Fuel 173 (2016) 285–297

Contents lists available at ScienceDirect

Fuel
journal homepage: www.elsevier.com/locate/fuel

Review article

Thermal/catalytic cracking of liquid hydrocarbons for the production

of olefins: A state-of-the-art review II: Catalytic cracking review
S.M. Sadrameli
Chemical Engineering Department, Tarbiat Modares University, P.O. Box 14115-114, Tehran, Iran

a r t i c l e i n f o a b s t r a c t

Article history: Light olefins such as ethylene and propylene, are considered as main raw materials for the production of
Received 25 October 2014 numerous plastic materials, synthesis fibers and rubbers in the petrochemical industry. The conventional
Received in revised form 18 October 2015 process for the production of light olefins is thermal cracking in the presence of steam called Steam
Accepted 13 January 2016
Cracking (SC). This has been the main technology for the production of olefins for more than ninety years.
Available online 29 January 2016
This technology has reached to its full capacity and cannot accommodate excessive demands of the petro-
chemical industry although still 95% of the light olefins are produced by this technology. In addition there
Keywords:
are a few drawbacks for this technology such as en extensive energy consumption, and production of
Catalytic cracking
Modeling
greenhouse gasses. An alternative and promising route for the production of light olefins which consumes
Light olefins less energy and produces fewer pollutants to the environment is Thermal Catalytic Cracking (TCC). This
Liquid hydrocarbons paper reviews the main research works done on the process in the literature in the last five decades. An
eight-lump mathematical model is presented for the catalytic cracking kinetics. Some of the main
experimental laboratory setup systems in the world have also been reviewed and parts of the results
are presented and discussed.
Ó 2016 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 285
2. Catalytic cracking . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 286
2.1. Previous research works on TCC. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 286
2.1.1. Oxides catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 286
2.1.2. Zeolite based catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 287
2.1.3. Carbon nanotubes based catalysts. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 289
2.1.4. SAPO-34 based catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 290
3. Kinetic mathematical model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 292
3.1. Development of the model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 292
3.2. Model solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 293
3.3. Prediction of the eight-lump kinetic model. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 293
4. Experimental setup systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 294
5. Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 296
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 296

1. Introduction the most important chemicals and raw materials in the petrochem-
ical industry. The commercial production of ethylene has been first
Olefins which are in the class of unsaturated hydrocarbons with patented by Union Carbide in 1922 [1] and three years later the
a single double bond and a chemical formula of CnH2n are one of first commercial plant for ethylene production was built in Virginia
in the United States. Since then the plants for the production of
olefins have been bigger, more efficient in energy consumption,
E-mail address: sadramel@modares.ac.ir

http://dx.doi.org/10.1016/j.fuel.2016.01.047
0016-2361/Ó 2016 Elsevier Ltd. All rights reserved.
286 S.M. Sadrameli / Fuel 173 (2016) 285–297
Nomenclature
C/H atomic ratio of carbon to hydrogen in feeds
Ci concentration of lump i, mol/ggas
E activation energy, kJ/mol
kij rate constant for the reaction of lump i to lump j
Mi molecular weight of lump i, g/mol
Rco catalyst to oil weight ratio
Rso steam to oil weight ratio
and more environmentally friendly. The plant capacity for today’s
world scale crackers is more than 1.5 million MTY. The conven-
tional technologies for the production of light olefins are Steam
Cracking (SC), Fluidized Catalytic Cracking (FCC) using zeolites,
Deep Catalytic Cracking (DCC), and Methanol to Olefins (MTO).
Worldwide olefin’s demand is primarily driven by economic
growth and the associated increased demand for consumer goods.
The demand for ethylene is increasing and the present demand by
petrochemical industry is over 155 million tons per annum [2,3].
Ethylene producers in the world are looking for the more acces-
sible lower price feeds for the production of olefins. Ethane sepa-
rated from natural gas and natural gas liquids is one of the more
available feeds for the cracking in the world and therefore most
of the cracking furnaces utilize this feed for the production of light
olefins. The ethane crackers produces the minimum amounts of
propylene and the recovery of this product is not feasible in such
industrial plants. Normally for each tone of ethylene production,
0.4 tone of propylene is produced in the thermal cracking furnace.
It is expected that by growing ethane cracking furnaces by 2014
the ratio of propylene to ethylene reaches to the lowest value of
0.36 while this ratio by the petrochemical demands is 0.62 [2].
Nearly 68% of the world propylene is produced besides ethylene
by thermal cracking process, 29% by FCC process with catalytic
cracking in the refineries, and 3% produced with other process
[4]. The steam cracking furnaces produce propylene as a byproduct
when using feeds other than ethane which is always less than
ethylene. The propylene market grew more than ethylene and
the demand for the propylene exceeded the demand for ethylene
in recent years as illustrated in Fig. 1 [5]. Therefore, there is a need
for the new technologies that can fill the market gap for the pro-
duction of propylene using the commonly available feeds. This
can be achieved by using thermal catalytic cracking with more
selectivity to the propylene production. The thermal catalytic
Fig. 1. Propylene demand growth [5].
t residence time, s
tc residence time of catalyst, s
T reaction temperature, K
vij stoichiometric coefficient for the reaction of lump I to
lump j
Greek letters
a deactivation constant
/ deactivation function
cracking process is performed in different types of reactors such
as a fixed-bed or a fluidized bed reactor at moderate temperature
in the presence of catalyst. The main objective of the process is
cracking of low value hydrocarbons for the production of higher
valued products. The catalyst can increase the selectivity of the
process at lower temperature than in the thermal cracking for
the production of light hydrocarbons.
In the first part of this review paper [6] the thermal cracking of
gaseous and liquid hydrocarbon feeds for the production of light
olefins has been discussed. This paper reviews the thermal
catalytic cracking of liquid hydrocarbons for the production light
olefins. Some of the experimental research works done in the last
decades on the catalytic cracking of liquid hydrocarbons for the
production of light olefins using different types of catalysts are
reviewed and parts of the results are presented. A kinetic mathe-
matical model for the simulation of the fixed bed reactors is pre-
sented and finally some of the main experimental setup systems
in the world in which the catalytic cracking for the production of
light olefins are studied are discussed.
2. Catalytic cracking
Thermal cracking or steam cracking is still the main route for
the production of light olefins and currently produce 95% of the
world’s ethylene and 60% of the world’s propylene as a byproduct
to ethylene production [7]. A schematic diagram of a steam cracker
including the furnace, an indirect quench system called transfer
line exchange (TLE or TLX), and direct quench system using quench
oil is shown in Fig. 2. The main production of propylene from
steam cracking is mainly from LPG and heavier liquid feeds such
as naphtha and gas oil; and even then this is limited to about half
that of ethylene typically with the weight ratio approximately
0.4–0.6 parts of propylene to ethylene [8]. This would not satisfy
the world’s demand for propylene by petrochemical industry and
therefore the new sources of propylene will be necessary to satisfy
the expected industrial demand in the future. Thermal cracking
furnaces are also one of the most energy-intensive processes that
typically operate at 850–900 °C and produce a large amount of
greenhouse emissions. Pyrolysis section alone utilizes 65% of the
total energy use and 75% of the total exergy loss in the plant. Such
furnaces also require being out of service for decoking as a result of
high process temperature [8]. One of the solutions to address all of
these drawbacks will be the application of new technologies for the
olefin production. Liquid and wasted solid hydrocarbons such as
polymers can be cracked by thermal catalytic cracking to produce
large amount of ethylene and propylene.
2.1. Previous research works on TCC
2.1.1. Oxides catalysts
Thermal catalytic cracking has been investigated experimen-
tally by Mjukhopadhyay and Kunzru [9] using modified alumina
 S.M. Sadrameli / Fuel 173 (2016) 285–297
Fig. 2. A schematic of a typical steam cracking furnace, photo courtesy of BASF Qtech.
catalysts in a fixed bed reactor at 760–820 °C and atmospheric
pressure. The alumina catalyst has been impregnated by potassium
carbonate with 0–8.8 wt.% to reduce the coke formation. They con-
cluded that although the coke deposition has been reduced by this
modification but the amounts of methane, ethylene, and propylene
has all been decreased.
Jeong et al. [10] cracked naphtha catalytically over
KVO3-impregnated a-Al2O3 in a fixed bed reactor and showed that
the yields of ethylene and propylene have been increased to 10 wt.
% and 5 wt.% in comparison to the bare tube reactor at the same
operating conditions. They concluded that the amount of coke gen-
erated and deposited on the catalyst surfaces during the pyrolysis
increases with the reaction temperature and the axial length of the
reactor and decreases with the catalyst amount. Their results also
show that addition of B2O3 to the catalyst causes a strong interac-
tion between KVO3 and a-Al2O3.
Catalytic cracking of n-hexane over MoO2 catalyst has been
tested in the temperature range of 557–640 °C by Song et al.
[11]. They concluded that the selectivity of olefins has been
increased while the selectivity of alkanes has been decreased. In
the first experimental tests a layer of MoOxCy is formed on the
catalyst that makes a positive resistance to deactivation of catalyst
by coke deposition on the surfaces.
The catalytic pyrolysis of naphtha has been investigated by
Jeong et al. [12] in a quartz reactor with 5 mm a-Al2O3 spheres
for the production of light olefins. The yields of ethylene and
propylene has been increased to about 10% and 5% when compared
with thermal cracking in the absence of catalyst with the same
operating conditions. They have also studied the coke formation
on the surface of the spheres and showed that the coke deposition
on a-Al2O3 spheres increased continuously along with the axial
length of the reactor as well as with reaction time. The coke forma-
tion was influenced strongly by the physical properties of the
a-Al2O3 spheres.
Steam pyrolysis of n-heptane has been investigated by Pant and
Kunzru [13] over different calcium aluminates and potassium
impregnated calcium aluminate in a fixed bed reactor at atmo-
spheric pressure. Their results showed that K2CO3 impregnated
287
catalyst significantly reduced the coke deposition on the catalyst
surface but only had marginal effect on the products severities.
The calculated activation energy for the coke gasification reaction
was 140 kJ/mol.
2.1.2. Zeolite based catalysts
Zeolites as catalytic cracking catalysts have been used exten-
sively in the oil and gas industry in the recent years [14,15] and
the application of HZSM-5 in the catalytic cracking of hydrocar-
bons is more than other zeolite types. This is due to the fact that
they have higher activation and specific structure in their pore
sizes [16,17]. Thermal catalytic cracking of cyclohexane over
HZSM-5 with Si/Al ratio of 28, 85, and 200 at temperature range
of 400–650 °C and partial pressure of 2 bars has been investigated
recently by Slagtern et al. [18]. The main cracking products were
olefins and benzene and selectivity of ethylene and propylene
has been increased up to 60% by increasing temperature. They also
presented a kinetic mathematical model for the catalytic cracking
with Si/Al = 200.
N-octane has been used as a feed for thermal catalytic cracking
using zeolites with different pore structure and acidity [19]. They
concluded that although the conversion of n-octane is mainly
based on the number of acidic sites in the catalyst but the rate of
deactivation of the catalyst with coke deposition has been deter-
mined by the pores structure. They also showed that the selectivity
of light olefins is almost the same for all of the zeolites used in the
experiments.
Li et al. [20] investigated the effects of adding zeolites with
large pore sizes on the selectivity of light olefins in the catalytic
cracking of n-decane at 625 °C. A mixture of zeolite catalysts with
a large pore sizes such as Hb, Y and HZSM-5 with small pore sizes
has been used in a fixed bed reactor at WHSV = 20 h
1 and catalyst
to hydrocarbon ratio of 3. They concluded that due to the pore size
limit in the zeolite catalysts a large hydrocarbon molecule cannot
be cracked in order to obtain light olefins and therefore use of zeo-
lites with a large pore size in cracking of large molecule hydrocar-
bons is inevitable. This conclusion may be challenged with other
researcher findings since in the catalytic cracking of wasted
288 S.M. Sadrameli / Fuel 173 (2016) 285–297
polymers the large molecules are cracked to lower hydrocarbons at
high temperature that could go through the pores of the catalyst. In
such processes, the selectivity to propylene could be considerable.
The effect of catalyst pore sizes on the catalytic cracking of
n-octane has been studied by Altwasser et al. [21]. ZSM-58,
HZSM-5, and Hb have been used as catalysts with small, interme-
diate and large pore sizes respectively. The selectivity of light
olefins has been increased by decreasing the pore size of the cata-
lysts. In another study they investigated the effects of aluminum in
the catalyst structure and concluded that lower amount of Al in the
catalyst structure leads to higher light olefin production which is
due to the fact that lower amount of Al in the catalyst decreases
the acidic sites in the catalyst that results higher selectivity to
the light olefins. The olefins are intermediate products which will
be converted to higher aromatics and poly-aromatics with further
reaction such condensation. The catalyst with lower acidity
reduces these secondary reactions, which results higher selectivity
to light olefins.
Xue and Chen [22] studied the performance of HZSM-5 modi-
fied with P for the catalytic cracking of butane to produce light
olefins and showed that the conversion of butane decreases with
adding P to the catalyst. This is due to the lower density of acidic
sites and lower specific area and pore sizes of the catalyst. The
selectivity to olefins has been increased sharply when the amount
of P reaches to 0.9 wt.%.
Effect of adding 0–2.1 wt.% P on HZSM-5 catalyst for the cat-
alytic cracking of butane has been investigated by Zhao et al.
[23]. Their results indicated that adding P to the zeolite increases
the selectivity to propylene and the optimum yields of propylene
has been obtained at 1.5 wt.%.
Lu et al. [24] studied the effect of Fe on HZSM-5 in the catalytic
cracking of isobutene at 600 and 625 °C and the amount of Fe from
zero to 0.331 mmol/g. The results showed that by adding small
percentage of Fe to the zeolites the selectivity to olefins increases
and reaches to the amounts of 24.6% and 32.4% for ethylene and
propylene respectively. Addition of more Fe to the catalyst
decreases the selectivity to methane and ethylene, propylene and
total olefins and increases the selectivity to aromatics.
Lu et al. [25] in another study investigated the effect of Cr on
HZSM-5 in the catalytic cracking of isobutene. The amount of Cr
has been changed from zero to 0.231 mmol/g and at the tempera-
ture of 600 °C and 625 °C. The yields of ethylene and propylene
Fig. 3. Scheme of the three step surface modification of multilayer HZSM-5 coating [27].
exhibit about 30.8% and 25.3% at temperature of 625 °C and the
amount of Cr of about 0.004 mmol/g in the catalyst. Addition of
Cr to the catalyst also increases the selectivity to aromatics and
butane and decreases the selectivity to methane and olefins. The
cracking temperature has also been decreased from 625 °C to
575 °C.
Li et al. [26] considered the catalytic cracking of isobutene with
HZSM-5 and modified HZSM-5 with Fe and Cr in different ratio of
SiO2/Al2O3. Higher yields of light olefins on the zeolites catalysts of
Fe/HZSM-5 and Cr/HZSM-5 in the ratio of SiO2/Al2O3 of 80% have
been obtained.
A multilayer b-oriented HZSM-5 coating has been used by Ji
et al. [27] with the assistance of surface modification using tita-
nium alkoxide solution for the supercritical catalytic cracking of
n-dodecane at 4 MPa and 550 °C. The surface modification is con-
sisted of three main processes: (1) nanoaqueous condensation of
the titanium alkoxide precursor molecules, (2) removing the
remaining unreacted alkoxide precursor and (3) aqueous hydroly-
sis of the adsorbed metal alkoxide species to generate the surface
Ti–OH groups as shown in Fig. 3. They concluded that the catalytic
activity of bilayer coatings improves more than 60% and the deac-
tivation rate sharply decreases from 17.3% to 2.3% when Fb
(a fraction index of b-oriented crystals) changes from 38.5% to
89.7% due to the enhanced diffusion rate in the b-axial channels.
The conversion of n-dodecane to lower gaseous and liquid hydro-
carbons has been improved by more than 50% but the catalytic
reaction rate slightly decreased with increasing the number of
b-oriented layers from one to three which was due to the
increased zeolite loadings and diffusion limitations in the zeolite
channels.
Naphtha catalytic cracking has been performed by Wei et al.
[28] at lowered temperature of 650 °C over modified ZSM-5 cata-
lyst for the production of light olefins. The catalyst has been mod-
ified using Fe, Cu, La, P, and Mg. Their results showed that some
modifications such as Fe, Cu, and La increase the BTX production
while P and Mg modifications favored the light olefin production.
They have also made a comparison between using steam and nitro-
gen in the cracking stream and found that in N2 stream cracking
catalyzed by LaZSM-5 more than 50% of naphtha feed were con-
verted to BTX while in steam cracking with an improved modified
catalyst, P, La/ZSM-5, naphtha can be converted to light olefins
with high activity and long-term stability.
 S.M. Sadrameli / Fuel 173 (2016) 285–297
Fluid catalytic cracking of naphtha using monolithic catalysts
with zeolite washcoat has been studied by Shao et al. [29] for the
production of propylene in which the conversion of the olefin in
naphtha and the selectivity of propylene in gaseous product have
been investigated. Their results showed that the activity of thermal
cracking is not significant at temperature lower than 770 K with
200 cpsi monoliths since the feed and the catalyst may have short
hydrodynamics residence time in the monolithic channels and the
loading of zeolite ZSM-5 could not only enhance the conversion of
olefin cracking activity but also the selectivity of propylene via
catalytic cracking mechanism. The experimental data also showed
that the gaseous products mainly consisted of propylene and C4
olefin which could totally reach 60% and the yield of propylene
was about 31% while the olefin content in naphtha could reduce
15%.
Modification of ZSM-5 zeolite catalyst has been applied by Gao
et al. [30] for maximizing propylene production in catalytic crack-
ing reaction of light diesel from which they could increase the
propylene yield by 3% at least than the reference catalyst. The
zeolite catalyst has been modified by phosphorus using hydrother-
mal dispersion and it was shown that the loss of phosphorus in the
process is less than impregnation method.
HZSM-5 with varying ratio of Si/Al2 ratios has been modified
with Mn and alkaline treatment by Awayssa et al. [31] and used
for the catalytic cracking of Arab light vacuum gas oil (VGO) in a
FCC unit for the production of light olefins (in particular propy-
lene). The light olefin yields have been considerably increased
upon using Mn modified HZSM-5 catalyst with the highest yields
of 29.2% wt.% at Si/Al2 = 80 and 2.0 wt.% of Mn. They also concluded
that alkaline treatment of HZSM-5 exhibited high light olefins
yields compared with parent HZSM-5 due to the formation of
hierarchical micro–meso topology.
Catalytic cracking of vacuum gas oil (VGO: C 84.91%; H 12.13%;
N 0.36%; and sulfur content 100 ppm) has been investigated by
Ishihare et al. [32] using hierarchical ZSM-5 catalyst containing
mesoporous silica–aluminas by one pot sol–gel method with malic
acid. The modified catalyst showed higher activity than single
ZSM-5 and when the content of aluminum species increased in
the catalysts both the conversion of VGO and the yields of gasoline
increased compared with that of single ZSM-5.
A small fixed bed (FFB) unit has been used by Gong et al. [33] to
study the protolytic catalytic cracking of Daqing VGO by conduct-
ing multiple series of experiments from the low reaction conver-
sion to high conversion over acid catalysts. Their results showed
that protolytic cracking plays a very important role for being the
initial reaction during the heavy oil catalytic cracking but at the
same time, it has a negative effect on the selectivity to the product
of interest due to the dry gas generated in the reaction.
The comparison between the results of thermal cracking and
catalytic cracking of hydrocarbons reveals that significant effect
of catalyst in increasing light olefins yield especially propylene
can be observed. Also catalytic cracking process can be run at lower
temperature than thermal cracking. This influences to the energy
consumption of the process which is one of the most energy inten-
sive processes in the industry. Finally the selectivity to propylene is
another advantage of the catalytic cracking over thermal cracking
which fill the gap in the market demands for the propylene in
the future.
2.1.3. Carbon nanotubes based catalysts
Carbon based materials are the best choices for the catalytic
reactions. This is due to the fact that they can be modified very
easily for the specific application. Activated carbon has been used
as a base for the catalysts in last decades due to its higher surface
area and resistance at high temperature [34]. Recently new mor-
phologies of carbon in nano scale have been applied as a base for
289
the cracking catalysts [35]. Carbon nanotubes (CNTs) can be
divided into two groups; single wall carbon nanotube and multi-
wall carbon nanotube as shown in Fig. 4 [36]. Higher stability
and ultimate physicochemical properties of CNT catalysts suggest
their promising future in material science. In addition, Sp3-like
bonds were introduced by curvature of grapheme layers and acted
as electronic promoter, resulting higher reactivity. The homoge-
neous microstructure, highly functionalized surface properties
and non-porosity are attractive in the catalysis community since
they might be good catalysts for the instant future instead of acti-
vated carbons or other type catalysts. An extensive studies has
been performed on the properties of single wall nanotubes
[37,38] which shows that they act as pure quantum elements in
which electrons move in the axial direction of the tube. Carbon
nanotubes are decomposed at temperature higher than 550 °C
and therefore for the higher temperature applications as in
catalytic cracking they have to be covered with metallic oxides
for resistance to higher temperature.
The modification of carbon nanotubes (CNTs) has been done by
Grobert et al. [39] by covering with a few layers of SiOx.
Tetraethoxysilane (TEOS) has been used as a raw material for sili-
con oxide that has been mixed with carbon nanotube at specific
PH. TG analysis of the samples indicated that the mixture initiates
burning at 580 °C and the thermal analysis curves reaches to the
saturation point at 800 °C. They concluded that this method can
convert the catalyst to the higher resistance catalyst at high tem-
perature. The same method has been applied by Seeger et al. [40]
at room temperature using TEOS as a raw material for silicon oxide.
The thickness of SiOx on the catalyst has been measured to be
10 nm.
The penetration of SiH4 on the carbon nanotube surface at
specific temperature and pressure has been studied as a new
method for the silicon impregnation on the carbon nanotube by
Wang et al. [41]. The oxidation temperature of the prepared cata-
lyst has been initiated at 650 °C and increases with the impregna-
tion percentage on the catalyst surface.
A new method has been applied on the impregnation of silicon
of carbon nanotubes by Fu et al. [42]. In this method
3-aminopropyltriethanoxysilane has been used that has the capa-
bility of absorption of the tube surface and can cover the surface
with a thin layer of silicon oxide. The advantage of this method
is controlling the thickness of silicon oxide.
There has been an extensive research studies at TMU on the
application of carbon nanotubes for the catalytic cracking of hydro-
carbons for the production of light olefins. Keyvanloo et al. [43,44]
studied the application of carbon nanotubes modified with rare
earth elements such as silicon and cerium for the production of
light olefins by catalytic thermal cracking of naphtha using a fixed
bed reactor as shown in Fig. 5. The reactor is made of stainless steel
with 450 mm length, 13.5 mm ID and 15.9 mm OD. The middle
part of the reactor with 100 mm length has been packed with
the catalyst using two stainless steel mesh type supports at the
ends. The furnace with maximum power capacity of 4.8 kW h is
made by Azar Furnace Manufacturing, an Iranian company with
600 mm length and 450 mm ID with the maximum attainable tem-
perature of 1250 °C. The thermocouple type of Cr–Al has been
installed at the middle part of the furnace and used for measuring
the furnace temperature. The modification of carbon nanotubes
with silicon layer improves its stability for the TCC process. Their
results show that yield of ethylene and propylene reached to max-
imum 26.5 wt.% at 680 °C, residence time of 0.5 s, and steam to
naphtha ratio of 0.5 g/g. In the same process with the same condi-
tion the yield of total olefins increased sharply to 36.31 wt.% by
increasing one gram of CNT as a catalyst.
Multi wall nanotubes has been used as a catalyst for the
catalytic cracking of naphtha for the production of light olefins
290 S.M. Sadrameli / Fuel 173 (2016) 285–297
Fig. 4. Single wall (a) and multiwall (b) carbon nanotubes [36].
by Sheibani [45] using the same experimental setup illustrated in
Fig. 5. Table 1 lists the results of the thermal catalytic cracking
using carbon nanotubes with different silicon coatings. As shown
from the results the maximum yields of ethylene of 20.23 wt.%
have been obtained at 680 °C with 10 wt.% of SiO2 and modified
with 10 wt.% of CeO2. The total yields of olefins at 680 °C and res-
idence of 0.5 s, and steam to hydrocarbon ratio of 0.5 g/g is 0.43
(18% for ethylene and 25% for propylene) which approximately
280% higher than the yields obtained from thermal cracking with
no catalyst at the same operating conditions. Fig. 6 illustrates the
comparison of ethylene yields for the bare tube and carbon nan-
otube coated with silicon and cerium [43]. The yields and conver-
sion of catalytic cracking of naphtha for the production of ethylene
and propylene versus temperature are shown in Fig. 6 for different
catalysts. As illustrated in the figure, the conversion increases with
temperature and reaches to 66.56% at 680 °C with 10 wt.%
Ce–CNT–10 wt.% Si catalyst. The yield of ethylene is also increased
with increasing temperature.
Due to the high energy consumption and limitation on the
propylene production in thermal cracking process of naphtha the
catalytic process can be substitute the process. Carbon nanotubes
are one of the suitable types of catalysts for this process but due
to its low stability at high temperature over 550 °C they must be
modified with silicon layer. The results showed that the yields of
light olefins were stable during the process and CNT as a support
has been proved to have high catalytic stability. The application
of carbon nanotubes as a catalyst for the catalytic cracking of
hydrocarbons for the production of light olefins might be interest-
ing in the distance future but there are still some limitations for the
application of this type of catalyst which makes the zeolite based
catalysts an advantageous type for the process.
2.1.4. SAPO-34 based catalysts
Molecular sieves of aluminophosphate (ALPO) have been first
used as a catalyst in 1982. They are very similar to zeolites but
the initial structure is from Al–O–P instead of Si–O–Si or Si–O–Al.
 S.M. Sadrameli / Fuel 173 (2016) 285–297 291

Fig. 5. Schematic diagram of the experimental setup for naphtha cracking [43–45].

Since the molecular structure of ALPO is neutral, its ability for being
as a catalyst is very week and therefore adding silicon to ALPO
leads to molecules of silicoaluminophosphate or SAPO. Also substi-
tution of ions Si4+ with P5+ leads to the acidic sites in the catalyst
and the ability for being as a catalyst is increased [43]. The selec-
tion of SAPO-34 between other types of SAPO catalysts has more
selectivity to the light olefins and has been used extensively in
MTO [41,42]. SAPO-34 has a shape of Chabazite and with pore size
of 3.5–6 Å with an open oval octagonal shape [46].
Generally the acidity of HZSM-5 decreases with adding Si/Al but
in SAPO-34 catalyst the acidic sites increases with Si/Al. This is due
the conversion of SAPO-34 crystals to aluminophosphate that has
more acidic sites [47]. There are a few research works reported
in the literature regarding the application of SAPO-34 in the cat-
alytic cracking of hydrocarbons for the production of light olefins
but its use for the MTO and ETO (ethanol to olefins) has been
extensively studied [48–50].
The catalytic cracking of C4-olefins has been investigated by
Zhao et al. [51] using three types of zeolites including SAPO-34.
The acidity of SAPO-34 and HZSM-5 is less than H-mordenite
but its stability is twice than H-mordenite. Their results showed
that the yields of light olefins are the highest for HZSM-5
catalyst.
Zu et al. [52] studied the selectivity of different types of zeolites
for the catalytic cracking of butane. Their observation shows that
the selectivity to light olefins is higher for SAPO-34 but its deacti-
vation is much quicker than other types due to its small pore sizes.
Performance of SAPO-34 and HZSM-5 impregnated with cerium
and lanthanum has been studied by Taghipour [53]. They con-
cluded that increasing cerium and decreasing lanthanum at high
temperature has positive effect on the ethylene yields. Their results
indicate that the catalyst which has lower loaded lanthanum that
is 0.8 wt.% and higher amount of cerium which is 8 wt.% at temper-
ature of 750 °C produces the maximum yield of propylene while

Table 1
Yields of products from TCC with different catalysts [45].

Experimental. no. Furnace setpoint (°C) Si coating (wt.%) Yield (wt.%)

CH4 C2H6 C2H4 C3H8 C3H6 C4H10 C4H8 1,3C4H6 H2–COx C+5
1 620 5 10.8 5.03 18.21 0.45 10.2 0.95 0.78 0.63 5.33 51.2
2 650 5 10.31 5.31 20.26 0.52 13.17 1.59 1.68 0.79 2.56 41.8
3 680 5 9.69 5.72 21.32 0.69 16.82 2.73 3.09 1.63 2.85 35.3
4 620 10 8.32 5.42 15.13 0.51 10.48 0.85 0.99 0.29 7.58 50.4
5 650 10 7.4 5.44 18.91 0.57 15.75 1.24 1.32 0.59 8.13 40.6
6 680 10 9.65 6.06 20.23 0.74 19.45 3.94 4.76 2.45 2.83 30.3
7 620 15 10.31 3.67 14.28 0.34 11.12 1.14 1.48 1.21 4.88 51.54
8 650 15 8.7 5.71 17.64 0.68 16.50 2.99 3.67 1.99 3.20 39.2
9 680 15 9.74 6.75 19.56 0.83 18.95 3.62 4.25 1.68 3.18 31.41
292
Fig. 6. Ethylene (a) and propylene (b) yields vs. temperature for different catalysts [43].
higher yield of ethylene has been reached at 750 °C with 0.8 wt.%
loaded lanthanum and 12 wt.% of cerium [53].
Synthesis of nano-SAPO-3 catalysts modified with cerium and
zirconium elements using wet impregnation method for the pro-
duction of light olefins from naphtha has been studied by Zeinali
[54]. The comparison between thermal cracking and thermal
catalytic cracking results at the same operational conditions
showed better performance for the catalytic cracking. The light
olefins yields improved noticeably after modification so that with
2% cerium and 2% zirconium on SAPO-34 and reached to
21.78 wt.% and 23.8 wt.% ethylene and propylene respectively [54].
Table 2
Operating conditions for the catalytic cracking of heavy oil [56].
Item
Reaction temperature (°C)
Steam furnace temperature (°C)
Oil inflow (g/min)
Water inflow (ml/min)
Residence time (s)
Steam ratio (g/g)
Catalyst loaded (g)
Catalyst to oil weight ratio (g/g)
Steam/oil weight ratio
S.M. Sadrameli / Fuel 173 (2016) 285–297
An extensive review on the catalytic cracking of hydrocarbons
over modified ZSM-5 zeolited for the production of light olefins
has been done by Rahimi and Karimzadeh [55].
The comparison between the catalytic performance of SAPO-34
and HZSM-5 in catalytic cracking of naphtha reveals that the yields
of propylene and total olefins were higher for HZSM-5 while the
production of ethylene is higher for SAPO-34 catalyst. The deacti-
vation tests over SAPO-34 and HZSM-5 catalysts also indicate that
HZSM-5 had a better catalyst lifetime compared to SAPO-34 and
the lifetime enhancement can be achieved on both catalysts after
modifications with cerium and zirconium.
3. Kinetic mathematical model
3.1. Development of the model
Value
600–716 A eight-lump kinetic mathematical model has been developed
300 by Meng et al. [56] for the catalytic pyrolysis of heavy oils over
2.0–10.0
zeolite catalyst containing 17 kinetic constants and one for the
1.0–6.0
1.5–4.5 catalyst deactivation. In the model for catalytic cracking of heavy
0.2–1.6 oils, lump I generating lump J can be expressed with the following
20–80 mathematical model:
6–27
I ! v ij J
ki
0.2–1.6 ð1Þ
 S.M. Sadrameli / Fuel 173 (2016) 285–297 293

A kinetic expression (ri) can be formulated as a function of lump Table 4

concentration (Ci), rate constant (ki) and catalyst deactivation func- Apparent activation energies and frequency factors [56].

tion (/) in a fixed bed reactor and an isothermal plug flow regime Reaction Unit Frequency factor E (kJ/mol)
with operating conditions shown in Table 2. Eq. (1) is a second Value
order irreversible reaction for heavy oils catalytic reaction while
k13 g mol
1 s
1 1.04 ⁄ 1011 115
for other reactions; Eq. (1) means irreversible first order reactions. k14 g mol
1 s
1 1.48 ⁄ 1010 113
Based on these assumptions, equations of eight-lump kinetic k15 g mol
1 s
1 1.21 ⁄ 109 85
model for catalytic cracking of heavy oil can be derived from the k16 g mol
1 s
1 1.72 ⁄ 1012 141
continuity equation and reaction rate equation as follows: k17 g mol
1 s
1 1.15 ⁄ 1013 159
k18 g mol
1 s
1 7.31 ⁄ 108 87
dC 1 k23 g mol
1 s
1 1.49 ⁄ 108 74
¼
ðk13 þ k14 þ k15 þ k16 þ k17 þ k18 ÞC 21 / ð2Þ k28 g mol
1 s
1 9.36 ⁄ 108 81
dt
k34 g mol
1 s
1 2.66 ⁄ 108 138
dC 2 g mol
1 s
1
¼
ðk23 þ k28 ÞC 22 / ð3Þ k35 1.02 ⁄ 1010 171
dt k36 g mol
1 s
1 5.10 ⁄ 108 137
dC 3 k37 g mol
1 s
1 2.33 ⁄ 1011 169
¼ ½v 13 k13 C 21 þ v 23 k23 C 21
ðk34 þ k35 þ k36 þ k37 þ k38 ÞC 23 / ð4Þ k38 g mol
1 s
1 3.24 ⁄ 109 136
dt
k46 s
1 1.36 ⁄ 106 139
dC 4
¼ ½v 14 k14 C 21 þ v 34 k34 C 23
ðk46
k47 ÞC 4 / ð5Þ k47 s
1 5.15 ⁄ 108 181
dt k56 s
1 1.07 ⁄ 109 180
dC 5 s
1 8.48 ⁄ 1010
¼ ½v 15 k15 C 21 þ v 35 k35 C 23
ðk56 þ k57 ÞC 5 /
k57 208
ð6Þ
dt
dC 6
¼ ½v 16 k16 C 21 þ v 36 k36 C 23 þ v 46 k46 C 4 þ v 56 k56 C 5 / ð7Þ
dt
dC 7
¼ ½v 17 k17 C 21 þ v 37 k37 C 23 þ v 47 k47 C 4 þ v 57 k57 C 5 / ð8Þ
dt h i
1
1þRco

C 1 M1
C 2 M2
C 3 M3
C 4 M4
C 5 M5
C 6 M6
C 7 M7
C8 ¼ ð9Þ
M8
The catalyst deactivation model (/) is described by the follow-
ing equation for catalytic cracking of naphtha:
/ ¼ expð
2atc Þ ð10Þ
where / is defined as:
 4:3889
C
/ ¼ exp
2:55 T 0:2838 t
0:1774 ð1 þ Rco Þ
0:4795
H

ð1 þ Rco Þ
0:3963 t 0:2276
c ð11Þ

3.2. Model solutions

Fig. 7. Predicted yields of catalytic pyrolysis products vs. residence time [56].
The rate constants have been estimated by solving a system of
differential in Matlab language and inserting four reaction temper-
atures of 600 °C, 630 °C, 660 °C and 700 °C. An objective function predicted and experimental data for all the products and coke
subjected to Eqs. (2)–(9) has been defined to optimize the kinetic yields:
parameters. This function represents the difference between the 2 exp 3
Xset X
n Y i;j
Y sim
i;j
Ea Wj4 5 ð12Þ
Table 3 i¼1 j¼1
Y exp
i;j
Rate constants for the catalytic pyrolysis [56].
In the above equation i and j denote compound j in experiment i
Reaction Unit Reaction temperature (°C)
condition.
600 630 660 700 The obtained rate constants are listed in Table 3. The frequency
k13 g mol
1 s
1 14587 24829 37831 75288 factors and activation energies have been calculated on the basis of
k14 g mol
1 s
1 22705 43019 72028 112815 the following Arhenius equation and are listed in Table 4:
k15 g mol
1 s
1 10252 15107 21240 34275
k16 g mol
1 s
1 5829 12097 22828 42866
 
E
k17 g mol
1 s
1 3327 8062 17965 30667 k
k0 exp
ð13Þ
k18 g mol
1 s
1 4365 7029 9862 15170
RT
k23 g mol
1 s
1 5846 8295 10524 16955
k28 g mol
1 s
1 12591 18045 27605 38996
k34 g mol
1 s
1 1.4 208 501 9.9 3.3. Prediction of the eight-lump kinetic model
k35 g mol
1 s
1 0.6 1.4 208 7.2
k36 g mol
1 s
1 3.1 5.6 10.7 21.1
k37 g mol
1 s
1 18.7 39.0 85.7 200.0
Scatter diagram has been used between the predicted data and
k38 g mol
1 s
1 22.5 45.3 80.6 155.1 experimental values to validate the kinetic model [56]. The varia-
k46 s
1 0.007 0.013 0.023 0.050 tion of product yields including the yields of ethylene and propy-
k47 s
1 0.008 0.018 0.039 0.11 lene with residence time at constant temperature of 660 °C,
k56 s
1 0.020 0.042 0.093 0.250
steam ratio of 0.6 g/g is shown in Fig. 7 [56]. The predicted product
k57 s
1 0.032 0.058 0.210 0.610
yields increases with residence time as expected until residence
294 S.M. Sadrameli / Fuel 173 (2016) 285–297

Table 5 are higher in the presence of catalyst and incorporation of K2CO3

Conversion and product yields obtained with different un-promoted catalysts [59]. in the catalyst reduces the coke deposition on the catalyst [58].
Product yields (wt.% feed) Non- Catalyst type Using the same setup and reaction scheme various calcium alumi-
catalytic
CA1 CA2 CA3 CA4 nate catalysts have been prepared and tested in the catalytic crack-
ing of n-heptane [59]. The results of the experimental studies
Methane 6.5 8.2 8.7 8.8 9.2
Ethane 2.3 3.6 3.4 1.8 2.6
including conversion and product yields for different catalysts
Ethylene 32.1 35.0 38.5 39.1 39.7 and non-catalyst conditions are shown in Table 5. Their results
Propane 0.3 0.4 0.3 0.3 0.3 clearly prove the positive effects of catalyst on the product yields.
Propylene 45.8 16.0 18.2 16.5 13.0 The variation of cracked gas yields were from 70.9 wt.% for CA1 to
1-Butene 3.0 2.6 4.9 3.5 1.8
75.1 wt.% for CA4 catalysts.
1-3-Butadiene 1.5 1.5 1.0 1.8 2.0
Total cracked gas 62.7 70.9 71.7 72.2 75.1 Most of the research studies performed at Ghent University,
C4+ 7.3 8.5 7.3 6.8 6.5 Belgium have been concentrated on olefin production by thermal
Carbon monoxide Trace 8.1 Trace 6.4 6.1 cracking as reported in the first part of this paper by Sadrameli
Carbon dioxide Trace 1.8 Trace 0.85 1.3
[6] but there are a few publications in the literature regarding on
Conversion (%) 69.0 88.7 81.0 78.8 86.7
Coke deposited after 3 h (wt.% of – 4.81 3.80 4.29 3.84
the catalytic cracking of hydrocarbons for the production of olefins
catalyst) using renewable resources [61,62].
An alternative production route for the production of light
olefins has been studied by Steven Pyl et al. [61] at Ghent Univer-
sity in which triglycerides from bio oil have been converted cat-
time of 0.3 is reached and then the yields of ethylene, coke and alytically to the renewable feeds such as naphtha which is then
light alkanes increase slowly, while others decrease slowly which thermally cracked with steam for the production of renewable
is due to the secondary reactions. olefins. The schematic diagram of the experimental set up systems
It can be concluded that the developed kinetic model for naph- for the naphtha conversion is shown in Fig. 8. The characteristics of
tha catalytic cracking can predict the yields of light olefins with an the experimental setup are reported by Steven Pyl et al. [62]. The
acceptable accuracy. The direct prediction of the main products yields of the main products are shown in Fig. 9. The study also
such as ethylene and propylene is one of the advantages of the shows the attractive character of this feed over fossil based naph-
model. The simulated results have shown that production of light tha in coke formation and deposition during the thermal cracking
olefins is higher at higher temperature and a short residence time. process.
An extensive review on the kinetic equations for chemical reac- Catalytic cracking of C4 fraction over a commercial FCC equilib-
tions and processes has been recently published by Froment [57]. rium catalyst for the production of light olefins has been investi-
gated by Meng et al. [63] and Li et al. [64] in China. The
4. Experimental setup systems schematic diagram of the experimental setup is shown in Fig. 10.
It was shown that the conversion of butenes to olefins were easier
There are a few main experimental setup systems for the than butanes and 1-butene. Their results also reveal that the yields
catalytic cracking of hydrocarbons in the world which are the base of light olefins increases with reaction temperature and decreases
for the research in this area. with WHSV (weight hourly space velocity) as listed in Table 6.
Catalytic thermal cracking of n-heptane has been investigated Secondary cracking of gasoline and diesel from heavy oil
at Indian Institute of Technology, India (IIT) by Pant et al. catalytic pyrolysis for the production of light olefins has been stud-
[58–60]. The steam pyrolysis has been performed over potassium ied by Liu et al. [65]. They concluded that the secondary cracking
carbonate impregnated calcium aluminate (12CaO–7Al2O3) cata- reactivity of gasoline and diesel is not significant and the only
lyst in a fixed bed reactor at atmospheric pressure in a temperature 10% (by mass) of them is converted to the light olefins. Their
range of 680–750 °C. They concluded that the yields of products results also reveal that ethylene yield increases with reaction

Fig. 8. Schematic diagram of bio oil production from triglycerides [61].

 S.M. Sadrameli / Fuel 173 (2016) 285–297 295

Fig. 9. Yields of main products from cracking of renewable naphtha [61].

Fig. 10. Schematic diagram of experimental set up for hydrocarbon cracking [63,64]. 1: water tank, 2: filter, 3: water pump, 4: steam furnace, 5: C4 feed tank, 6: electronic
balance, 7: C4 buffer tank, 8: constant pressure nitrogen, 9: C4 feed pump, 10: counterbalance valve, 11: preheater, 12: thermocouple, 13: reactor, 14: heater, 15: entrance
and exit catalyst, 16: condenser, 17: liquid product sampler, 18: wet gas flow meter, and 19: gas sample bag.

catalytic cracking of naphtha. The experimental setup is shown

Table 6
Production yields as function of temperature and WHSV [63,64]. in Fig. 5. Different types of zeolites have been studied.
Teimouri Sendesi et al. [66] studied the effect of Si/Al, Fe, P load-
Reaction 400 450 500 550 600 650 700
ing on the stability of HZSM-5 for the catalytic cracking of naphtha.
temperature (°C)
They modified the catalyst with different Si/Al molar ratios and it
Dry gas 0.03 0.21 0.45 0.63 1.29 4.62 12.58
was demonstrated that dealumination of the catalyst had a signif-
C3 2.80 3.81 4.64 6.12 8.22 15.86 26.64
C4 84.01 83.76 82.81 81.91 79.70 68.47 48.66 icant role in catalyst stability with the highest stability for Fe(6)-P
Liquid 12.47 11.37 10.98 10.06 9.43 9.16 8.84 (2)/HZSM-5(25).
Coke 0.69 0.85 1.28 1.28 1.36 1.89 3.28 A six-lump kinetic model has been proposed by Sedighi et al.
WHSV (h
1) 1 3 5 7 9 [67] for the catalytic cracking of naphtha similar to that proposed
Dry gas 14.05 12.58 11.62 11.34 10.97 by Meng et al. [56] for heavy oils. Their model contains 20 kinetic
C3 28.39 26.64 26.07 25.38 24.84 parameters and one for the catalyst deactivation. The variation of
C4 45.10 48.66 50.16 51.24 52.06 ethylene yields versus residence time at different reaction temper-
Liquid 8.85 8.84 9.06 9.24 9.45 atures and fixed steam ratio of 0.5 (g/g) is illustrated in Fig. 11 [67].
Coke 3.61 3.28 3.09 2.80 2.68
The results clearly show that as residence time increases, the yield
of ethylene increases and the predicted yields at high temperatures
are more than those at low temperatures.
temperature while propylene shows a maximum with an optimum Catalytic cracking of naphtha over carbon nanotubes have been
temperature of 670 °C for the production of light olefins. investigated by Alyani et al. [68] and Keyvanloo et al. [69]. They
An extensive research has been performed at Tabiat Modares concluded that using the synthesized catalysts the yields of
University, in Tehran, Iran [66–69] in the last decade on the ethylene and propylene were stable during the process and carbon
296 S.M. Sadrameli / Fuel 173 (2016) 285–297
Fig. 11. Variation of ethylene yields vs. residence time at different temperature [67].
nanotube as a support was proved to have high catalytic stability
which made this type of cracking a more promising process for
the industrial application.
5. Conclusions
Light olefins are among the most important raw materials for
the petrochemical industry. The main process for the production
of light olefin in large scale is thermal cracking although there
are different processes available chemically. Among the processes
for the production such materials is catalytic cracking which has
been under consideration in the last decades as a substitute for
thermal cracking due to its flexibility of producing propylene
besides ethylene. There are different types of zeolites which can
be utilized in the fixed bed reactor for the catalytic cracking of
hydrocarbons. The most utilized catalysts are modified zeolites
with metals, SAPO-34 and carbon nanotubes. Application of each
type in the catalytic cracking of naphtha has been discussed. An
eight-lump model has been introduced for the mathematical mod-
eling of the reaction kinetics. The model utilizes the experimental
data and predicts the rate constants, activation energies and
frequency factors. Finally some of the main experimental setup
systems for the catalytic cracking of hydrocarbons in the world
have been introduced and some of the results have been presented.
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