Molecular Catalysis 461 (2018) 80–85

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Molecular Catalysis
journal homepage: www.elsevier.com/locate/mcat

Catalytic properties of microporous zeolites in the catalytic cracking of m- T

diisopropylbenzene
⁎
Byung-Geon Parka, Kyong-Hwan Chungb,
a
Department of Food and Nutrition, Kwangju Women’s University, 165 Sanjung-dong, Gwangju, 62396, Republic of Korea
b
Department of Environmental Engineering, Sunchon National University, 255 Jungang-ro, Sunchon, Jeonnam, 57922, Republic of Korea

A R T I C LE I N FO A B S T R A C T

Keywords: The catalytic cracking of m-diisopropylbenzene, which is produced as a byproduct of the phenol production
Catalytic cracking process, was studied over various microporous zeolite catalysts. The zeolites had different acidity and pore
m-Diisopropylbenzene structures. The highest conversion of m-diisopropylbenzene in catalytic cracking was achieved on the MWW
MWW zeolite zeolite catalyst. BEA and FAU zeolite catalysts also showed considerably high conversion. The MWW zeolite
Cumene
exhibited a high selectivity for benzene and cumene compared to the other zeolites. The conversion of m-dii-
Benzene
sopropylbenzene on a MWW zeolite catalyst exceeded 90% at 400 °C. The yield of cumene plus benzene was
approximately70% in catalytic cracking over MWW zeolite. The deactivation of MWW zeolite catalysts by
carbon deposition on the catalyst could be neglected at high reaction temperatures, whereas it was quite serious
on the zeolite catalysts with the MOR structure. Benzene might be produced by a secondary reaction of inter-
mediates in the large pore channels during the retention time.

1. Introduction chloride catalysts [18]. In the process of cumene production, wasteful

Aromatic compounds, such as benzene, toluene and xylene, are
important raw materials in the petro-chemical and fine chemical in-
dustry. On the other hand, their demand is not always met by the
supply. The amount of benzene produced is insufficient to meet the
demand, whereas the production of toluene exceeds its demand. To
control the proportion between demand and supply, benzene from p-
xylene is produced from selective toluene disproportionation [1–3] and
the alkylation of aromatic compounds [4–6]. In other methods, benzene
is supplied from the catalytic cracking of aromatic byproducts formed
in the naphtha cracking or phenol production process [7–9]
Many processes have been developed as industrial syntheses for the
production of phenol, but only the Hock process for cumene oxidation
[10,11] and the Dow process for toluene oxidation [12–14] are im-
portant industrially. The other processes have been rejected because of
their high cost. The cumene-phenol process is derived from the dis-
covery of cumene hydroperoxide and its cleavage to acetone and phenol
[15,16]. Phenol is produced predominantly by this cumene-phenol
process in plants. The process consists of the cumene production pro-
cess and phenol production process. Two byproducts were also pro-
duced during all processes, which reached approximately 10% against
the total amount of phenol production [17]. Cumene is produced from
benzene alkylation with propene on phosphoric acid or aluminum
byproducts are obtained, which consist of isomers of diisopro-
pylbenzene (DIPB), triisopropylbenzene (TIPB), butylbenzene, and
heavy unknown aromatics [19].
m-Diisopropylbenzene (m-DIPB) contains two isopropyl groups on
benzene and is formed in higher quantities than other DIPB isomers and
TIPB in the byproduct. DIPBs react with benzene and can be used as an
intermediate for the phenol production process. The byproduct can be
used as a fuel oil in the industrial field without treatment, but it has a
problem because aromatic compounds in the byproduct do not burn
completely.
The catalytic cracking behaviors of aromatic compounds depend on
the acidity and pore structure of the catalyst. The strength of acidity
affects the cracking behavior and catalyst deactivation by the deposi-
tion of polymerized high boiling hydrocarbons. The cracking behavior
on zeolite catalysts, which have linear pore channels, exhibit high para-
selectivity, but serious catalyst deactivation can occur in the pore
channels, which block the pores easily by high-boiling aromatic com-
pounds. On the other hand, MWW zeolite has a pillow-type structure
formed with two 10-membered rings, which are multidimensional
channels [20]. One of them is sinusoidal and the other containing large
supercages is defined by the 12-membered rings with a 7.1 Å inner
diameter and an 18.2 Å height [21]. In MWW zeolite, no high-boiling
aromatic products were produced due to restrictions by the pore

⁎
Corresponding author.
E-mail address: chung-sea@hanmail.net (K.-H. Chung).

https://doi.org/10.1016/j.mcat.2018.10.008
Received 25 June 2018; Received in revised form 11 October 2018; Accepted 14 October 2018
2468-8231/ © 2018 Published by Elsevier B.V.
B.-G. Park, K.-H. Chung Molecular Catalysis 461 (2018) 80–85

entrance, so carbon deposition was difficult. Thus, MWW zeolite has
been used in the reaction process using relatively large molecular re-
actants, such as the alkylation of isopropy1naphtalene [22], skeletal
isomerization of 1-butene [23], and disproportionation of toluene [24].
In this study, the catalytic cracking behaviors of m-DIPB and the
byproduct were examined on various zeolite catalysts, which have
different pore structures and acidity. Variation of the product dis-
tribution by the difference in pore structure of the zeolite catalysts was
also investigated based on the adsorption-desorption behavior of o-xy-
lene. The product distribution suggested a potential route for the re-
covery of profitable raw materials from the byproducts formed in the
isopropylation of benzene as a step in phenol production.
2. Experimental
2.1. Materials
m-Diisopropylbenzene (m-DIPB, Aldrich, 96%) and byproducts were
provided from Kum-Ho P&B Co. and used as reactants. MWW (MCM-22;
Si/Al = 13) zeolite was prepared according to the methodology re-
ported elsewhere [25]. A gel containing hexamethyleneimine was em-
ployed as the structure directing agent. The gel was crystallized in a
Teflon-lined autoclave at 150 °C for 9 days with stirring. Na-form zeo-
lites were transformed to the H-form by ion exchange with 0.2 M
NH4NO3. Hydrothermally synthesized MFI (ZSM-5; Si/Al = 13) was
applied after ion exchange into the H-forms. MOR (Si/Al = 10, Tosoh
Co.), FAU (Si/Al = 14, Tosoh Co.), and BEA (Si/Al = 13, PQ Co.)
zeolites were also introduced in the reaction. The Si/Al ratios of the
catalysts were adjusted to 10 to 14 to exclude the influence of the
different acidity. Table 1 lists the Si/Al molar ratios and physical
properties of the zeolites.
2.2. Catalytic cracking of m-DIPB
The catalytic cracking reactions were performed in a fixed bed and
continuous flow reactor at atmospheric pressure. After the catalyst was
pretreated at 500 °C for 1 h, the reactant (m-DIPB) was fed from a mi-
crofeeder with nitrogen gas as a carrier at the desired W (catalyst
weight) / F (flow rate of total gas) ratio and temperature. The eluted
compounds were trapped by an ice bath and analyzed by gas chroma-
tography (GC, Donam Co., FID, column; DB-1, J&W Scientific Co.).
Conversion was defined as 1-(rate of m-DIPB recovery) / (rate of m-
DIPB feed). The yield was defined as the (rate of formation of the dis-
cussed compound) / (rate of m-DIPB feed).
compositions of the zeolites were analyzed by energy dispersive X-ray
(EDS; Norans, S-MAX 400) as an attachment to the scanning electron
microscope. The N2 isotherms were recorded using an automatic vo-
lumetric adsorption apparatus (Miraei SI, Porosity-QX) at the liquid N2
temperature. Evacuation of the samples was carried out at 130 °C for 1 h
before N2 adsorption.
Gravimetric measurements of o-xylene adsorption-desorption were
performed on a highly sensitive microbalance (quartz glass spring
balance). After the zeolite catalysts (0.1 g) were evacuated at 550 °C for
2 h under a pressure of less than 10−4 Torr, the measurements were
taken at 120 °C and at an o-xylene pressure of 10 Torr. The Brunauer-
Emmett-Teller (BET) surface area of the catalysts before and after the
cracking reaction was measured from the N2-adsorption isotherm at
liquid nitrogen temperature. NH3-temperature programmed desorption
(NH3-TPD) was performed according to the typical method. The cata-
lysts were evacuated at 550 °C for 1 h and then exposed to NH3 gas flow
at room temperature for 30 min. The temperature was increased to
550 °C at a constant heating rate of 10 °C/min under helium gas flow.
The relative amount of ammonia desorbed from the catalysts was de-
termined by TCD.
3. Results and discussions
3.1. Physicochemical properties of the zeolites
Fig. 1 presents XRD patterns of the zeolites. The characteristic peaks
of the zeolites were in accordance with those reported elsewhere [26].
Fig. 2 presents SEM images of the zeolites. The MWW zeolite was larger
than 10 μm, whereas that of BEA zeolite was less than 0.2 μm. The
particle sizes of FAU and MFI were uniform at 0.5 μm. The type of N2-
isotherms of the zeolites is represented as a Langmuir isotherm, which
was derived from a uniform micropore. The BET surface areas were
200–700 m2/g, as listed in Table 1.
Fig. 3 presents the NH3-TPD profiles of the zeolites. The profile of
FAU zeolite revealed a single desorption profile. In contrast, the profiles
of the other zeolites were obtained as double profiles at 200 °C and
300 °C–500 °C, respectively. The first profile appeared at approximately
200 °C due to the desorption of NH3 adsorbed physically on the surface
of the zeolites. The second profile was assigned to the desorption of NH3
on the acid sites of the zeolites [27]. The NH3-TPD profiles of MFI and
MOR zeolites indicated the presence of acid sites on the structure. In

2.3. Characterization of the zeolites

MWW
X-ray diffraction (XRD, D-MAXS-3000/PC, Rigaku) was carried out
using nickel filtered Cu Kα X-rays (40 kV, 40 mA) with a 2°/min scan
MFI
rate. The morphologies and particle sizes of the zeolites were estimated
Intensity (a. u.)

by scanning electron microscopy (SEM, Hitachi S-4800). The Si and Al

Table 1 MOR
Physical properties of the zeolite catalysts used in this work.
Zeolite Si/Al Pore BET Micropore Source
molar diameter (Å) Surface volumea (cm3/
ratio (-) area (m2/g) g)
FAU
MWW 13 5.6 × 5.6 420 0.15 synthesized
BEA 13 7.6 × 6.4, 690 0.19 PQ Co.
5.5 × 5.5
FAU 14 7.4 × 7.4 700 0.24 JRC-Z-HY5.5 BEA
MOR 10 6.5 × 7.0, 410 0.13 JRC-Z-HM10
2.6 × 5.7
5 10 15 20 25 30 35 40
MFI 14 5.3 × 5.6, 260 0.12 synthesized
5.1 × 5.5 2
a
determined from t-plot method. Fig. 1. XRD patterns of MWW, BEA, MOR, FAU, and MFI zeolites.

81
B.-G. Park, K.-H. Chung Molecular Catalysis 461 (2018) 80–85

Fig. 2. SEM images of MWW, BEA, MOR, FAU, and MFI zeolites.

contrast, the amount of NH3 desorbed at lower temperatures was larger
on the BEA and FAU zeolites. The acid strength can be evaluated by the
maximum peak temperature (Tmax) of desorption peak relating to the
activation energy for desorption of ammonia [28]. The acid strength of
MWW zeolite was similar to that of MFI zeolite. The order of the acid
strength was FAU≒BEA < MWW≒MFI < MOR.
Fig. 4 presents the adsorption behavior of o-xylene on MWW, BEA,
MOR, FAU, and MFI zeolites. The behaviors indicate the diffusion of o-
xylene inside the pores of the zeolites. o-Xylene adsorbed rapidly on
BEA and FAU, which have a wide pore space. The levels of o-xylene
adsorption on MOR and MWW were smaller than those on the BEA and
FAU zeolite catalysts. The adsorption of o-xylene on MFI zeolite, which

82
B.-G. Park, K.-H. Chung Molecular Catalysis 461 (2018) 80–85

BEA MWW
FAU MOR Tmax
MFI

TCD response (a. u.)

Tmax Tmax

0 200 400 600 0 200 400 600

Temperature (oC) Temperature (oC)
Fig. 3. NH3-TPD profiles from MWW, BEA, MOR, FAU, and MFI zeolites.

has a narrow pore entrance and bent pore structure, was slower than
250 BEA those of the other zeolites. This suggests that the stereo hindrance by
FAU different pore structures of the zeolites might be influenced in the re-
actions.
200

3.2. Influence of the pore structure of the zeolites in cracking

150
Conversion and selectivity are influenced by the acidity and pore
structures of the catalysts in the catalytic reaction using porous solid
100
-

acid catalysts. Therefore, the Si/Al molar ratios of the zeolite catalysts
MWW
were adjusted to10-14 to reduce the effect of acidity of the catalysts.
The catalytic properties of the zeolites might be influenced by the dif-
50 MFI ference in pore structure and acidities derived from different zeolite
MOR
structures. Fig. 5 shows the conversion and chemical composition of the
0 products from the catalytic cracking of m-DIPB on the zeolites. The
0 30 60 90 120 results differed remarkably according to the zeolite species. Conver-
sions on the MWW and BEA zeolite catalysts were as high as 80% at the
initial reaction. Deactivation of MWW and BEA zeolites occurred slowly
Fig. 4. Adsorption of o-xylene on MWW, BEA, MOR, FAU, and MFI zeolites.
as the reaction proceeded. In contrast, conversions on the MOR and
FAU zeolites were ca. 50%, and the conversions were reduced to below
20% after a 2 h process time. The conversion on MFI zeolite was ex-
cessively low.

m-DIPB p & o-DIPB Cumene Benzene Others

MWW
100
MFI FAU MOR BEA MWW

80 BEA
Catalysts

60 MOR

40
FAU

20
MFI

0
0 1 2 3 4 5 0 20 40 60 80 100

Time on stream (h) Composition (%)

Fig. 5. Changes in the conversion with time on stream (A) and chemical composition of outlet gas (B) in the dealkylation of m-DIPB on various zeolites at 350 °C W/
F = 5.90 g·h·mol−1 and loading amount of catalyst = 0.2 g. Product was collected for 60 min after 2 h of time on stream.

83
B.-G. Park, K.-H. Chung Molecular Catalysis 461 (2018) 80–85

Fig. 6. Changes in the conversion with time on stream (A) and chemical composition of outlet gas (B) in the dealkylation of m-DIPB on MWW zeolites. W/
F = 5.90 g·h·mol−1 and loading amount of catalyst = 0.2 g. Product was collected for 60 min after 2 h of time on stream.

m-DIPB p & o-DIPB Cumene Benzene Others zeolites because MOR zeolite has a linear type pore structure. Heavy
0.05 g
carbon deposition also occurred on the FAU zeolite because large mo-
lecular products might be generated in their supercage. Carbon de-
position on the catalysts led to the deactivation of the reaction.
Conversion on MFI zeolite was low due to the narrow pores inside the
MFI zeolite, which suppressed the diffusion of m-DIPB inside its pore. In
0.1 g contrast, the catalytic activities of BEA and MWW zeolite were main-
Loading amount

tained without deactivation because their pore structure hindered the

formation of an intermediate polymer. Their yield of the products was
also high. In particular, the yield of benzene increased on MWW zeolite.
0.2 g
Benzene might be formed due to cumene, which is generated by the
dealkylation of m-DIPB inside the pores.

3.3. Catalytic cracking of m-DIPB on MWW zeolite

0.3 g
0.4 g
0 20 40 60
Composition (%)
Fig. 7. Chemical composition of products with the loading amount of MWW
zeolite in the dealkylation of m-DIPB at 350 °C. Product was collected for
30 min after 30 min of time on stream.
The product distribution varies with the species of zeolite in the
reaction. Fig. 5(B) shows the composition of products obtained in cat-
alytic cracking. The product obtained from the isomerization and
cracking reaction was less than 10% on the FAU and MFI zeolite cat-
alysts. o-DIPB and p-DIPB were generated mainly by the isomerization
of m-DIPB on MOR zeolite. In contrast, small amounts of benzene and
cumene were produced by the dealkylation of m-DIPB. On the BEA and
MWW zeolites, the products of the dealkylation of m-DIPB were larger
in quantity than those by the isomerization of m-DIPB. The yields of
benzene plus cumene were as high as ca. 50% on MWW zeolite com-
pared to the other zeolites.
Carbon deposition inside the pores took place easily on the MOR
Cumene, benzene, and p-DIPB were the main products in the m-
DIPB cracking reaction. Light hydrocarbons consisting of C3∼C5, tri-
isopropylbenzene (TIPB), and o-DIPB were produced in much smaller
quantities. As shown in Fig. 5(A), high conversion was observed on
MWW, FAU, and BEA zeolite, which have a relatively large pore size
compared to MFI zeolite. The pore structure of MWW zeolite is com-
80 100 posed of a 10-oxygen member ring pore entrance and a 12-oxygen
member ring pore inside the channel [25]. Fig. 6 shows the variation of
conversion of m-DIPB and the chemical composition of the products in
the dealkylation of m-DIPB on MWW zeolite. The conversion of m-DIPB
increased and zeolite deactivation decreased with increasing reaction
temperatures, as shown in Fig. 6(A). The intermediates of the aromatic
compounds are formed easily at high reaction temperatures. The pro-
duct distribution also varied with the reaction temperature, as shown in
Fig. 6(B). p-DIPB and o-DIPB were generated mainly by the iso-
merization of m-DIPB at 250 °C. At 350 °C, the main product was cu-
mene formed by the dealkylation of m-DIPB. The production of benzene
and light hydrocarbons increased with increasing reaction temperature.
Fig. 7 presents the chemical composition of products with the
loading of MWW zeolite in the dealkylation of m-DIPB at 350 °C. The
conversion of m-DIPB was improved and the yields of cumene plus
benzene were also enhanced as the catalyst loading was increased. In
particular, the conversion of m-DIPB exceeded 90%, and the yield of
benzene plus cumene was ca. 70% under a 0.4 g catalyst loading at
350 °C.

84
B.-G. Park, K.-H. Chung
4. Conclusion
The conversion of m-DIPB and product distribution were influenced
by the pore structure of the zeolites in the catalytic cracking of m-DIPB.
MWW zeolite showed higher conversion than the other zeolites as well
as longer catalytic activity with slow deactivation. The selectivity of the
MWW zeolite for benzene and cumene was higher than those of the
other zeolites. The pillow-type pore structure of MWW zeolite could
suppress secondary reactions, such as isomerization, which led to high
yields of cumene and benzene. The catalytic behavior of MWW zeolite
in the catalytic cracking of m-DIPB was superior to that of the other
zeolites.
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