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Optimal design and operation of an industrial fluidized catalytic cracking

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Article  in  Fuel · October 2017

DOI: 10.1016/j.fuel.2017.05.092

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 Fuel 206 (2017) 657–674

Contents lists available at ScienceDirect

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

Full Length Article

Optimal design and operation of an industrial fluidized catalytic cracking

reactor
Aysar T. Jarullah a, Noor A. Awad a, Iqbal M. Mujtaba b,⇑
a
Chemical Engineering Department, College of Engineering, Tikrit University, Iraq
b
Chemical Engineering Division, School of Engineering, University of Bradford, Bradford BD7 1DP, UK

h i g h l i g h t s

Fluid catalytic cracking (FCC) is an important process in petroleum refining.

FCC process model is developed and validated against experimental data.

Maximum conversion of VGO to lighter products in Industrial FCC process considered.

Cost of the process is minimized while octane number is maximised.

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

Article history: Fluidized catalytic cracking (FCC) is regarded one of the most significant operations in the oil refining
Received 10 March 2017 industries to convert feedstock (mainly vacuum gasoil) to valuable products (namely gasoline and diesel).
Received in revised form 23 May 2017 The behavior of the fluidized catalytic cracking process is playing a main part on the overall benefits of
Accepted 25 May 2017
refinery units and improving in process or control of fluidized catalytic cracking plants will result in
exciting benefits economically. According to these highlights, this study is aimed to develop a new math-
ematical model for the FCC process taking into account the complex hydrodynamics of the reactor regen-
Keywords:
erator system with a new six lumps kinetic model for the riser. The mathematical model, simulation and
Fluidized catalytic cracking
Modelling
optimization have done utilizing vacuum gas oil (VGO) as a feedstock and zeolite as a catalyst under the
Optimisation following operating conditions: temperature (733 K, 783 K, and 813 K), weight hourly space velocity (5,
Vacuum gas oil 20 and 30 h1) and catalyst to oil ratio (4, 7 and 10). The best kinetic parameters of the relevant reactions
are estimated using the optimization technique based on the experimental results taken from literature.
The effect of operating condition (mainly, reaction temp (T), catalyst to oil ratio (CTO) and weight hourly
space velocity (WHSV) on the product composition has also been discussed. The optimal kinetic param-
eters obtained from the pilot plant scale have been employed to develop an industrial FCC process, where
optimal operating condition based on maximum conversion of VGO with minimum cost in addition to
maximizing the octane number of gasoline (GLN), have been studied. Minimum coke content deposition
the catalyst within the regenerator is also investigated here. New results (the highest conversion and
octane number, and the lowest coke content) have obtained in comparison with those reported in the
literature.
Ó 2017 Elsevier Ltd. All rights reserved.

1. Introduction
Cracking is the process where the large undesirable compounds
break down into smaller compounds and extra beneficial mole-
cules. Such process is conducted without catalyst at high reaction
temperature (T) and pressure (P), or with the catalyst at low or
⇑ Corresponding author.
E-mail addresses: A.T.Jarullah@tu.edu.iq (A.T. Jarullah), I.M.Mujtaba@bradford.
ac.uk (I.M. Mujtaba).
moderate T and P. Based on the market request, oil industries have
used the FCC processes for the purpose of increasing the valuable
products (mainly car fuels) and decreasing the heavy oil fractions
obtained by oil distillation. The riser reactors of the fluidized cat-
alytic cracking process have designed based on acidic catalyst,
where heavy cuts (namely reduced crude residue and vacuum
gas oil (VGO)) are decomposed into more valuable products at a
specified process conditions. Also, the quality of the products in
the reactors depends on the operating conditions and such prod-
ucts can be improved via changing the process conditions

http://dx.doi.org/10.1016/j.fuel.2017.05.092
0016-2361/Ó 2017 Elsevier Ltd. All rights reserved.
658 A.T. Jarullah et al. / Fuel 206 (2017) 657–674

Nomenclature

Ai Rate coefficient, (–) n3 Order of gasoline concentration, (–)

Ar Archimedes number, (–) n4 Order of concentration of liquefied petroleum gases, (–)
A Riser, Regenerator cross section area, (m2) Ni Nickel content in the equilibrium catalyst, ppm
API Density parameter, (–) po2 Partial pressure of oxygen, atm
aij Pre-exponential factor, (cm3 gm s1) p Riser, regenerator pressure, atm
bij Cracking kinetic parameter of the reaction lump i ? j, Ret Reynolds number, (–)
(–) Rj rate formation, gm/cm3.s
ci Cracking kinetic parameter for the formation of lumpi, R Gas constant, j/mol.k
(–) rij Rate of reaction lump i ? j, gm/cm3.sec
Crge Weight fraction of coke on regenerated catalyst, kg of rP Radius of catalyst particle, cm
coke/kg of cat rg Mean pore radius, cm
Csc Weight fraction of coke on spent catalyst, kg of coke/kg SP Total geometric surface area of catalyst, cm2
of cat Sg Specific surface area of particle, cm2/gm
CH Weight fraction of hydrogen in coke, kg of H2/kg of coke S Sulfur content in feed stock, wt%
cpg Specific heat capacity of vacuum gas oil, j/g.k TmeABP Mean average boiling point, K
cpc Specific heat capacity of catalyst, j/g.k TR Riser temperature, K
cpair Specific heat capacity of air, k j/kg.k Tdil Temperature of dilute phase at any location, K
cpco Specific heat capacity of carbon monoxide, k j/kg.k Trge Regenerator temperature, K
cpco2 Specific heat capacity of carbon dioxide, k j/kg.k T Temperature of reaction, K
cpo2 Specific heat capacity of oxygen, k j/kg.k TVABP Volume average boiling temperature, K
cpN2 Specific heat capacity of Nitrogen, k j/kg.k Tsc Temperature of spent catalyst, K
De;vgo Effective diffusivity of vacuum gas oil, cm2/s T10 ; T30 T50 ; T70 ; T90 ASTM D86 distillation temperature at dis-
Dm;vgo Molecular diffusivity of gas oil in liquid phase, cm2/s tilled vol% equal to 10, 30, 50, 70, 90, respectively., K
Dk;vgo Knudsen diffusivity of vacuum gas oil, cm2/s Tbase Base temperature for heat balance calculation, K
dp Diameter of catalyst particle, cm ug Velocity of gas, m/s
dpe Equivalent particle diameter, cm ut The partial terminal velocity, m/s
dt Tube diameter, cm up Velocity of solid particle, m/s
D Riser, Regenerator diameter, cm uo Superficial gas velocity, m/s
Ei Activation energy, k j/kmol VP Total geometric volume of catalyst particle, cm3
Fg Vacuum gas oil mass flow rate, kg/s Vg Total pore volume, cm3/gm
Fcat Catalyst mass flow rate, kg/s Vcat Volume of catalyst, cm3
Fr Frond number, (–) V Vanadium content in equilibrium catalyst, ppm
Frt Terminal Frond number, (–) xpt Relative (catalytic) co combustion rate, (–)
fi Molar flow rate of i gas in regenerator, k mol/s z Height of riser, regenerator, m
f TOt Total gas flow rate at any location in the regenerator,
k mol/s Greek symbols
Fsc Mass flow rate of spent catalyst, kg/s bc CO/CO2 ratio at catalyst surface in regenerator, (–)
Fsc Mass flow rate of regenerated catalyst, kg/s bi Frequency factor, (–)
Hco Heat of formation of carbon monoxide, k j/k mol e Void fraction in regenerator at any location, (–)
Hco2 Heat of formation of carbon dioxide, k j/k mol eg Void fraction of gas phase in riser, (–)
HH2O Heat of formation of water, k j/k mol 2B Porosity, (–)
Kij Cracking kinetic constant of the reaction in riser lump 2s Catalyst particle porosity, (–)
i ? j, cm3/gm.s DHcrk Heat of cracking per unit mass of gas oil converted, j/kg
k1 ; k2 ; k3 k3c ; k3h Reaction rate constant for composition reaction DT sc Stripper temperature drop, °C
in regenerator, (–) go Effectiveness factor, (–)
kc Overall rate combustion of coke, (–) ll Liquid viscosity, Pa.s
kco Frequency factor for ith reaction, (–) lg Gas viscosity, Pa.s
mw Mass flow rate of cooling water, gm/s qp Particle density, gm/cm3
MMI Mobil metal index, ppm qc Catalyst density, gm/cm3
MWg Molecular weight of vacuum gas oil, gm/g mol qg Gas density, gm/cm3
MWLCO Molecular weight of light cycle oil, gm/g mol u Catalyst activity factor, (–)
MWGLN Molecular weight of gasoline, gm/g mol U Thiele modulus, (–)
MWLPG Molecular weight of liquefied petroleum gases, Sph Sphericity, (–)
gm/g mol XRS Cross section area of riser, m2
MWL Molecular weight of liquid phase, gm/g mol Tortuosity factor, (–)
MWDG Molecular weight of dry gas, gm/g mol v cg Critical volume of vacuum gas oil, cm3/g mol
MWT Average vapor phase Molecular weight, gm/g mol vg Molar volume of liquid, cm3/g mol
MWCK Molecular weight of coke, gm/g m vl Molar volume of liquid, cm3/g mol
n1 Order of vacuum gas oil concentration, (–)
n2 Order of light cycle oil concentration, (–)

[62,32]. Recently, the worldwide is producing approximate 45% of such as alkylation process [6]. During 2006, fluidized catalytic
the car fuel (gasoline) via fluidized catalytic cracking plants cracking process have reported at 400 oil industries and about
(directly) in addition to other supplementary process (indirectly) 1/3 of those petroleum refining companies were operated in the
 A.T. Jarullah et al. / Fuel 206 (2017) 657–674
fluidized catalytic cracking process resulting car fuel with higher-
octane number (ON) and engine fuels [33]. In 2007, the fluidized
catalytic cracking plants in the USA has been processed a total of
8343  108 m3/day of feedstock, while double amount of such
feedstock has been processed other countries [47].
The fluidized catalytic cracking operating have improved as a
results of evolving in petroleum refining industries in the last dec-
ades, achieving the goals expected of improving heavier, to more
contaminate feed stocks, to increase process flexibility accommo-
dating environmental regulation in addition to maximize reliabil-
ity [40]. According to the environmental impact, fluidized
catalytic cracking process has played an important factor via pro-
duction car fuel with lower benzene content [7]. The thermal
cracking (THC) process (using T and P without catalyst) and cat-
alytic cracking (CAC) process (similar to THC with catalyst to pro-
duce light compound from heavy compounds) are considered the
main cracking processes. Using catalysts in CAC reaction can
increase the yield and improves the products quality a moderate
or lower process conditions in comparison to THE process, which
mean that the car fuels with higher ON, lower heavy fuel oils in
addition to light gases (LG) are obtained. The LG obtained by CAC
process contains higher olefin compounds than those obtained by
THE process [26,55].
In this study, a mathematical process model is developed
which can accurately simulate industrial FCC reactor. The reaction
kinetic models are developed based on six lump models and
experimental data taking hydrodynamic factors into considera-
tion. The model is then employed to optimize the process condi-
tions of the operation which will maximize the conversion and
the octane number while minimizing the cock content in the
regenerator.
2. FCC process
At the conventional process, the VGO and any feedstock is
heated utilizing the heat generated via main fractionators bottoms
pump around and/or fired heaters. The feedstock of fluidized cat-
alytic cracking process is heated earlier and then channeled to
the reactor to meet with the regenerated catalyst. The desired tem-
perature of the feed inside the reactor is achieved based on the
heating of the catalyst in the regenerator. The FCC reaction in the
riser is endothermic and the cracking process is occurred in the
vapor phase making the feed in the vapor phase. Due to the crack-
ing reactions, the activity of the catalyst is gradually deactivated as
a result of coke deposition on the catalyst and increased owing to
the cracking reactions, and the reaction is promoted by the catalyst
without changing chemically. The catalyst and cracking products
will be separated at the stripping process while the hydrocarbons
will adsorbed upon the surface of the spent catalyst during the
way to the stripper. For stripping and removing the hydrocarbons
entrained by catalyst molecules, steam is mostly utilized for this
purpose. Product vapor is left the cyclone section, whereas hot pro-
duct vapor of the reactor goes near to the fractionators, where the
hydrocarbon compounds will be condensed and then vaporized in
such device. The unstabilized GLN and LG obtained from the top of
the main fractionators are sent to the wet gas compressor. The
regeneration of the catalyst should be kept constant due to coke
(poisoning). In the generator, such issue is taking place, where
the activity of the catalyst is restored and providing heat that
makes the endothermic reactions of cracking process. The fresh
air is coming by blower for the purpose of burning off the coke
(consisting of C, H2, S and N) by air distributor found at the bottom
of the regenerator container. The dry gases producing by coke com-
bustion are passed into cyclones located near the top of the regen-
erator, while in some operations sends to a carbon monoxide boiler
659
[21,36,52]. The main parts of the FCC unit that have been modeled
are:
A) Preheat system
B) Riser
C) Reactor
D) Regenerator
2.1. Preheat system
The VGO and reduced crude residue produced by atmospheric
and vacuum fractionators tower are regarded the main feedstock
for the fluid catalytic cracking process. Such feed stocks are heated
earlier before going to the reactor, which is carried out via heating
system providing the heat required for both fresh and recycled
feedstock. Many heat exchangers are employed for this purpose
and the temperature required is approximate 260–372 °C. The
gas oil includes paraffins, aromatics and naphthenes compounds
in addition to some impurities (mainly, S, N) having harmful
impact upon the activity of the catalyst. Thus, for the purpose of
protecting the pre-treating of the catalyst feed, it is necessary to
get rid such impurities before entering to the FCC process to get
higher quantity and quality for the products.
2.2. Riser
All the cracking reactions are carried out in this device (which is
considered the major reactor) in endothermic behavior. The con-
tact time in this reactor is reported to be two to ten seconds. The
gases generated pass to the fractionators from the top of the reac-
tor, whereas the some liquid product (heavy) and catalyst return in
the disengaging section. The oil is separated from the catalyst uti-
lizing the baffles located in the stripping device by steam, which is
supplied to the stripping area. The optimal diameter as well as the
length of such reactor has observed to be 2 m and 30–35 m, respec-
tively [13,36].
2.3. Reactor
The previous practice for the implementation of cracking reac-
tions (CR) in the reactor was completely modified by implementing
it at the riser section for the purpose of employing the highest effi-
ciency of the catalyst beside temperature in the riser. Previously, no
significant efforts have observed to control the processes of the
riser, while recently, by using efficient zeolite catalyst leads to
enhance the cracking reactions inside the riser. After that, the reac-
tor is then applied to separate both the catalyst and products gen-
erated. The improvement of the reactions in the riser is enhanced by
an increase in the speed of regenerated catalyst to the required
level. In general, the aims of reactor are separating the catalyst
deactivated of the cracked vapors, and passing the catalyst used
downward through a steam stripper part to the regenerator.
When the hot catalyst meets the feedstock inside the riser, the
reactions required are continuously occurred until product vapor is
removed from the catalyst in the reactor separator. After that, the
products are passed to the fractionators in order to separate the
liquids and gases products. The CTO inside the reactor should be
kept properly due to ability of changing the product selectivity.
The sensible heat of the catalysts can be employed for the CR as
well as to vaporize the feedstock [22,36].
2.4. Regenerator
The deactivated catalyst obtained via steam stripper part is sent
to the regenerator, where the catalytic activity is maintained
(owing to the coke deposited upon the catalyst surface) by using
660 A.T. Jarullah et al. / Fuel 206 (2017) 657–674

the regeneration process, which is also utilized to supply the heat
required to the reactor [51,36]. The air is used for this purpose pro-
vided by blowers and the air velocity is kept at high level in the
regenerator in order to make the reaction section fluidized in nat-
ure and the air is passed to the regenerator via distributor to burn
off the large amount of the coke content. The hot catalyst is left the
regenerator into a catalyst and the dry gaseous (DG) allow to get
out and flowing back to the top section of the regenerator and
the fresh catalyst flow is controlled using a slide valve. Two
cyclones are used to send the hot DG to the regenerator in order
to remove the entrained catalyst from DG. The design and model
of the regenerator is selected to burn the coke to CO and CO2.
Nowadays, the modern design of such unit is aimed to convert C
into CO2 with minimum capital cost and coke content [23,36].
Fig. 1 shows the typical UOP fluidized catalytic cracking unit.
3. Mathematical model of riser
The modeling of riser reactor includes the selection of kinetic
model and hydrodynamic model. The most important factor con-
sidered in the modeling is the balance of simplicity and precise-
ness. Mathematical model is a set of ordinary algebraic and
differential equations related to mass and energy balance and the
physical properties of a system. The basic mathematical model
for a chemical reaction rate should take into consideration the rate
of mass and heat transfer together with the kinetic equation. Math-
ematic model of such reactor involves the feedstock vaporization,
the riser as well as the stripper column and the modeling process
is based on an adiabatic plug-flow (PF) reactor with a six-lump
kinetics model. The lumped model used in this work is presented
in Fig. 2 and consisting of vacuum gas oil (VGO), gasoline (GLN),
light cycle oil (LCO), liquefied petroleum gas (LPG), dry gas (DG)
and coke (CK).The complexity of reversible catalyst deactivation
by coking during catalytic cracking makes the problem very diffi-
cult to analyze from fundamental points of view. Thus in this work,
the approach considered is that the pore blockage (external coke
deposition) disables higher number of active sites than the site
coverage (internal coke deposition), thus the former should be
included as the major point of backward catalyst deactivation
owing to form the coke [53]. This pore blockage is found because
of growth in the coke, where the out surface of the catalyst has
mainly deactivated by nickel upon the catalyst matrix. As reaction
proceeds, the activity of the catalyst is decreasing by increasing in
the coke generated on the catalyst leading to reduce the active
sites of the catalyst and the effective rate of the reaction is reduced
as a result of reducing the effective diffusivity of the reactants.
Therefore, it is an important to take into account the effectiveness
factor (g) of the catalyst [18].
3.1. Mass balance of riser
The riser is a PFR under adiabatic conditions. To estimate the
concentration behavior for each lump along the reactor, the follow-
ing equation is used for this purpose [61] as follows:



1 @ðqv :Y i Þ

@Y i


: þ U : ¼ Ri ð1Þ
qv @tc
z V
@z
tc




As reported by Ali and Rohani [3], the left term 1
qv  @ðq@tvc:yi Þ
is
z
ignored. Thus the above equation can be written to be:

Hydrocarbon
Steam vapors to main
fractionators

FG

Flue gas

RT

RG

Stripping
steam

Fluffing air
RCRSV

SCSV
RC steam
SV

Raw oil
Combusion
air

Fig. 1. UOP fluid catalytic cracking unit (Adapted from Fernandes et al. [16]).
 A.T. Jarullah et al. / Fuel 206 (2017) 657–674 661

VGO 3.4. Effectiveness factor

5 4 3 2 1 The effectiveness factor (g) is based on a Thiele modulus (U) as

presented in the following relation applied for sphere particles
[20,27]:
3ðUcothU  1Þ
g ð11Þ
CK DG LPG GLN LCO U2
The generalized Thiele modulus (U)
7 10 9 8 6 sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
 
n þ 1 K ij ðyVGO Þ qp
n1
V
U p¼ ð12Þ
Sp 2 Dei
The Particle density (qp ), can estimating using the following simple
Fig. 2. Kinetic scheme of propose the cracking reactions taking place in the riser. relation as follow:
qcat


qp ¼ ð13Þ
1  2B
@y

U V : i

¼ Ri ð2Þ The Bed porosity (2B) of the catalyst can be estimated for undiluted
@z tc
sphere packed catalyst from the following equation [20,29]:
X X 0  2 1
Ri ¼ ^rji  ^rij ð3Þ dt
j j B dpe
2 C
2B ¼ 0:38 þ 0:073@1 þ 1  2 A ð14Þ
dt
^r ij ¼ K ij Ai ug n
yi ij CTO ð4Þ dpe

For spherical shape of particle, the external volume (V p ) and the

3.2. Rate constant surface area (Sp ) of particle can be calculated as shown below:
4
Reaction rate constant can be described by Arrhenius equation Vp ¼ pðr3p Þ ð15Þ
3
as follow:  
  Sp ¼ 4p r 2p ð16Þ
E
K ij ¼ aij exp ð5Þ
RT
The effective diffusivity ðDei Þ, where the porosity and tortuosity
The sophisticated lumps model has recently been modified to of the pore matrix in the particle should be taken into account in
include the characterization of the catalyst and the feed stock. Such the model [59,43].
modification is proposed to calculate the kinetic constants as a
function of API gravity for the lumps. 2s 1
Dei ¼ ð17Þ
K ij ¼ aij ð6Þ
1
Dmi
þ D1
ki

Calculation of such kinetic constant of cracking process related

The effective diffusivity [59] which consists of two diffusion
to the conversion of vacuum gas oil to DG is then modified to
contributions: Knudsen diffusivity ðDki Þ and molecular diffusivity
include the sulfur content in the feed:
ðDmi Þ. Dki is evaluated as shown below [39,42]:
K ij ¼ aij Sbij ð7Þ  0:5
T
The mobil metal index, MMI (consider for metals impact, namely Dki ¼ 9700rg ð18Þ
MW VGO
vanadium and nickel) related to ai above is taken into account
within the rate equations [52]:
Mean pore radius (rg), can be estimated by [45,30]
V
MMI ¼ Ni þ ð8Þ
4 Vg
rg ¼ 2 ð19Þ
Sg
3.3. Catalyst deactivation
While the Dmi is calculated by a Tyn-Calus equation [28,41]
The catalyst deactivation function ðuÞ occurs owing to coke v 0:267 T
generated on the catalyst. Generally, there are two paths of its rep- Dmi ¼ 8:93  108 L
ð20Þ
resentation: the first is based on the residence time upon the cat-
v 0:433
VGO l L

alyst, and the second is dependent upon the coke content. In this The molar volume of VGO is evaluated by the following
study, a single deactivation function based on the catalyst coke relation:
content has been formulated to take into account the regenerator
efficiency as follows: v VGO ¼ 0:285ðv cVGO Þ1:048 ð21Þ
du
¼ aYck ð9Þ The critical specific volume vacuum gas oil is calculated by a
dY ck
Riazi–Daubert equation [2]:
Integration Eq. (9) will give:
 
u ¼ ½1 þ ðd  1Þ  aYck Y ck 
1
1d ð10Þ
v cL ¼ 7:5214  103 ðT meABP Þ0:2896 ðq15:6 Þ0:7666 MW L ð22Þ
662 A.T. Jarullah et al. / Fuel 206 (2017) 657–674

The mean average boiling points can be estimated as follows Ret lg

ut ¼ ð36Þ
[24,31]: qg dp
h
0:6667
T meABP ¼ T VABP  0:5556exp 0:9440  0:0087ð1:8T VABP  491:76Þ The vapor phase density is calculated by the following
i equation:
0:3333
þ2:9972ðSlÞ ð23Þ
PMW g
where: qg ¼ ð37Þ
RT
T VABP ¼ 0:2ðT 10 þ T 30 þ T 50 þ T 70 þ T 90 Þ ð24Þ
The average vapor phase molecular weight expressed [1] as:
ðSlÞ ¼ 0:0225ðT 90  T 10 Þ ð25Þ
1
MW g ¼ y1 ð38Þ
MW VGO
þ MWy2LCO þ MWy3GLN þ MWy4LPG þ MW
y5
DG
y6
þ MW CK
þ MWy7H2O
3.5. Riser hydrodynamic
Substituting the equations related to the reaction rate constant
When the vaporization process of the feed is completed, the cat- and deactivation in the mass balance equation leads to get the gen-
alyst, coke and gases are left. Depending on the mathematical
eral mass equations of the catalytic cracking reactions, which are
modeling, the next relation reported by Patience et al. [44] to esti- as follows:
mate the slip factor (defined as a ratio between velocity of the
average solids and the interstitial gas) is used:  
dyi 1  1 E 1 n1
¼ kij Ai ½1 þ ðd  1ÞaYck Y ck  d1 exp  y gCTO ð39Þ
ug uo 5:6 dz UV RT 1
w¼ ¼ ¼1þ þ 0:47F 0:41 ð26Þ
up eg up Fr rt

Finally, the following differential equations are used to describe

uo the FCC model for each lump
F r ¼ pffiffiffiffiffiffi ð27Þ
gD

rVGO!LCO
ut
F rt ¼ pffiffiffiffiffiffi ð28Þ  
gD dy1 1 1
d1 E1 n1
¼ k1 M0:43
MI API 1:5
½1 þ ðd1Þ a Y
Yck ck  exp  y gCTO
The superficial gas velocity is evaluated utilizing the following dz UV RT 1
correlation: ð40Þ
Fg
rVGO!CLN
uo ¼ ð29Þ  
Aqg dy1 1 1 E2 n1
d1
¼ k2 M0:42
MI API 1:62
½1 þ ðd  1Þa Y
Yck ck  exp  y gCTO
The average particle velocity is calculated as follows [1]: dz UV RT 1
Fc ð41Þ
uo ¼ ð30Þ
qcat ð1  eg Þ
rVGO!LPG
 
Combining Eqs. (26), (27) and (28), the average void fraction of dy1 1 1
d1 E3 n1
¼ k3 M 0:52
MI API 1:7
½1 þ ðd  1Þ aYck Y ck  exp  y gCTO
the gas phase is calculated as follows: dz UV RT 1
qcat F g ð42Þ
eg ¼ ð31Þ
qg F c w þ qcat F g

rVGO!DG
 
Hence, the velocity of the vapor (ug) and solid (up) is determined dy1 1  1 E4 n1
as:
¼ k4 M 0:22
MI S1:7 ½1 þ ðd  1ÞaYck Y ck  d1 exp  y gCTO
dz UV RT 1
uo ð43Þ
ug ¼ ð32Þ
eg

rVGO!CK
 
ug dy1 1  1 E5 n1
up ¼ ð33Þ ¼ k5 M 0:43 ½1 þ ðd  1ÞaYck Y ck  d1 exp  y gCTO ð44Þ
w dz UV MI
RT 1
In order to calculate the particle terminal velocity, many corre-

rLCO!GLN
lations were used in the literatures. In general, the terminal veloc-  
dy2 1 1
d1 E 6 n2
ity is generally estimated for three areas: Stokes (SK), Intermediate ¼ k6 M0:42
MI ½1 þ ðd  1Þ a Y
Yck ck  exp  y gCTO ð45Þ
(IN) and Newton (N) areas and it is classified according to Archi- dz UV RT 2
medes numbers (Ar). Where, Ar is reported to be <32.9, 32.9–

rLCO!CK
106.5 and >106.5 for SK, IN and N, respectively. In this work, (Eq.  
dy2 1 1
d1 E7 n2
(35)) for intermediate regime has been employed for calculating ¼ k7 M0:42
MI ½1 þ ðd  1Þ aYck Y ck  exp  y gCTO
Reynolds number based on particle terminal velocity [57,49]. dz UV RT 2
ð46Þ
qg ðqcat  qg Þgd3p
Ar ¼ ð34Þ
l2g
rGLN!LPG
 
dy3 1  1 E 8 n3
Ar ¼ k8 M0:52
MI ½1 þ ðd  1ÞaYck Y ck  d1 exp  y gCTO ð47Þ
Ret ¼ ð35Þ dz UV RT 3
18 þ ð2:3348  1:7439sphÞA0:5
r
 A.T. Jarullah et al. / Fuel 206 (2017) 657–674 663

r GLN!DG 1 K4
  H2 þ O2 ! H2 O ð59Þ
dy3 1  1 E9 n3 2
¼ k9 M 0:22
MI ½1 þ ðd  1ÞaYck Y ck  d1 exp  y gCTO ð48Þ
dz UV RT 3 The coke combustion reaction above is expressed given by Eq.

r LPG!DG (57) and (56), which are proportional to the coke on regenerated
 
dy4 1 1
d1 E10 n4 catalyst (C rge ), and to partial pressure of oxygen (P O2 ). The combus-
¼ k10 M0:22
MI ½1 þ ðd  1Þ aYck Y ck  exp  y gCTO tion reaction of carbon monoxide equations (Eq. (57) (Heteroge-
dz UV RT 4
neous CO combustion) and (58) (Homogeneous CO combustion))
ð49Þ
are proportional to ðPO2 ) as well as the partial pressure of CO inside
the regenerator (P CO ). These reaction rate equations are:
3.6. Octane number Rate of reaction 1
C rge C rge f O2
The gasoline octane number can be estimated using the follow- r1 ¼ ð1  eÞqcat k1 PO2 ¼ ð1  eÞqcat k1 Prge ð60Þ
MW ck MW ck f TOt
ing equation:
Rate of reaction 2
MON þ RON C rge C rge f O2
octanenumber ¼ ð50Þ r2 ¼ ð1  eÞqcat k2 PO2 ¼ ð1  eÞqcat k2 Prge ð61Þ
2 MW ck MW ck f TOt

The following equations are employed to calculated the motor Rate of reaction 2
octane number (MON) and the research octane number (RON) f O2 f CO
[12]: r3 ¼ K 3 P O2 PCO ¼ ðX pt ð1  eÞK 3c qcat þ eK 3h Þ 2
P2rge ð62Þ
f TOt
MON ¼ 72:5 þ 0:05ðT  900Þ þ 0:17ðcv  0:55Þ ð51Þ
F sc C sc ð1  C H Þ  ðf co þ f co2 ÞMW ck
C rge ¼ ð63Þ
RON ¼ 1:29MON þ 12:06 ð52Þ F rge ð1  C H Þ

0:305u1 þ 1
3.7. Stripper model e¼ ð64Þ
0:305u1 þ 2

The stripper model equations are introduced as: F air

u¼ ð65Þ
qg Arge
T sc ¼ T R  DT sc ð53Þ
Prge
qg ¼ ð66Þ
F sc ¼ F rge þ C sc F rge ð54Þ RT rge
Reaction constant depends on the temperature and are calcu-
3.8. Regenerator model late based on Arrhenius equation [19]
 
CO K1 Eb
In the regenerator, the cock generated on the catalyst particles ¼ ¼ bc ¼ bco exp ð67Þ
CO2 K 2 RT
having carbon (C) and H2, where all the H2 converts to vapor
whereas the carbon converts to either carbon monoxide dioxide. K c is overall coke combustion rate and
The regenerator model is proposed to have two zones: the Dense  
Ec
bed and the Dilute phase. Based on the literature, the following K c ¼ K 1 þ K 2 ¼ kco exp ð68Þ
RT
points are reported: [35,38,34,10]:
where:


The gases follow PF mode through the bed and are thermal bc K c bc kco exp E c

equilibrium with surrounding bed in nature. K1 ¼ ¼ RT

ð69Þ
bc þ 1 bc þ 1

Very well mixing for catalyst in dense bed and isothermal mode

with uniform C on catalyst. Kc kco exp E c

The mass transfer resistance from gas phase to solid phase can K2 ¼ ¼ RT
ð70Þ
bc þ 1 bc þ 1
be ignored.

The specific heat capacity of gas and compound are constant.

The cyclones return all entrained catalyst. 3.8.1. Dense bed modeling
The used catalyst obtained from the reactor is entered to the
The following reactions are reported to be in the regenerator: dense bed where coke is burned-off in by air to carbon monoxide,
carbon dioxide and vapor. The H2 oxidized is proposed to be com-
1 K1 pleted, thus the amount of O2 available is what is left over after the
C þ O2 ! CO ð55Þ H2 combustion reaction [9].
2
Differential Balances of Dense Bed:
The following mass balance and heat balance are employed for
K2
C þ O2 ! CO2 ð56Þ the dense bed:
Material Balance of dense bed:
1 r r3 
K 3c
CO þ O2 ! CO2 ð57Þ dfO2 1
2 ¼ Arge þ r2 þ ð71Þ
dz 2 2
1 K 3h
CO þ O2 ! CO2 ð58Þ dfco
2 ¼ Arge ðr 3  r 1 Þ ð72Þ
dz
664 A.T. Jarullah et al. / Fuel 206 (2017) 657–674

dfco2 and heat balance equation in such area are expressed as follows
¼ Arge ðr 2 þ r 3 Þ ð73Þ
dz [9].
Energy Balance of dense bed: Material Balance dilute Phase:

dfO2 r r3 
dT rge 1
¼0 ð74Þ ¼ Arge þ r2 þ ð84Þ
dz dz 2 2

Energy balance across the regenerator dense bed is given as dfco

follows: ¼ Arge ðr 3  r 1 Þ ð85Þ
dz
Q c þ Q H þ Q air þ Q sc þ Q ent ¼ Q rge þ Q sg þ Q loss ð75Þ
dfco2
¼ Arge ðr 2 þ r 3 Þ ð86Þ
dz
Q c ¼ f co Hco þ f co2 Hco2 ð76Þ
dfc
Q H ¼ f H2O HH2O ð77Þ ¼ Arge ðr1 þ r2 Þ ð87Þ
dz

Q air ¼ F air C Pair ðT air  T bace Þ ð78Þ Energy Balance of dilute Phase:

Q sc ¼ F sc C Pc ðT sc  T bace Þ ð79Þ dT dil 1 dfco dfco2

¼ Hco þ Hco2 ð88Þ
dz f Tot C PTot dz dz
Q ent ¼ F ent C Pc ðT dil  T bace Þ ð80Þ
C PN2 f N2 þ f o2 C Po2 þ f co C Pco þ f co2 C Pco2 þ C PH2O þ F ent C Pc
Q rgc ¼ F rge C Pc ðT rge  T bace Þ ð81Þ C PTot ¼
f Tot
ð89Þ
Q sg ¼ f co2 C pco2 þ f co C pco þ f N2 C pN2 þ f o2 C po2 þ f H2O CpH2O ð82Þ
The overall process model results in a set of differential and
The final expression related to the temperature of the dense bed algebraic equations (DAEs).
is


Q C þ Q H2O þ Q air þ Q sc  Q loss;rge 4. The experimental data
T rge ¼ T base þ ð83Þ
Q sg
To develop first the kinetic models of the process and then the
overall FCC process model, the experimental data from Xiong et al.
3.8.2. Dilute phase modeling [63] are used. A brief description about the materials, apparatus (as
Converting carbon monoxide to carbon dioxide is regarded the shown in Fig. 3 (Xiong et al. [63]) and experimental procedure used
main chemical reaction in the dilute. Thus, both carbon concentra- by Xiong et al. [63] is given below for the convenience of the
tion and T are varied based on the height in the dilute phase. Mass readers:

Fig. 3. Schematic diagram for experimental setup: (1) oxygen; (2) air; (3) constant temperature box; (4) electronic balance; (5) feedstock; (6) oil pump; (7) water tank; (8)
water pump; (9) steam generator; (10) preheater; (11) reactor; (12) thermocouple; (13) first condenser; (14) receiver for liquid products; (15) second condenser; (16) cold
trap; (17) gas collection bottle; (18) water bottle; (19) gas sample connection; (20) drain sump; (21) CO converter; (22) drier; (23) CO 2 infrared detector.
 A.T. Jarullah et al. / Fuel 206 (2017) 657–674 665

Table 1 Mathematically, the problem is stated as:

Specifications of the experimental apparatus [63]. Min SSE
Specifications Values n1 ; n2 ; n3 ; n4 ; Ai ; Ei (i = 1–10)
Length of reactor 65 cm
diameter of reactor 1.5 cm s. t. ~ðzÞ, a(z), p) = 0,
f (z, g(z), g
Volume of catalyst in bed 65 cm3 [zo, zf]
[model, equality constraint]
nL1 6 n1 6 nU1 [inequality constrain

The reaction take place in a plug flow reactor (specifications in
nL2 6 n2 6 nU2 [inequality constraint]
Table 1).
nL3 6 n3 6 nU3 [inequality constraint]

New catalyst is charged before starting with a new experiment.

The CTO is maintained via keeping the catalyst (which is the nL4 6 n4 6 nU4 [inequality constraint]
zeolite) loading amount and the feedstock (which is the VGO) ALi 6 A 6 AUi [inequality constraint]
rate constant. ELi 6 E 6 EUi [inequality constraint]

Steam flow rate is remained constant and is passed continu-
ously over the catalyst bed with different T for 20 min with a
new experiment. ~ðzÞ, a(z), p) = 0 represents the process models that
where: f (z, g(z), g

The condensed liquid products are obtained by the presented in Section 3. Z is the length of the reactor bed (indepen-
container while the gasses will be received in a gas receiving dent variable), a(z) is the decision variables (n1, n2, n3, n4, Ei, Ai), g(z)
bottle. refers to the differential and algebraic variables (yVGO, yLCO, . . .), g~ðzÞ

The stripper is used to separate the used catalyst steam for refers to the derivative of differential variables with respect to bed
30 min for the purpose of recovering entrapped hydrocarbons dy
length of reactor such as ( dzv go ; dydzGLN ; ldots) and p is length (indepen-
and the coke is burned off with O2 by heating the catalyst at
dent constants parameters) or design variables such as (R, . . .). [z0,
953 K leading to convert the carbon monoxide to carbon
zf], is the length interval of interest.
dioxide.
The solution way for the optimization utilizing gPROMS is by
two-way approach known as feasible path approach.
5. Estimation of kinetic parameters of the model

The first way is to perform the simulation for converging all the
In efferent areas of science and engineering, kinetic parameters
equality constraints (described by f ) and satisfying the inequal-
evaluation is important due to several physical and chemical oper-
ity constraints.
ations stated by a set of relations with unknown factors. Estimation

The second way is performing the optimization (to update the
of kinetic parameters is a significant and not a simple step in the
values of the decision variables such as the kinetic parameters).
improvement of models but can be facilitated by utilizing model
based techniques and experimental data. Minimizing the errors
The optimization problem is posed as a NonLinear Program-
between experimental results and predicted data are required
ming (NLP) problem and is solved using a Successive Quadratic
when adequate estimation of kinetic parameters is needed. In this
Programming(SQP) method with in gPROMS software.
work, a non-linear regression method is utilized to determine the
reaction orders of VGO (n1), LGO (n2), gasoline (n3) and LPG (n4),
activation energy (Eij) and pre-exponential factor (Aij) for each 6. Scale up of fluidized catalytic cracking reactor
reaction.
The minimization of the sum of squared errors (SSE) between Optimal operating conditions based on maximum conversion
the experimental concentrations of product (yexp and octane number, and minimum coke content of the catalyst
i ) and predicted
regenerated of an industrial scale FCC is investigated here, which
(ypred Þ is utilized for parameter estimation and the objective func-
i was not considered in the experimental system. Here the goal is
tion (OBJ), which is minimized can be written as follows:
minimizing the cost and maximizing the profitability of the scaled
Nt 
X 2 up process.
OBJ ¼ yexp
i  ypred
i ð90Þ
n¼1 6.1. Energy balance in riser

The heat supplied to the reactor is coming from the regenerator

5.1. Optimization problem Formulation for parameter estimation of via hot circulating catalyst [56]. For heat balance, the risers are
FCC (OP1) regarded as adiabatic PFRs and the resistance among gases and
solids are negligible. The enthalpy of cracking reactions related to
The parameter estimation problem formulation can be stated as vacuum gas oil cracked represents the overall energy consumed
follows: via endothermic CRs and both solids and gases having the same
T owing to pseudo-homogeneity for the heat balance, both gas
Given The reactor characterization, the catalyst, the and solids share the same temperature [8]. The temperature profile
VGO, the process conditions along riser can be estimated utilizing the following energy balance
Optimize The reaction orders of FCC reactions (n1, n2, n3, equation [16]:
n4), reaction rate constants (k) at various
temperatures dT RS ec DHcrk rVGO XRS
¼ ð91Þ
So as to The sum of square errors (SSE) dz F g Cpg þ F c Cpc
minimize
The following polynomial equation expresses the cracking
Subject to Constraints on the conversion and linear
enthalpy to the riser reactor temperature:
bounds on all optimization variables
DHcrk ¼ aDH T 2RS þ bDH T RS þ cDH ð92Þ
666 A.T. Jarullah et al. / Fuel 206 (2017) 657–674

⁄
where: aDH, bDH and cDH the model parameters where, is the target value.
2
Cpg ¼ a þ bT þ cT ð93Þ
6.3. Minimum coke content of the regenerated catalyst (OP3)

6.2. Optimization of operating conditions (OP2)
The process conversion mainly depends on the operating condi-
tions and it is necessary to find the optimal operating conditions
which will enable high conversion with high octane number. Many
of process variables affect the feedstock conversion. In previous
studies, it has been observed that the maximum conversion
obtained is about 85% [4], while the maximum octane number
reported is about 91% [60]. In this study, one of the goals is to
achieve higher conversion and octane number than those reported
in the literatures.
6.2.1. Optimization problem Formulation (OP2)
The optimization problem can be stated as:
As mentioned previously, the cock will be generated upon the
catalyst during CRs and such spent catalyst will be regenerated
inside the regenerator in order to return it to the reactions area
[48]. In previous studies related to the coke content, the minimum
coke content in regenerated catalyst is reported to be 0.002% [24].
Thus, another challenge is to achieve coke content lower than
those reported in the literature.
6.3.1. Optimization problem formulation for minimum coke content
(OP3)
In regenerator model, minimize the coke content on the regen-
erated catalyst is used here utilizing the following objective
function:
W ¼ C rge ð94Þ

Given Length of the reactor (L), the diameter of the The optimization problem formulation can be stated as follows:
reactor (D) and reaction orders (n1, n2, n3, n4),
Aij, Eij Given Reactor configuration, kinetic parameters, Fc,
Optimize reaction temperature (TR), CTO, WHSV Csc, CTO and TRS
So as to Conversion function (CV) Optimize Air flow rate, coke on regenerated catalyst,
maximize regenerator temperature
Subjected to Process constraints and linear bounds on all So as to W
decision variables minimize
Subjected to Process constraints and linear bounds on all
decision variables (mentioned above).
Mathematically, the optimization problem can be written as:
Max CV
WHSV, TR, CTO Mathematically, the optimization problem can be written as:
Min W
s. t f(x(z), u(z), v) = 0 F air
(model equation, equality
constraint)
WHSVL 6 WHSV 6 WHSVU (Inequality constraints)
s.t f(x(z), u(z), v) = 0 (model equation, equality constraint)
TLR 6 TR 6 TU
R
(Inequality constraints)
F Lair 6 Fair 6 FU (Inequality constraints)
air
CTOL 6 CTO 6 CTOU (Inequality constraints)
T Lreg 6 Treg 6 TU (Inequality constraints)
reg
CV > CV  (Inequality constraints)
W P0 (Inequality constraints)

Table 2
Values of constant parameters and coefficients used in this model.

Parameter Symbol Unit Value

Gas constant R J=mol:K 8.314
Critical volume of liquid vacuum gas oil vLc cm3 =g mol 1190
Molecular weight Vacuum gas oil, VGO MWVGO gm=g mol 400
Molecular weight Light cycle oil, LCO MWLCO gm=g mol 200
Molecular weight Gasoline, GLN MWGLN gm=g mol 100
Molecular weight Liquefied petroleum gases, LPG MWLPG gm=g mol 50
Molecular weight Dry gas, DG MWDG gm=g mol 25
Molecular weight Coke, Ck MWCK gm=g mol 400
Volume of catalyst Vcat cm3 65
Catalyst bulk density qcat gm=cm3 0.9
pressure of reactor Pr atm 2.28
Diameter of catalyst particle dp cm 0.0075
Total geometric volume of catalyst particle VP cm3 1.78  106
Total geometric surface area of catalyst particle SP cm2 7.06  104
Specific surface area of particle Sg cm2 =gm 388.8  102
Total pore volume Vg cm3 =gm 0.37
Regenerator pressure Preg atm 2.588
weight fraction of H2 in coke CH ð—Þ 0.165
relative (catalytic) CO combustion Xpt ð—Þ 0.10
Deactivation order d ð—Þ 1.6
 A.T. Jarullah et al. / Fuel 206 (2017) 657–674 667

Table 3 100
Values of constant cracking factors used in this model.
95
Parameters Value 90
bVGO?LCO 1.5 85

Conversion, %
bVGO?GLN 1.62
bVGO?LPG 1.7
80
bVGO ?DG 0.14 75
ci?LCO 0.43
70
ci?GLN 0.42
ci?LPG 0.52 65
ci?DG 0.22 60 pred exp
ci?CK 0.43
ðLogaDH Þ 2.0116 55
ðLogbDH Þ 5.17720 50
ðLogcDH Þ 7.7388 720 740 760 780 800 820
Temperature, K

7. Results and discussions Fig. 4. Effect of temperature on vacuum gas oil conversion at WHSV = 15h1 and
CTO = 6.

7.1. The kinetic parameters estimation

The values of constant parameters used to simulate the mathe-
matical model are given in Tables 2 and 3. The activation energy
(Ei), pre-exponential factor (Ai) and reactions orders of (ni) have
been determined simultaneously by solving optimization problem
OP1 and are presented in Table 4. The values of the activation
energy (Ei) and pre-exponential factor (Ai) applied to find the con-
centrations of the lumps gave error less than 5% among all results
(as shown in Figs. 4–9). The optimal value of the order of vacuum
gas oil, light cycle oil, gasoline and liquefied petroleum gases con-
centration (ni) are estimated to be (0.925367, 1, 0.999785,
0.999413) respectively. A wide range of values of activation energy
and pre-exponential factor have been reported in literatures and
such parameters were within the range reported in the public
domain [4,18,17,63].
7.2. Effect of operating variables on vacuum gas oil conversion
The effect of each operating variables upon the vacuum gas oil
conversion can be summarized as follows:

Reaction temperature: a set of experiments (taken from litera-
ture) were carried out at various temperatures (460, 510 and
540 °C) while keeping the others parameters constants
(WHSV = 15 h1, CTO = 6).

Catalyst to oil ratio (CTO): different CTO (4, 7 and 10) have been
tested to show the effect of catalyst to oil ratio upon the vacuum
gas oil conversion, keeping others parameters constant (tem-
perature = 490 °C, WHSV = 15 h1).

Table 4
Optimal kinetic parameters obtained for FCC model.

Parameter Symbol Unit Value

Order of vacuum gas oil concentration n1 (–) 0.925367
Order of light cycle oil concentration n2 (–) 1.000001
Order of Gasoline concentration n3 (–) 0.999785
Order of liquefied petroleum gases concentration n4 (–) 0.999413
Activation energy for reaction VGO ? LCO E1 kJ/mol 20431.1
Activation energy for reaction VGO ? GLN E2 kJ/mol 23082.6
Activation energy for reaction VGO ? LPG E3 kJ/mol 23082.6
Activation energy for reaction VGO ? DG E4 kJ/mol 22271.8
Activation energy for reaction VGO ? CK E5 kJ/mol 9006.57
Activation energy for reaction LCO ? GLN E6 kJ/mol 49215.6
Activation energy for reaction LCO ? CK E7 kJ/mol 19854.4
Activation energy for reaction GLN ? LPG E8 kJ/mol 70463.8
Activation energy for reaction GLN ? DG E9 kJ/mol 88051.1
Activation energy for reaction LPG ? DG E10 kJ/mol 65992.4
Pre-exponential factor for reaction VGO ? LCO A1 ðcm
3 0:074633
s1 8.15295  106
gm Þ
Pre-exponential factor for reaction VGO ? GLN A2 ðcm
3 0:074633
s1 391.828
gm Þ
Pre-exponential factor for reaction VGO ? LPG A3 ðcm
3 0:074633
1 1276.72
gm Þ s
Pre-exponential factor for reaction VGO ? DG A4 cm3
ð gm Þ
0:074633 1
s 1656.55

Pre-exponential factor for reaction VGO ? Ck A5 ðcm

3 0:074633
1 1204.11
gm Þ s
Pre-exponential factor for reaction LCO ? GLN A6 s1 598.233
Pre-exponential factor for reaction LCO ? CK A7 s1 20986.8
Pre-exponential factor for reaction GLN ? LPG A8 ðcm
3 0:000215 1 3.0214  107
gm Þ s
Pre-exponential factor for reaction VGO ? DG A9 ðcm
3 0:000215
s1 1.46191  107
gm Þ
Pre-exponential factor for reaction LPG ? DG A10 ðcm
3 0:000215
s1 28090.8
gm Þ
Sum of Square Errors SSE (–) 4.42621  107
668 A.T. Jarullah et al. / Fuel 206 (2017) 657–674

Fig. 5. Effect of reaction temperature on product distribution (A (LCO), B (GLN), C (LPG), D(CK), E(DG)) at WHSV = 15 h1 and CTO = 6.

Wight hourly space velocity (WHSV): various runs of weight

hourly space velocity (5, 20 and 30 h1) were carried out to
declare the effect of time contacting between reactants upon
95
the vacuum gas oil conversion. Other parameters were also kept
90 constant (temperature = 490 °C, CTO = 6).
85
Conversion, %

80
7.2.1. Effect of temperature
75 Fig. 4 shows the experimental data and the model prediction on
70 the effect of temperature on VGO conversion (460–540 °C) at con-
stant WHSV of 15 and the CTO of 6. Clearly there is a good match
65
between experimental conversion of VGO and model prediction
60 exp pred
conversion. The conversion of VGO increased and higher conver-
55 sion of vacuum gas oil IS obtained at higher temperature. This
50 behavior can be attributed to the fact that at high temperature,
3.5 4.5 5.5 6.5 7.5 8.5 9.5 10.5 11.5 reaction rate constants are effectively influenced resulting in an
Catalyst to oil rao (CTO) increase in vacuum gas oil conversion depending on the Arrhenius
equation where the rate constants are a function of reaction tem-
Fig. 6. Effect of catalyst to oil ratio on vacuum gas oil conversion WHSV = 15 h1 perature (direct proportion) and activation energy (inverse
and T = 490 °C. proportion).
 A.T. Jarullah et al. / Fuel 206 (2017) 657–674 669

Fig. 7. Effect of catalyst to oil ratio on product distribution (A (LCO), B (GLN), C(LPG), D(CK), E(DG)) at WHSV = 15 h1 and T = 490 °C.

as shown in this figure. As the temperature increased from 733 K to

100
813 K, the yields of DK and LPG has increased with rising in tem-
90
perature, and that of the light cycle oil (LCO) decreased. While,
80 the yields of gasoline (GLN) increased initially and to decrease
70 thereafter, and the maximum yield is achieved at 773 K, and there
Conversion, %

60 was slight difference in gasoline yields at 763 K and 773 K. Also,

50 the yield of coke (CK) was decreased with increasing in tempera-
40
ture below 763 K and rapidly increased higher than 763 K. Such
behavior is explained as follows: an increase in the rate of reac-
30
pred tions by increasing the reaction temperature, higher cracking are
20
obtained according to low vaporization impact with low tempera-
10 exp
ture [63]. Such behavior related to the results above may also be
0 attributed to that an increase in reaction temperature leading to
2 7 12 17 22 27 32 accelerate intermolecular motions giving higher conversion of
WHSV (h-1) the reactants to new components, hence enhancing the chemical
reaction rate. Better feed vaporization can be obtained at high tem-
Fig. 8. Effect of weight hourly space velocity on vacuum gas oil conversion at
CTO = 6 and T = 490 °C.
perature in addition to reduce the coke content of unvaporized
feed compositions by condensation reactions. The diffusion of feed
compositions can be enhanced when higher temperature and
Fig. 5 shows the product distribution of FCC reaction (both lower coke is achieved [11,53]. It has also been observed from this
experimental and model predictions) as a function of T at WHSV Figure based on the results that the error was less than 5% among
of 15 and CTO of 6. Again there is a good match between experi- all results with high agreement between the predicted and exper-
mental data and predicted results related to the yields of the lumps imental results.
670 A.T. Jarullah et al. / Fuel 206 (2017) 657–674
Fig. 9. Effect of weight hourly space velocity WHSV on products distribution (A (LCO), B (GLN), C(LPG), D(CK), E(DG)) at CTO = 6 and T = 490 °C.
7.2.2. Effect of catalyst to oil ratio (CTO)
Fig. 6 shows the conversion of VGO as a function of CTO at the
reaction temperature of 763 K and the weight hourly space veloc-
ity of 15 h1 (for both experimental and model predictions). Very
good match between the experimental and model conversion is
observed in this Figure. Increasing in CTO from 4 to 10, the conver-
sion of vacuum gas oil increased. In other words, as the CTO
increased, the concentration of the catalyst will increase leading
to increase the reaction rate of primary and secondary cracking.
Such behavior enhances the total number of molecules cracked
on the catalyst surface leading to increase the amount of coke gen-
erated on the particles of the catalyst. As well as, increasing the
CTO, higher temperature of the reactor riser is obtained as more
heat is enhanced in by the hot regenerated catalyst.
Fig. 7 shows the product distribution of FCC reaction (both
experimental and model predictions) at different CTO ratio, where
an increase in CTO, the yields of gasoline (GLN), dry gas (DG), liq-
uefied petroleum gases (LPG) and coke (CK) has increased whereas
decreasing in light cycle oil (LCO). Increasing the catalyst to oil
ration CTO leads to increase the catalyst active sites concentration
that contributes and more reaction rates of cracking reactions are
achieved in addition to higher selectivity toward CRs. Thus, a large
catalyst to oil ration is more suitable for the production of gasoline.
As can also be seen from this Figure, a good agreement between
experimental and predicted results with average absolute error
less than 5% among all the results have obtained via employing
such modified model.
7.2.3. Effect of weight hourly space velocity
Fig. 8 shows the conversion results as a function of weight
hourly space velocity at T of 763 K and the CTO of 6. As the WHSV
increased from 5 to 30 h1, the conversion of VGO has decreased
and higher weight hourly space velocity gives lower residence time
between VGO and catalyst leading to inhibit the THC as a result of
reducing the chemical reactions.
Fig. 9 illustrates the product distribution of FCC reaction at sev-
eral WHSV, where the yield of light cycle oil (LCO) increased by
increasing in WHSV. Opposite phenomena can be observed with
the yields of DG, LPG) and CK (the yields decreased with increasing
in WHSV) as a results of decreasing in contact time. While the yield
of gasoline increased initially and then decreased, and the maxi-
mum yield is obtained at 15 h1 owing to the above reasons.
 A.T. Jarullah et al. / Fuel 206 (2017) 657–674 671

It is also noticed from this Figure that the comparison results
between the experimental and predicted values showed a very
well agreement with an average absolute error less them 5%
among all results.
7.3. Optimal values of operating conditions (OP2)
confident to reactor design, operation and control leading to get
higher profit (higher quality (the highest conversion) and quantity
(the highest octane number).
7.4. The optimal values of the coke content in the regenerated catalyst
(OP3)

The optimal values of the best operating conditions related to It is necessary to take into account the optimal values of the
maximum conversion and the octane number is listed in Table 5. coke content in the regenerated catalyst because of such parame-
Tables 6 and 7 show the results obtained from this study and those ters can effect on the process efficiency, the conversion and the
obtained by last studies related to conversion and the octane num- activity of the catalyst. The optimal values of the best operating
ber. It has clearly been noticed from these Tables that the new conditions used in the regenerator model process with the best
operating conditions obtained via optimization approach gave bet- operation conditions obtained by the last case studies are
ter results where the highest conversion is found to be 87.61% and employed for this purpose. As shown in Table 8, the optimal coke
highest octane number is found to be 97.57. The gaseous and liq- content in the regenerated catalyst of the industrial FCC process
uids mass velocities, molecular diffusivity of the compounds, reac- is minimized to be 0.000362 wt% based on the optimal flow rate
tion rate constants of FCC process, viscosities and densities of the of the air feed to the regenerated catalyst at 0.55 kmol/s and the
components are influenced by the reactor temperature and WHSV optimal temperature of the regenerator of 968.58 K, which is
leading to increase the conversion of such process. Such behavior regarded one of the goals of this study. Such new results can be
supports the fact that the TR is very effective to enhance the degree attributed to the accuracy of the model studied here under process
of catalytic conversion. conditions and constraints, where all the necessary design param-
The WHSV is also an important reaction parameter, which eval- eters, reaction rate equations as a function of operating conditions
uates the reaction severity as well as the FCC efficiency. A decrease (collected depending on the experimental results, mass and energy
in WHSV leads to increase the contact time enhancing the reaction balance, hydrodynamic parameters, physiochemical properties in
severity. Also, the Successive Quadratic Programming (SQP) addition to the catalyst activity that ignored in the literature) have
method used in this work to maximize the process conversion as taken into considerations here. Such design and kinetic parameters
well as the octane number is better than those applied in last stud- can effect on the process leading to reduce the sensitivity analysis
ies (using various approaches to maximize the OBJ getting optimal of the process and giving high deviation and as a results the perfor-
design of FCC reactor). This solution method utilized here having mance and the behavior of the process cannot be predicted confi-
high accuracy to determine the decision variables of FCC operation dently in addition to the advanced solution method utilized here
in gPROMS package in addition to the high trust for solving such (SOP (discussed previously)). The comparative results with those
models, which means that this model can be applied with high obtained by previous studies are listed in are Table 9.
The new results obtained in this study (the highest conversion
and octane number, and the lowest coke content in the regener-
Table 5 ated catalyst) compared with those reported in the literature can
Optimal operating conditions obtained for industrial FCC process.
be attributed to the reasons summarized in Table 10.
Values Unit Symbol Operating conditions
820.012 K TR Reaction Temperature 7.5. The behavior of the industrial FCC reactor
2.002 h1 WHSV Weight Hourly Space Velocity
10.00 (–) CTO Catalyst to Oil Ratio
87.6075 (–) CV Conversion The best kinetics parameters obtained and model developed can
97.5722 (–) Octane number Octane number now be employed for simulating the behavior of the industrial flu-
idized catalytic cracking reactor by varying different process oper-
ating parameters to gain deeper insight of the process. The product
Table 6 yield profiles have been modeled along the riser height as shown in
Comparison between the results obtained in this study and pervious work for vacuum
gas oil conversion.
Table 8
Author(s) (year) Conversion% Optimal operating conditions obtained for regenerated model.
Ancheyta and Sotelo [4] 78
Variables Symbol Unit Values
Han et al. [25] 80
Twaiq et al. [58] 85 Coke in regenerated catalyst Crge Wt% 0.000362
Han and Chung [23] 70 flow rate of air feed to the regenerator Fair Kmol s1 0.55
Han and Chung [24] 75 Regenerator temperature Trge K 968.58
Fernandes et al. [15] 75
This study (2017) 87.61
Table 9
Comparison between the results obtained in this study and pervious work for coke in
Table 7 regenerated catalyst.
Comparison between the results obtained in this study and pervious work for Author(s) (year) Coke in regenerated catalyst (wt%)
gasoline octane number.
Han and Chung (2001) [24] 0.002
Author(s) (year) Octane number Souza et al. (2003) [54] 0.012
Li et al. [37] 85 Penteado et al. (2005) [46] 0.016
Stratiev and Dinkov [56] 89 Fernandes et al. (2005) [14] 0.005
Svoboda et al. [57] 92 Fernandes et al. (2005) [15] 0.003
Watanabe et al. [60] 90 Shuyan et al. (2008) [53] 0.100
Rankovic et al. [50] 91 Chuachuensuk et al. (2013) [5] 0.015
This study (2017) 97.57 This study (2017) 0.000362
672 A.T. Jarullah et al. / Fuel 206 (2017) 657–674

Table 10
Comparison of the new results with those from other simpler models.

Parameter Other models This study

Order of reactions Usually are kept constant (assumed first or second order) Have been estimated based on experiments with minimum errors
Effectiveness factor Usually ignored Has taken into accounts
Kinetic parameters They are kept constant Have estimated based on experiments
Catalyst deactivation Generally has not taken into accounts Has been taken into considerations
Physical properties Usually are kept constant Have been estimated as a function of operating conditions
Hydrodynamic parameters Usually ignored Has taken into accounts
Coke deposited Mostly ignored Have widely been studied
Estimation of kinetic parameters Numerical methods Advanced optimization technique

Fig. 10. This Figure shows the chemical reaction is higher at the
riser entrance than other where the high gradient of the variables
occur. The molecular weight (MW) of gas phase as a function of the 6
riser length is described in Fig. 11, where an increase in the amount
of light products within this phase leads to decrease the molecular 5
weight. Despite the amount of steam is few compared with the

Gas dencity (kg/m3)

overall gas phase, the model can give good data of MW based on 4
such amount of steam and giving low gas density as a function
of MW as stated in Fig. 12. The gas phase and solid phase velocities 3
are plotted in Fig. 13, where the velocity of the process can be
obtained at the higher values of the riser exit with two phases. 2
The slip factor (SF) is shown in the Fig. 14, where higher slip factor
is observed at the entrance of the riser and the velocities of the 1
gases are bigger than velocities of the particles, and these velocities
increased owing to CRs. It accelerates the catalyst velocity result- 0
ing decrease in slip factor. The SF values has ranged to be from 0 5 10 15 20 25 30 35 40
1.2 to 4, and 2 is regarded as typical in a industrial fluid catalytic Riser height (m)
cracking process [15].
Fig. 12. Gas phase density vs. height.

0.8

0.7
20
0.6 VGO 18
0.5 LCO 16
Wt%

14
Velocity (m/s)

0.4 GLN
12
0.3 LPG
10
0.2 CK 8
0.1 FG 6
4
0 gas velocity soild velocity
0 10 20 30 40 2
Riser height (m) 0
0 5 10 15 20 25 30 35 40
Fig. 10. Six lumps concentration profile vs. riser height. Riser height (m)

Fig. 13. Gas phase and catalyst velocities vs. riser height.

160

140 4

120 3.5

100 3
MWt

2.5
Silp factor

80
2
60
1.5
40
1
20 0.5
0 0
0 5 10 15 20 25 30 35 40 0 5 10 15 20 25 30 35 40
Riser hieght (m) Riser height (m)

Fig. 11. Gas phase molecular weight vs. riser length. Fig. 14. Slip factor vs. riser height.
 A.T. Jarullah et al. / Fuel 206 (2017) 657–674
8. Conclusions
From the present study, the following conclusions can be
reported according to the description of such process:

A new mathematical of FCC unit models for the riser and regen-
erator were developed. The best kinetic parameter of the FCC
unit to predict the performance of catalytic cracking kinetic
reaction in reactor in princess catalyst under different operating
conditions (temperature (460, 510 and 540 °C), WHSV (5, 20
and 30 h1), CTO (4, 7 and 10) were investigated here. The
results obtained were compared with the pilot plant results
and a vary good agreement is observed. The commercial unit
results compared with model results indicated that the descrip-
tion of such unit in more accurate compared with those
reported in the public domain.

The best kinetic parameters of this model were estimated via
optimization technique using (Non-Linear methods) based on
experimental results depending on minimizing the sum of
squared error between experimental and predicted results with
average absolute error les that 5% among all the results at var-
ious conditions.

The reaction orders of vacuum gas oil, LCO, GLN and LPG have
also been evaluated to be 0.925367, 1, 0.999785 and 0.999413
respectively.

The feedstock conversion is based on the operating conditions,
therefore the optimal process conditions (mainly, T, WHSV,
and CTO) have studied here for the purpose of getting the high-
est conversion .The maximum conversion of FCC (87.61%) with
high octane number (97.57) for the process is obtained at 820 K,
2 h1 and 10 for T, WHSVand CTO respectively.

The highest conversion and octane number of FCC unit com-
pared with those reported in the literature have obtained.

The optimal coke content in regenerated catalyst is 0.000362 wt
% (the lowest content in comparison with previous studies).
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