-xylene, however, took only 10 min on the
MFI(0.5) zeolites, even though its uptake amount was larger
than that of the MFI(orig.) zeolite by seven times. The
uptake of o-xylene on the MFI(1.0) zeolite was too rapid to
measure the saturation time, but the uptake amount did not
increase compared with the MFI(orig.) zeolite. The alkali-
treatment enhanced both the rate and the amount of o-xylene
uptake on the MFI zeolite by forming mesopores when its
structure was maintained. The treatment with strong alkali
solution, however, induces the formation of meso- and
macropores, resulted in very rapid mass transfer in catalyst
particles.
The removal of aluminium atoms from skeletal during the
alkali treatment reduces the number of acid sites. The

Table 2
Surface areas and pore volume of alkali-treated MFI zeolites
Catalyst Surface area Pore volume
(m2 g1) (cm3 g1)
BET Meso Micro Meso
MFI(orig.) 275 32 0.092 0.063
MFI(0.1) 279 34 0.090 0.068
MFI(0.3) 259 49 0.054 0.114
MFI(0.5) 297 75 0.029 0.230 Fig. 5. Adsorption of o-xylene on alkali-treated MFI zeolites: (*)
MFI(1.0) 154 67 0.002 0.330 MFI(orig.), (^)MFI(0.1), (4) MFI(0.5) and (&) MFI(1.0).
154 J.S. Jung et al. / Applied Catalysis A: General 288 (2005) 149–157
Fig. 6. TPD profiles of ammonia from alkali-treated MFI zeolites.
destruction of zeolite structure also causes the loss of strong
acid sites. Fig. 6 shows TPD profiles of ammonia from the
alkali-treated MFI zeolites. The decrease in the number of
strong acid sites on the MFI(0.5) zeolite was clear. The
MFI(1.0) zeolite did not show any peaks at the high
temperature region, indicating that most of the strong acid
sites disappeared due to the destruction of the zeolite structure.
3.2. Catalytic cracking of n-octane
The alkali-treated MFI zeolites showed a negligible
deactivation in the catalytic cracking of n-octane at 300–
600 8C when their structures were retained. Their sinusoidal
pore structure prevents the formation of large molecules,
suppressing carbon deposits [11]. But the MFI(1.0) zeolite,
which lost the MFI crystallinity completely due to alkali
treatment, deactivated slowly as expected. Although the
Fig. 7. The conversion (A) and the selectivity for alkene (B) over the MFI(orig.) zeolite in the catalytic and thermal cracking of n-octane at different reaction
temperatures.
deactivation rate was different according to the concentra-
tions of the employed alkali solutions, the decrease in the
conversion after 1 h was not significant. The conversions,
yields and selectivities obtained after the lapse of 1 h,
therefore, were used for the discussion about the catalytic
properties of the alkali-treated MFI zeolites.
Fig. 7 shows the conversion and the selectivity for alkene
over the MFI(orig.) zeolites at various temperatures. The
increase in the conversion with the reaction temperature was
natural. The increase in the selectivity for alkene with the
reaction temperature, however, was due to further cracking
of cracked alkane into smaller alkanes and alkenes at higher
temperatures. The dotted lines in Fig. 7 denote the
conversion of n-octane and the selectivity for alkenes in
thermal cracking, respectively. The conversion without
catalyst was extremely low, about 2% at 550 8C, but it
increased rapidly and reached about 20% at 600 8C. The
selectivity for alkene in the thermal cracking showed
different behavior from that of catalytic cracking because of
the differences in their reaction mechanisms. Since small
alkenes are major products in the thermal cracking, the
selectivity for alkene is high compared with the catalytic
cracking. Even though the extent of thermal reaction was
considerably smaller than that of the catalytic reaction at
550 8C, the thermally formed intermediates might affect the
catalytic cracking. The catalytic properties of the MFI
zeolite with the alkali treatment, therefore, were discussed,
based on the results obtained at the temperature of 500 8C, to
exclude completely the contribution of thermal cracking.
Since the alumina and silica of the zeolite framework are
dissolved by alkali solution, the alkali treatment on the MFI
zeolite brings about a considerable difference in the product
composition of the catalytic cracking. Table 3 presents the
product composition and conversion of n-octane over the
alkali-treated MFI zeolites. Various hydrocarbons – even
xylene – were produced on the MFI(orig.) zeolite, but the
product composition on the MFI(1.0) zeolite was -very
simple. Only the alkenes and alkanes of C2–C5 were
obtained. This simple product distribution can be explained
 J.S. Jung et al. / Applied Catalysis A: General 288 (2005) 149–157 155

Table 3
Product composition of the catalytic cracking of n-octane over alkali-treated MFI zeolites at 500 8C
Catalyst MFI(orig.) MFI(0.1) MFI(0.3) MFI(0.5) MFI(0.6) MFI(1.0)
Product composition (%)
C1 0.7 0.5 0.4 0.3 0.2 –
C¼2 14.2 10.9 8.7 5.2 3.1 0.3
C2 3.5 2.9 2.3 1.6 1.2 0.2
C¼3 21.4 19.0 15.6 11.9 9.5 1.2
C3 12.5 11.5 9.6 5.2 3.1 0.3
C¼4 6.1 6.0 5.3 3.2 2.7 0.5
C4 9.9 9.6 8.1 3.7 2.9 0.5
C¼5 0.2 0.6 0.5 0.1 0.1 –
C5 3.7 4.3 3.5 2.5 2.1 0.5
C¼6 0.4 0.5 0.4 0.3 0.2 –
C6 0.7 0.3 0.3 0.1 – –
C¼7 – – – – – –
C7 3.0 1.5 1.6 0.61 0.1 –
Xylene 1.4 0.9 0.7 – – –
C8 22.2 31.8 43.2 65.4 74.7 96.6
Conversion (%) 77.7 68.2 56.8 34.6 25.3 3.4

by protolytic cracking [12]. The primary cracking of n- usually cracked into smaller alkane and alkene molecules,
octane produces C4 and C¼ ¼ ¼
4 , C3 and C5 (either C3 and C5), the yields of alkane and alkene increase simultaneously with
¼ ¼
and C2 and C6 (either C2 and C6); further cracking of longer conversion. The contents of lower alkanes and alkenes,
alkenes above C5 produces smaller alkanes and alkenes. As however, were considerably different: the contents of C¼ 2 þ
the number of strong acid sites of catalysts and the residence C¼3 were high in alkene, while those of C2 + C3 were
time in catalyst particles increase, consecutive reactions relatively low. The higher alkene was easily cracked on
such as cracking, hydride transfer and oligomerization strong acid sites, so its contents should be low, resulting in
results in complex reaction products. The content of C2–C4 high contents of C¼ ¼
2 þ C3 in the product stream. On the
hydrocarbons was high over the MFI(orig.) and MFI(0.1) other hand, the low reactivity of higher alkane brought about
zeolites. A simultaneous increase in the contents of C5, C6 its high contents in the product streams even at high
and C7 alkanes might be due to the oligomerization of lower conversions. Moreover, the oligomerization of small alkenes
alkanes and alkenes on increasing their contents in zeolite and alkanes produced poorly reactive alkanes, resulting in a
pores. Relatively inactive alkenes and alkanes were low fraction of C2 + C3 in alkane. As a result, it is impossible
accumulated in the product stream with further reactions. to enhance solely the selectivity for alkene in the catalytic
The variations of conversion and the selectivity for cracking of alkane.
propene with the concentration of alkali solution seem to
indicate the effects of acidity and pore structure on the
catalytic cracking. Fig. 8 shows the gradual decrease of the
conversion along with the increase in the concentration of
employed alkali solution. The loss of strong acid sites with
alkali treatment was clear, as shown in the 27Al MAS NMR
spectra (Fig. 3) and TPD profiles of ammonia (Fig. 6). Thus,
the conversion decreased with the decrease in the acidity of
the MFI zeolite. On the other hand, the selectivity for alkene
maintained a level of 55–62% without a large variance,
regardless of the conversion level. There may be a balance
between opposite reactions: those which produce alkenes
and those with consume alkanes. Strong acid sites worked as
active sites for oligomerization as well as for cracking. The
simultaneous progress of alkene consuming through
oligomerization and alkene producing through cracking
maintained the selectivity for alkene.
The suggestion was supported by the variations of the
yields of alkane and alkene with the conversion (Fig. 9). In Fig. 8. The variation of the conversion and the selectivity for alkene with
the calculation of the yield of alkane, n-octane was excluded NaOH concentration over the alkali-treated MFI zeolites in the catalytic
because it was just a reactant. Since alkane molecules are cracking of n-octane.
156 J.S. Jung et al. / Applied Catalysis A: General 288 (2005) 149–157
Fig. 9. The variations of the yields of the alkane (A) and alkene (B) with conversion over the alkali-treated MFI zeolites in the catalytic cracking of n-octane.
Fig. 10 shows the variation of the selectivity for ethene
and propene with the conversion. At a low conversion, the
selectivity for propene was high, while that for ethene was
low. The protolytic cracking of n-octane tended to produce
propene, resulting in a high selectivity for propene at the
initial stage. On the catalysts with meso- and macropores
formed by the alkali treatment, further oligomerization and
cracking were suppressed by rapid elution of primary
cracking products, maintaining high selectivity for propene.
The decrease in the selectivity for propene with
increasing the conversion is related to the reactivity of
propene being than higher that of ethene. Its large
consumption in the oligomerization with alkane lowered
its selectivity at high conversion. On the contrary, the
selectivity for ethene increased. The relatively low reactivity
of ethene compared with propene accumulated it in the
product stream. The long residence time of cracking
Fig. 10. The variation of the selectivity for ethene and propene with
conversion over the alkali-treated MFI zeolites in the catalytic cracking
of n-octane.
products in micropores and consecutive reactions over
highly concentrated strong acid sites induced further
oligomerization and cracking, resulting in a gradual increase
of the selectivity for ethene with increasing the conversion.
4. Conclusions
The alkali treatment on the MFI zeolite induced the
dissolution of alumina and pore walls, resulting in the
lowering of acidity and the formation of mesopores. The
alkali-treated MFI zeolites showed different catalytic
behaviors from the original MFI zeolite: the conversion
decreased with the loss of strong acid sites and the reduction
of the residence time. The overall selectivity for alkene was
not varied largely, due to the simultaneous occurrences of
further cracking and the oligomerization of cracking
products. The number of strong acid sites was the
predominant factor in determining the conversion, but the
mesopores also influenced the selectivity for propene, due to
its rapid elution from zeolite particles.
Acknowledgement
This work was supported by a grant (BB1-201) from the
Carbon Dioxide Reduction and Sequestration R&D Center,
one of the 21st century frontier programs funded by the
Ministry of Science and Technology of the Korean
Government.
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