Chemical Engineering Science 62 (2007) 4510 – 4528

www.elsevier.com/locate/ces

A new generic approach for the modeling of fluid catalytic cracking (FCC)
riser reactor
Raj Kumar Gupta a , Vineet Kumar a,∗ , V.K. Srivastava b
a Department of Chemical Engineering, Thapar University, Patiala 147 004, India
b Department of Chemical Engineering, Indian Institute of Technology, Delhi 110 016, India

Received 17 April 2006; received in revised form 4 November 2006; accepted 14 May 2007
Available online 21 May 2007

Abstract
A new kinetic model for the fluid catalytic cracking (FCC) riser is developed. An elementary reaction scheme, for the FCC, based on
cracking of a large number of lumps in the form of narrow boiling pseudocomponents is proposed. The kinetic parameters are estimated using
a semi-empirical approach based on normal probability distribution. The correlation proposed for the kinetic parameters’ estimation contains
four parameters that depend on the feed characteristics, catalyst activity, and coke forming tendency of the feed. This approach eliminates the
need of determining a large number of rate constants required for conventional lumped models. The model seems to be more versatile than
existing models and opens up a new dimension for making generic models suitable for the analysis and control studies of FCC units. The
model also incorporates catalyst deactivation and two-phase flow in the riser reactor. Predictions of the model compare well with the yield
pattern of industrial scale plant data reported in literature.
䉷 2007 Elsevier Ltd. All rights reserved.

Keywords: Fluid catalytic cracking; Mathematical modeling; Simulation; Cracking kinetics; Pseudocomponents; Computational fluid dynamics

1. Introduction separation into various fractions, and the deactivated catalyst

Fluid catalytic cracking (FCC) is a process in which
the heavy hydrocarbon molecules are converted into lighter
molecules. The hydrocarbon feed enters a transport bed tubu-
lar reactor (riser) through feed atomizing nozzles and comes
in contact with the hot catalyst coming from the regenera-
tor. The feed gets vaporized and cracks down to the lighter
molecules as it travels upwards along with the catalyst. As a
result of cracking, the velocity of the vapors increases along
the riser height. Coke, the byproduct of cracking reactions,
gets deposited on the catalyst surface thus causing the catalyst
to loose its activity. The cracked hydrocarbon vapors are sep-
arated from the deactivated catalyst in a separator; the vapors
adsorbed onto the surface of the catalyst are also stripped off
using steam in the catalyst stripper. The cracked hydrocarbon
vapors are sent to the main distillation column for further
∗ Corresponding author. Tel.: +91 175 2393063.
E-mail address: vikumar@tiet.ac.in (V. Kumar).
flows into the regenerator. In the regenerator, the coke deposited
on the catalyst surface is burned off to regenerate the catalyst.
The catalyst also becomes hot during the regeneration process.
This hot-regenerated catalyst is recycled back to the riser re-
actor. Thus the catalyst acts as a heat carrier also and provides
the heat required for endothermic cracking reactions in the riser
reactor as well as the heat required for the vaporization of feed.
Detailed modeling of the riser reactor is a challenging task
for theoretical investigators not only due to complex hydrody-
namics and the fact that there are thousands of unknown hydro-
carbons in the FCC feed but also because of the involvement
of different types of reactions taking place simultaneously. It
is believed that catalytic cracking begins with the formation of
carbenium ion (R1–CH+ +
2 –R2 or R–CH3 ) by the interaction of
olefin molecules with the acidic site on the catalyst followed
by the beta scission of the carbenium ion. In the beta scis-
sion reaction, the  bond of carbenium ion breaks to form an
olefin and a new carbenium ion. The carbenium ion formed
by beta scission can undergo further cracking reaction. The
olefin can also be cracked further after being converted to a

0009-2509/$ - see front matter 䉷 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ces.2007.05.009
 R.K. Gupta et al. / Chemical Engineering Science 62 (2007) 4510 – 4528
carbenium ion through hydrogen addition. Thus, large hydro-
carbon molecules can be cracked repeatedly producing suc-
cessively smaller hydrocarbons. However, as the hydrocarbon
chain becomes smaller, cracking rates become slower. At the
same time, a short, less reactive ion can transfer its charge to a
larger, more reactive molecule by hydrogen transfer that makes
the cracking reaction of larger molecules still faster (Wilson,
1997). Such detailed chemistry of catalytic cracking coupled
with a large number of unknown compounds present in the
feedstock is very difficult to be used in the mathematical mod-
eling of an industrial scale FCC riser reactor because of the
analytical and computational limitations.
The traditional and global approach of modeling of crack-
ing kinetics is based on lumping of compounds. Mathematical
models dealing with riser kinetics can be categorized into two
main types. In one category, the lumps are made on the ba-
sis of boiling range of feed stocks and corresponding products
in the reaction system. This kind of model has an increasing
trend in the number of lumps of the cracked components. The
other approach is that in which the lumps are made on the ba-
sis of molecular structure, characteristics of hydrocarbon group
composition in reaction system. This category of models em-
phasizes on more detailed description of the feedstock (Wang
et al., 2005).
These both categories of models do not include chemical
data such as type of reaction and reaction stoichiometry. The
number of kinetic constants in these models increases very
rapidly with the number of lumps. All these models assume
that FCC feed and products are made of a certain number of
lumps, and kinetic parameters for these lumps are estimated
empirically considering the conversion of one lump to the other.
In both of these categories, however, reaction kinetics being
considered is that of ‘conversion’ of one lump to another and
not the ‘cracking’ of an individual lump.
As the reactivity of the feed depends on the composition of
the feed, and catalyst composition and reactivity is important
in determining conversion and product selectivity, the values
of kinetic constants obtained by the above discussed models
depend on the particular pair of feedstock and catalyst for which
they are obtained. Hence, these kinetic constants cannot be used
for different feed and catalyst pairs.
Other modeling schemes include, models based upon reac-
tions in continuous mixtures (Aris, 1989), structure oriented
lumping (Quam and Jaffe, 1992), and ‘single-events’ cracking
(Feng et al., 1993). Nevertheless, the application of these mod-
els to catalytic cracking of industrial feedstocks (vacuum gas
oil), is not realized because of the analytical complexities and
computational limitations. Liguras and Allen (1989a) proposed
a lumped kinetic model so as to utilize the pure components
cracking data for the catalytic cracking of oil mixtures. The
authors in their subsequent work (Liguras and Allen, 1989b)
divided the petroleum feedstock into a number of pseudo-
components. These pseudocomponents were characterized by
grouping the feedstock components into compound classes and
selecting a set of representative compounds in a compound
class and then assigning the concentrations to the representative
compounds. This pseudocomponents characterization method
4511
requires extensive use of analytical procedures and suffers from
the same drawbacks that are cited above. A more detailed com-
pilation of various lumping schemes, and their use in advanced
modeling and control of FCC unit are presented in our recent
work (Gupta et al., 2005).
Even today, in the advanced models of the FCC riser (models
considering various aspects of reactor modeling) three lump or
four lump kinetic schemes are being used by the investigators
to avoid the mathematical complexities and load of computa-
tion that will be there if more number of lumps are considered
in the kinetic scheme as the number of cracking constants in-
creases rapidly with the number of lumps. With this in view, in
the present work, a new approach of kinetic scheme, consider-
ing a large number of lumps (the lightest being methane and
the heaviest containing all compounds of the feedstock having
boiling point close to its end-point), for the FCC riser is intro-
duced. These lumps are characterized using constant Watson
characterization factor, which is an indicator of the feedstock
composition. Characterization was made in such a way that all
physico-chemical properties of the lumps are known and they
can be treated as hypothetical pure components. The proposed
model considers that each lump on cracking gives two other
lumps in one single reaction step. The proposed model falls
under the category of models in which lumps are formed on
the basis of boiling point, but in this approach, each individual
lump is considered as a pure component with known physico-
chemical properties. A separate coke lump is also considered
and it is assumed that when one mole of a lump cracks down
it gives one mole each of two other lumps and the balance ma-
terial gives the coke.
The proposed model also incorporates two-phase flow and
catalyst deactivation. Since a new cracking reaction mechanism
is introduced, a new semi-empirical approach based on normal
probability distribution is also proposed to estimate the crack-
ing reactions’ rate constants. The proposed correlation contains
four parameters that depend on the feed characteristics, cata-
lyst activity, and coke forming tendency of the feed. This elim-
inates the need of estimating the rate constants by regression
analysis. Stangeland (1974) had proposed a kinetic model, for
the prediction of hydrocracker yields, in which the feedstock
was divided into a series of 50 ◦ F boiling range cuts without
characterizing these cuts. In the present work we have charac-
terized the pseudocomponents as discussed in Appendix A.
2. Riser model
The riser is modeled as a vertical tube comprising of a
number of equal sized compartments (or volume elements)
of circular cross section. Volume elements are designated by
symbol j (j = 1, 2, . . . , NC ) and numbering of the volume ele-
ments is done from bottom (inlet) to top (outlet). Each volume
element is assumed to contain two phases (i) solid phase (cat-
alyst and coke) and (ii) gas phase (vapors of feed and product
hydrocarbon, and steam). In one volume element, each phase is
assumed to be well mixed so that heat and mass transfer resis-
tances can be ignored. Model equations are written for both the
phases in each j th volume element for all pseudocomponents
4512 R.K. Gupta et al. / Chemical Engineering Science 62 (2007) 4510 – 4528
PCi (i = 1, 2, . . . , N ). Cracking reactions’ rate constants in
each volume element are evaluated at the local temperature of
the j th volume element and are subsequently used for calculat-
ing the change in molar concentration of each component and
the heats of reactions. This approach of finite volume method
(FVM) is widely used in computational fluid dynamics (CFD)
and has been elaborated elsewhere for membrane separation
process by Kumar and Upadhyay (2000). It is assumed that
known amount of reactants enter the j th volume element, crack-
ing reactions take place in the element for a period equal to the
residence time of the hydrocarbons entering the element. The
concentration of the reacting mixture at the outlet of j th volume
element serve in defining the feed for the (j + 1)th volume ele-
ment. To start computation from volume element number one,
i.e., the inlet of the riser reactor, the known process parameters
at the inlet of the riser are used. To simplify this FVM based
approach for solving material and energy balance equations
in FCC riser reactor, following commonly used assumptions
were made.
2.1. Assumptions
• At the riser inlet, hydrocarbon feed comes in contact with
the hot catalyst coming from the regenerator and instantly
vaporizes (taking away latent heat and sensible heat from
the hot catalyst). The vapor thus formed moves upwards in
thermal equilibrium with the catalyst (Corella and Frances,
1991; Martin et al., 1992; Fligner et al., 1994; Ali et al.,
1997; Derouin et al., 1997).
• There is no loss of heat from the riser and the tempera-
ture of the reaction mixture (hydrocarbon vapors and cata-
lyst) falls only because of the endothermicity of the crack-
ing reactions (Corella and Frances, 1991; Ali et al., 1997;
Theologos et al., 1999; Gupta and Subba Rao, 2001).
• Ideal gas law is assumed to hold while calculating gas
phase velocity variation on account of molar expansion due
to cracking and gas phase temperature (Gupta and Subba
Rao, 2001).
• Catalyst particles are assumed to move as clusters to ac-
count for the observed high slip velocities (Gupta and
Subba Rao, 2001).
• Heat and mass transfer resistances are assumed as negli-
gible (Corella and Frances, 1991; Martin et al., 1992; Ali
et al., 1997; Derouin et al., 1997; Theologos et al., 1999).
• Both phases are assumed in plug flow condition hence back
mixing in both phases is neglected.
2.2. Kinetic modeling
Most of the kinetic schemes currently being used for the
modeling of FCC riser reactor are based on the specified num-
ber of lumps (four lump and 10 lump schemes being the most
common). In the proposed model, any suitably large number of
lumps can be considered. However, in the present work number
of lumps, N, is taken as 50. Each of these lumps is characterized
on the basis of average boiling point and specific gravity, and
treated as hypothetical pure component with all physical, ther-
modynamic, and critical properties known. A brief description
for generating these pseudocomponents is given in Appendix
A. For the generation of these lumps, the feedstock is divided
into 12 lumps and average boiling point of each lump is deter-
mined by area averaging of the true boiling point (TBP) curve
of the feedstock. Thus one individual lump is a collection of
all compounds having boiling point close to each other. The
temperature range between boiling point of the lightest lump of
the feedstock and the boiling point of propane is divided into
31 equal intervals which were considered to be boiling points
of 31 lumps of liquid products to be formed after cracking.
Molecular weight of each lump is also calculated using empiri-
cal correlation proposed by Edmister and Lee (1984) assuming
constant Watson characterization factor for product and feed
lumps. Constituents of dry and wet gas are also considered as
seven lumps consisting of methane, ethane, propane, butene,
butane, pentene, and pentane. Properties of these seven lumps
were taken equal to that of pure components due to the fact that
empirical correlations fail to predict properties of very light hy-
drocarbons and also due to the fact that gaseous products are
rather known mixtures of these hydrocarbons. Thus we have
lumps of seven pure components and 43 hypothetical compo-
nents. Henceforth, all these components are collectively called
pseudocomponents and abbreviated as PCs. Apart form these
50 components, a separate coke lump is also considered which
is formed as a byproduct of the cracking reactions.
The pseudocomponent based approach for design and simu-
lation of crude distillation unit is highly successful. Sufficient
empirical correlations are available in literature to predict al-
most all physico-chemical, thermodynamic, and critical prop-
erties of pseudocomponents. Vapor–liquid equilibrium of these
pseudocomponents are predicted fairly accurately without re-
solving these components in aromatics, olefins, naphthenes, and
paraffins. For applying this approach to FCC modeling, it is as-
sumed that one mole of a pseudocomponent on cracking gives
1 mole each of two other smaller pseudocomponents and some
amount of coke may also form. A schematic diagram of the re-
action mechanism is given in Fig. 1. There are total N blocks
in each column of the diagram and each block in a column
represents one pseudocomponent (blocks in a row represents
same pseudocomponent). Pseudocomponents are numbered in
increasing order of normal boiling point, which also ensures in-
creasing order of molecular weight. According to the proposed
scheme, there are several possible ways through which one par-
ticular pseudocomponent (say ith pseudocomponent, PCi ) can
crack down to give a pair of pseudocomponents PCm and PCn
along with some amount of coke as cracking byproduct accord-
ing to the following pseudoreaction mechanism:
ki,m,n
PCi → PCm + PCn + i,m,n , (1)
where i, m, and n are pseudocomponents’ numbers, i,m,n is
the amount of coke formed (kg) when one kmol of ith pseu-
docomponent cracks to produce one kmol each of mth and nth
pseudocomponents.
 R.K. Gupta et al. / Chemical Engineering Science 62 (2007) 4510 – 4528
Reactant Product 1
Mol. Wt.
MW1 1 1
MW2 2 2
MW3 3 3
MWm m m
MWn n n
MWi i PCi
ki , m ,n
PC m + PC n + coke
MWN-11 N-11 N-11
Feed { MWN N N
Fig. 1. Schematic diagram of reaction mechanism.
The proposed pseudoreaction mechanism is different from
the conventional reaction mechanism. In Eq. (1) PCi is the ith
pseudocomponent consisting of several hundreds of compounds
having molecular weight close to MWi . After cracking, each
individual molecule of PCi gives at least two product molecules
of molecular weight less than the cracking molecule. There is a
wide range of possibilities in which one particular molecule of
PCi can crack. In one case the products may be of widely differ-
ent molecular weights (i.e., one molecule is of small molecular
weight and other of high molecular weight close to the original
molecule). In other case both the product molecules can be of
almost equal molecular weight. Also, amongst these reactions,
some may be coke forming and some may not be coke forming
reactions. Eq. (1) represents the collection of only those reac-
tions in which each compound of molecular weight MWi gives
two molecules of molecular weights MWm and MWn along
with the associated coke formed in this process. Here it should
be noted that for incorporating all possible cracking reactions
of ith pseudocomponent, value of m varies from 1 to i as no
product can be heavier than the reactant. Similarly, value of n
ranges from 1 to m only as the products PCm and PCn are inter-
changeable. Therefore, in the proposed mechanism, there are
(i + 1) × i/2 possible ways in which an ith pseudocomponent
can crack.
For the law of mass conservation, it is required that mass
of reactant should be equal to the mass of products in one
reaction step. Therefore, when MWi kg of PCi cracks to give
MWm kg of PCm and MWn kg of PCn , rest of the material
gives coke (i,m,n ). Thus, the value of i,m,n can be calculated
by taking difference in molar masses of reactant and product
hydrocarbons as follows:
i,m,n = MWi − (MWm + MWn ). (2)
In Eq. (1) there are (i + 1) × i/2 possible ways in which
cracking reaction for one pseudocomponent PCi can be writ-
ten. Only two of such possible reactions are shown by solid
line in Fig. 1. The dashed line represents the same reaction, as
4513
+ Product 2 + coke
1
2
3
m
n
Amount of coke (gram)
=MWi - (MWm+ MWn)
N-11
N
the values of m and n in Eq. (1) are interchangeable. Thus the
total number of reactions that could be written for the com-
plete set of reactions becomes N × (N − 1) × (N − 2)/3 (for
N = 50, total number of reactions become 39 200). However,
all of these reactions are not feasible. The feasibility of a reac-
tion is found using the stoichiometry of the cracking reaction
(Eq. (1)). Only those reactions are considered feasible for which
the value of i,m,n calculated by Eq. (2) is either zero or posi-
tive. This natural constraint greatly reduces the number of fea-
sible cracking reactions but still the number is too large (more
than 10 000 in the present case with N = 50).
To handle such a large number of reactions in riser reactor,
special considerations for the estimation of reaction rate con-
stants and technique for solving material and energy balance
equations are required. In the present work, a new semi-
empirical scheme for the estimation of rate constants is devel-
oped. This scheme makes the kinetic model more versatile. In
the beginning, six parameters were introduced to adjust more
than 10 000 reaction rate constants (ki,m,n ) needed to explain
complete reaction mechanism in a typical FCC riser reactor.
Later, it was observed that only four of these parameters are
significant. However, for the pedagogical point of view, this
correlation is discussed in detail in Appendix B in the same
sequence as it was developed.
The final form of this correlation is given by the following
equation:
 2
ki,m,n = [k0 MWi ]e−1 (MWm −MWn )
 −i,m,n /2
− e−MWi

−E0 MWi /RT e
×e . (3)
1 − e−MWi
In the above equation, parameters to be estimated by using
experimental data are k0 , , E0 , , 1 , and 2 . Later it was
observed that two parameters  (correlating frequency factor
in terms of molecular weight of pseudocomponent) and 1
(an indicator of cracking tendency of pseudocomponents from
4514 R.K. Gupta et al. / Chemical Engineering Science 62 (2007) 4510 – 4528
middle or from sides) are insignificant, thus the correlation
reduces to the following four parameter equation:
 −i,m,n /2
− e−MWi

 e
ki,m,n = k0 e−E0 MWi /RT . (4)
1 − e−MWi
Therefore, the parameters required to be estimated are k0 ,
E0 , , and 2 . All these parameters are constant for a particu-
lar pair of feed and catalyst. Parameter 2 correlates the coke
forming tendency of the feed and parameter  correlates acti-
vation energy of individual pseudocomponent in terms of its
molecular weight.
The theoretical kinetic scheme developed in the present work
assumes that all the cracking reactions are of first order. This is
in agreement with the reported cracking rate of gas lump and
gasoline lump. Many researchers have reported the cracking of
heavier fractions of feed such as gas oil lump to be of second
order due to deeper cracking action. In the present case feed
is broken into large number of narrow boiling lumps (pseu-
docomponent), therefore, first order cracking can be assumed
safely even for heavier lumps.
Thus for first order reactions, rate of disappearance of ith
pseudocomponent due to cracking in j th volume element
through one reaction as indicated in Eq. (1) is given by
ri,m,n = j · ki,m,n · Ci,j · (Mcat · t Cat j ),
where the concentration of ith pseudocomponent at the inlet of
j th volume element is given by
Pi,j
Ci,j = . (6)
(ug,j · g,j )Ar
Pi,j in Eq. (6) is kmol of ith component entering per second
into the j th volume element. Ar , ug,j , and g,j are area of
cross-section of the riser, local gas velocity, and gas phase vol-
ume fraction in the j th volume element. t Cat j is the resi-
dence time of catalyst in the j th volume element, hence Mcat ·
t Cat j in Eq. (5) is the mass of catalyst present in j th volume
element.
Non-selective deactivation of catalyst, because of coke de-
position, is assumed. The activity coefficient (j ) depends on
the coke concentration on the catalyst. Pitault et al. (1995) pro-
posed the following correlation for the estimation of activity
coefficient:
B +1
j = , (7)
B + exp(A · Ccj )
The values for deactivation constants A and B reported
by the authors are 4.29 and 10.4, respectively; the same are
used in this work. Ccj is the concentration of coke on catalyst
surface (wt%).
2.3. Material balance
Calculation of material balances with several thousands of
parallel reactions is practically impossible by analytical solu-
tion of ordinary differential equations (ODE) representing rate
equations. Using higher order numerical techniques, such as
Runge–Kutta method, is also not feasible for solving these
ODEs due to excessive computational load. Therefore, an FVM
based approach was used for computing material balances. As
discussed earlier, in this FVM approach it is assumed that the
riser reactor is made up of a large number of volume elements
of circular cross-section and of very small height, placed one
over the other. Volume elements are numbered from bottom to
top, i.e., from inlet to outlet (Fig. 2).
Both gas phase and solid phase are moving through each vol-
ume element in upward direction, with different velocity. Since
the height of a typical j th volume element zj is very small,
therefore the residence-time for the gas phase, tj , and the
residence-time of the solid phase, t Catj , is also very small.
Applying concepts of finite volume approach, it is assumed that
all reactions take place for tj time at a constant rate deter-
mined by the prevailing temperature, pressure, and concentra-
tion at the inlet of j th volume element. After elapse of time
tj the temperature and concentration of the stream (which is
now outgoing stream from j th element) are determined by the
following material balance equations.
Material balance over j th volume element for the gas
phase:
Rate of mass in from the (j − 1)th element
(5)
− rate of mass out from j th element
= rate of mass converted to coke in j th element (8)
N N
 
or Pi,j −1 MWi − Pi,j MWi
i=1 i=1
 N 
 m
i 

= ri,m,n i,m,n . (9)
i=1 m=1 n=1 for all feasible reactions
Similarly, material balance over j th volume element for solid
phase:
Rate of mass out from j th element
− rate of mass in from the (j − 1)th element
= rate of mass accumulated in j th element
= rate of mass of coke formed (10)
or (Mcat + Mcokej ) − (Mcat + Mcokej −1 )
N i m
  

= ri,m,n i,m,n , (11)
i=1 m=1 n=1 for all feasible reactions
where Mcokej is the cumulative mass of coke formed upto
j th volume element. For the first volume element (j = 1),
Mcokej −1 is the mass of coke on regenerated catalyst.
In Eqs. (9) and (11) summation for i is done from 1 to N.
However, summation for m is done from 1 to i only because
no product species can have molecular weight greater than the
reactant species, whereas summation over n is done from 1 to
m only as the products PCm and PCn are interchangeable.
 R.K. Gupta et al. / Chemical Engineering Science 62 (2007) 4510 – 4528 4515

Fig. 2. A typical volume element in the riser reactor.

2.4. Heat balance H combi = − 0.4017 API2i + 57.859 APIi + 1953.14 ln(APIi )
+ 37037.09 for 25APIi 50, (13)
It is assumed that the hydrocarbon feed, after coming into
contact with hot catalyst from the regenerator, vaporizes com- H combi = 55.824 APIi + 43775.32 for APIi 50. (14)
pletely in the first volume element of the riser. Afterwards the
gas phase is in thermal equilibrium with the catalyst all along Eqs. (12)–(14) were obtained by curve fitting of graphical data
the reactor. At the entrance (the first volume element of the proposed by Maxwell (1968). Curve fitting was done in such
riser reactor) the equilibrium temperature, Tin , is calculated by a way that there is no discontinuity in the heats of combustion
taking into account the specific heat of catalyst and the latent values predicted by these three equations.
heat of vaporization of the feed. Thus for the cracking of ith pseudocomponent, giving mth
The pseudocomponents are chemically stable hypothetical and nth pseudocomponents, heat of reaction becomes
components, and according to the proposed reaction mech-
anism one pseudocomponent produces two other chemically H r i,m,n = i,m,n · H coke + (MWm H combm
stable pseudocomponents. This indicates that the proposed re-
action mechanism includes all possible reactions taking place + MWn H combn − MWi H combi ). (15)
during cracking (such as hydrogen-transfer, condensation,
isomerization, etc.) that leads to the formation of chemically Thus the energy balance equation for the j th volume element
stable products in the form of pseudocomponents. There- can be written as
fore, the overall heat of reaction (Hr ), of Eq. (1) can be 
estimated by finding the difference between the heat of com-
Mcat · Cpcat + Mcokej −1 · Cp coke + Mst · Cp st
bustion of all products and the heat of combustion of the
reactant.
N

Heat of combustion of pseudocomponents, H comb, is esti- 
+ Pi,j −1 MWi · Cp i (Tj −1 − Tj )
mated by the following equations in terms of the API gravity
i=1
of the hydrocarbon:  

= ri,m,n · H r i,m,n (16)
.
H combi = 133.976 APIi + 41170 for APIi 25, (12) i m n for all feasible reactions

Rearranging the above energy balance equation, we get

  
( i m n ri,m,n · H r i,m,n )for all feasible reactions
Tj = Tj −1 − . (17)
· Cp st + N

(Mcat · Cp cat + Mcokej −1 · Cp coke + Mst i=1 Pi,j −1 MWi · Cp i )
4516 R.K. Gupta et al. / Chemical Engineering Science 62 (2007) 4510 – 4528

The temperature (Tj ) thus calculated was used for the estima- g g |ug − uc |dc
tion of kinetic parameters in the next volume element and other Re = . (25)
g
temperature dependent properties of the pseudocomponents.
Eq. (19) can be solved as a difference equation and the value
2.5. Hydrodynamics of solid phase velocity in the next volume element can be cal-
culated with the initial condition of solid phase velocity at the
In the proposed riser model two phases (cluster phase and riser entrance calculated by the following equation:
gas phase) are considered. Cluster phase includes the loosely Mcat
held particles of catalyst and the coke. The cluster phase and uc0 = , (26)
c Ar c0
gas phase hold up vary along the riser height. Solid particles
spend more time in the riser than hydrocarbon vapor due to where uc0 and c0 are the values of solid phase velocity and
slip between the two phases. The slip velocities observed in the solid phase volume fraction at the entrance of first volume
riser are higher than the terminal settling velocity of a single element.
particle. The reason for the higher slip velocities is attributed The value of cluster volume fraction for the next volume
to particles moving in clusters (Subba Rao, 1986; Fligner et al., element is calculated by the equation
1994; Horio and Kuroki, 1994). The clusters are agglomerates Mcat
of loosely held particles (Fligner et al., 1994). Cluster voidage cj = . (27)
c Ar ucj
( c ) is assumed to be 0.5, in line with the two-phase theory of
fluidization. Gas phase volume fraction is obtained using the relation
As proposed by Tsuo and Gidaspow (1990), solid phase c + g = 1. (28)
momentum balance along the riser height may be written as
Having obtained the values of the solid phase velocity and
d( c c uc uc ) 2 cluster volume fraction for the second volume element, the total
= Cf (ug − uc ) + 2fs c c uc − c c g. (18)
dz pressure drop for the first volume element can be calculated.
Assuming the change in the mass of solids along the riser height The pressure drop is assumed to be composed of four main
as negligible (this assumption is valid as the change in the mass components (Pugsley and Berruti, 1996):
of solid phase from riser entrance to riser outlet due to coke 
dP

dP

dP

dP

dP
deposition is typically less than 1%, hence in a volume element = + + + ,
dz total dz s dz acc dz f s dz fg
of the riser the change in the mass of solids will be negligibly
small) solid phase continuity equation can be written as (29)
where (dP /dz)s is the pressure drop due to the hydrostatic
duc 2fs c c u2c head of the solids, (dP /dz)acc is the pressure drop due to solids
c c uc = Cf (ug − uc ) + − c c g. (19)
dz D acceleration, and (dP /dz)f s and (dP /dz)fg are the pressure
The frictional force per unit volume at the gas particle inter- drops due to solids friction (defined as the frictional force per
phase due to differing phase velocities can be calculated by the unit volume between solids and wall) and gas friction (defined
following expression (Markatos and Shinghal, 1982): as frictional force per unit volume between the gas and the
solids), respectively. These components can be calculated using
F = 0.5CD AP g |ug − uc |(ug − uc ) = Cf (ug − uc ), (20) the following relations:

where AP is total projected area of particles per unit volume, dP
= c gc , (30)
CD is interphase friction coefficient between the two phases. dz s
Projected area per unit volume can be calculated based on
c u2c

dP
equivalent spherical diameter as = c , (31)
dz acc 2 z
AP = 1.5 c /dc . (21)
2fs c c u2c

dP
= , (32)
In the above equations dc is cluster diameter, 6.0 × 10−3 m dz f s D
(Fligner et al., 1994), and c is cluster density. The cluster
fg 2
g ug

density can be approximated by the following expression: dP
= . (33)
dz fg D
c= p (1 − c) + g c p (1 − c ). (22)
Blasius friction factor given by the following empirical equation
The empirical correlations for CD used by Arastoopour and is used as the gas friction factor
Gidaspow (1979) are
fg = 0.316Re−1/4 . (34)
24
CD = (1 + 0.15Re0.687 ) for Re < 1000, (23) Konno’s correlation is used to calculate the solids friction factor
Re
CD = 0.44 for Re1000, (24) fs = 0.0025u−1
c . (35)
 R.K. Gupta et al. / Chemical Engineering Science 62 (2007) 4510 – 4528
The pressure in the next volume element is obtained by the
following relation:
 way that the deviation in predicted and actual data, at the riser
dP
Pj = Pj −1 − z. (36)
dz total
The gas phase density is calculated from the ideal gas law as
   these parameters, an iterative method was adopted in which one
Pj N i=1 yi,j MWi
gj = (37)
RTj
and the gas phase velocity is calculated by
 
Mst + N

i=1 Pi,j MWi
ugj = . (38)
Ar g,j gj
Residence time of catalyst in volume element j is
(z)j
t Catj = . (39)
uc,j
2.6. Model solution
Model simulation is done on a P-IV computer, which took
less than 5 min for giving the simulation results. Although we
can take variable height of volume elements, however, in the
present work the height of each volume element of the riser
was kept 10 mm. Further decrease in the height of the volume
element had no appreciable effect on the results.
3. Results and discussions
The material balance equations were combined with reaction
kinetics and the hydrodynamic model equations to obtain the
moles of each pseudocomponent coming out of any volume
element j (=1 to Nc) of the riser reactor. Thus, the model
could predict the yield pattern along the riser height. Model
validation is done as three case studies by using industrial data
reported in the literature. Results of the proposed model can
be obtained by adjusting six parameters as discussed earlier.
Numerical values of these parameters were obtained separately
for each case study. Results of the simulator are being discussed
in the following case studies.
Due to the unavailability of the feed TBP data for each case,
boiling point characteristic of feed (simulated distillation, SD)
reported by Pekediz et al. (1997) is used (Table A1) for all the
case studies. Various other parameters common to all cases are
given in Table 1 and plant data used in these cases are presented
in Table 2.
3.1. Case study 1
Industrial FCC plant data reported by Ali et al. (1997),
presented in Table 2, was used in this case study. In this
case five industrial data at the riser outlet—gasoline yield,
gas yield, unconverted hydrocarbon, coke yield, and riser
outlet temperature—are available to obtain the rate constant
parameters.
4517
Model results were obtained by adjusting four rate constant
parameters and two tuning parameters of Eq. (3) in such a
outlet, is minimum. To achieve this, these parameters (k0 , ,
E0 , , 1 , and 2 ) were determined by line-search technique
followed by golden-section method. To estimate the value of
parameter was varied at a time (keeping other five constant).
Starting with an initial guess value of all six parameters, a line-
search was made (by changing one parameter with a constant
increment/decrement) to find a condition where the sum of
absolute value of deviation in the predicted and experimental
values of product yield and temperature at riser outlet are mini-
mum. Then the value of this parameter was fine tuned between
two consecutive values considered during line-search by the
method of golden-section. Since the system of equations under
consideration is highly nonlinear, on-line graphical observa-
tion of reported and predicted data was made almost after each
iteration.
The simulator results, yield pattern and temperature profile,
are compared with the industrial data at the riser outlet in
Figs. 3 and 4, respectively. The values of six parameters are
k0 = 0.01,  = 0.01, E0 = 1540,  = 0.43, 1 = 0.0, 2 = 17.0.
Fig. 4 indicates that as the hydrocarbons and catalyst mixture
travel upwards, the temperature inside the FCC riser reactor
decreases because of the endothermic cracking reactions. The
catalyst temperature at the inlet of the riser (960 K) falls sharply
to 880 K because sensible heat of catalyst coming from the re-
generator is utilized in providing heat for raising the sensible
heat of the feed, for vaporizing the feed, and for further heating
of the vaporized feed. Afterwards, within first 10 m height in-
side the riser reactor the temperature drops from 880 to 790 K,
as most of the cracking takes place within first 10 m of the
riser height. The temperature at the outlet of the riser is 774 K
(Fig. 4). The decrease in reaction mixture’s temperature and
catalyst activity along the riser height cause a decline in the
reaction rate, hence the temperature gradient falls appreciably
with the increasing riser height.
Sensitivity analysis: Sensitivity analysis of these parameters
is presented in Figs. 5–7. Sensitivity analysis is the process of
varying the parameters over a wide range about the mean value
and recording the relative change in predicted gas, gasoline,
and coke yields (Figs. 5–7). The sensitivity of one parameter
relative to other is also demonstrated in these figures. Such
analysis is useful in cases when the experimental data are few
in number and statistical analysis cannot be applied to predict
confidence interval. A detailed discussion about the sensitivity
analysis is given by Saltelli (2000). Figs. 5–7 show that in the
proposed model, gas yield and coke yield, are strong functions
of E0 , , and 2 , and gasoline yield is very sensitive to E0 , and
 and moderately sensitive to k0 , and 2 , whereas,  is almost
insensitive parameter. It is evident from these figures that 
has virtually no effect on any product yield. This indicates
that the frequency factor (k0,i ) is independent of molecular
weight. Also, the value of parameter 1 is zero. Therefore only
four parameters may be used to match the model results with
the industrial data, with 1 = 0, and  = 0. Hence for all the
4518 R.K. Gupta et al. / Chemical Engineering Science 62 (2007) 4510 – 4528

Table 1
Parameters used for the simulation of riser reactor

Parameter Value Source

Heat of combustion of coke −32950 kJ/kg Austin (1984)

Molecular weight of coke 12 kg/kmol Arbel et al. (1995)
Volume fraction of clusters at inlet 0.5 Gupta and Subba Rao (2001)
Specific heat of catalyst 1.15 kJ/kg K Ali et al. (1997)
Specific heat of steam 2.15 kJ/kg K Blasetti and de Lasa (1997)
Mass flow rate of steam 1.33 kg/s Blasetti and de Lasa (1997)
Feed temperature at the riser inlet 494 K Ali et al. (1997)
Latent heat of feed vaporization 96 kJ/kg Gupta and Subba Rao (2001)
Catalyst particle density 1200 kg/m3 Gupta and Subba Rao (2001)
Catalyst particle diameter 75 m Gupta and Subba Rao (2001)
Specific gravity of feed 0.9292 g/cm3 Pekediz et al. (1997)
Cluster diameter 6 mm Fligner et al. (1994)

Table 2
Plant data used for simulation of riser reactor

Ali et al. (1997) (Case study—1) Derouin et al. (1997) (Case study—2) Theologos and Markatosa (1993) (Case study—3)

Riser height 33 m (32 m) 50 m

Riser diameter 0.8 m 1.0 m 1.24 m
Riser pressure 2.9 atm 3.15 atm (2.9 atm)
Catalyst temperature 960 K (960 K) 1025 K
Feed rate 20 kg/s 85 kg/s 17.5 kg/s
Feed temperature 496 K 650 K 568 K
C/O ratio 7.2 5.53 8.0

Data given in the parentheses are those used in the present work in place of data either not reported or reported in ranges.
a Literature data.

120 1000
Plant data Model predictions Model prediction
Gas yield Gas yield
100 Plant data (Source: Ali et al., 1997)
Gasoline yield Gasoline yield
950
Coke yield Coke yield
80 Unconverted Unconverted
Riser temperature (K)

900
Yields (wt%)

60

40 850

20
800

750
0 5 10 15 20 25 30 35 0 5 10 15 20 25 30 35
Riser height (m) Riser height (m)

Fig. 3. Case study 1, comparison with the data reported by Ali et al. (1997). Fig. 4. Axial temperature profile along the riser height.

subsequent simulations only four parameters (k0 , E0 , , and 2 ) values of the four parameters are k0 =0.01, E0 =1540, =0.43,
are used. and 2 = 17.0. The product yield profiles given in Figs. 3 and 8
Case study 1 with four parameters: The results for case study match very closely. Also, the temperature profiles obtained in
1 using the four parameters are presented in Figs. 8–11. The Figs. 4 and 9 are similar.
 R.K. Gupta et al. / Chemical Engineering Science 62 (2007) 4510 – 4528 4519

Fig. 5. Sensitivity analysis for gas yields. Fig. 7. Sensitivity analysis for coke yields.

120
Plant data Model prediction
Gas yield Gas yield
100 Gasoline yield Gasoline yield
Coke yield Coke yield
80 Unconverted Unconverted
Yields (wt%)

60

40

20

0 5 10 15 20 25 30 35

Riser height (m)

Fig. 6. Sensitivity analysis for gasoline yields.
The activity of the catalyst also decreases rapidly as byprod-
uct (coke) of the cracking reactions gets deposited on the cata-
lyst surface (Fig. 10). Fig. 11 shows an initial decline in the gas
velocity because of the sharp increase in the gas void fraction
due to increase in the moles of the gas as a result of cracking.
After this initial decline, the gas velocity starts increasing as
the cracking reactions along the riser height continues to in-
crease the moles of the gas causing a continuous decline in the
gas phase density. The initial sharp increase in the catalyst ve-
locity is due to the sharp fall in the solid volume fraction and
drag exerted by the gas. After this initial sharp increase the
Fig. 8. Case study 1, comparison with the data reported by Ali et al. (1997)
with four parameters.
catalyst velocity keeps on increasing gradually all along the
riser height.
Also, high values of slip factor are predicted in riser en-
try zone which gradually decreases along the riser height
and finally reaches at 1.8 (Fig. 11). Catalyst volume fraction
falls from about 0.5 to 0.1 in first few meters of riser height
(Fig. 12). This sharp decline can be attributed to the fact that
most of the cracking takes place within first few meters of the
riser height. Furthermore, the catalyst volume fraction along
the riser height is plotted for two initial values (0.5 and 0.3).
4520 R.K. Gupta et al. / Chemical Engineering Science 62 (2007) 4510 – 4528

1000 14 0.55

Plant data
12
0.50
Model prediction

Gas phase molar flux (kmol/m s)

950

2
10
Riser temperature (K)

0.45

Velocity (m/s)
8
900
0.40
6

850 0.35
4
Gas phase velocity
Catalyst velocity 0.30
2
800 Gas phase molar flux

0 0.25
0 5 10 15 20 25 30 35
750 Riser height (m)
0 5 10 15 20 25 30 35
Fig. 11. Predicted catalyst and gas velocity profiles and gas phase molar flux
Riser height (m)
along the riser height.
Fig. 9. Axial temperature profile along the riser height with four parameters.

0.50
1.2
0.45 Initial cluster volume fraction = 0.5
Initial cluster volume fraction = 0.3
1.0 0.40
Catalyst volume fraction

0.35
0.8
0.30
Catalyst activity

0.25
0.6
0.20

0.4 0.15

0.10
0.2
0.05

0.00
0.0 0 5 10 15 20 25 30 35
5
0 5 10 15 20 25 30 35
Riser height (m)
Riser height (m)
Fig. 12. Predicted catalyst volume fraction along the riser height.
Fig. 10. Predicted catalyst activity along the riser height.

The plots for both the values are almost similar because this
value gets adjusted very quickly at the riser entrance itself
(in the first 2 m of the riser height itself the catalyst volume
fraction value reaches 0.12 for both the cases) and hence the
yield profiles remain unaffected.
Since plant data for the product yields were available at the
riser outlet only, few more comparisons were made in subse-
quent case studies. Even without changing the values of the
parameters the results of the simulation were encouraging.
However, for better comparison, the parameters were adjusted
further in both the following case studies. It is observed that
the parameters k0 , and 2 are the two parameters those were
needed to be adjusted for different cases.
3.2. Case study 2
In this case FCC plant data (Table 2) reported by Derouin
et al. (1997) was used to compare the simulator predictions.
Authors have reported the product data for gasoline yield and
conversion at different positions along the riser height (Fig. 13).
 R.K. Gupta et al. / Chemical Engineering Science 62 (2007) 4510 – 4528 4521

80 ous transport equations. Riser operating conditions given in

Table 2 (Theologos and Markatos, 1993) were used for the
70 simulation. A comparison of the gasoline yield from the model
presented in this work, with the gasoline yield from 3-D, two-
60
phase flow, heat transfer and reaction model of Theologos and
Markatos (1993) is made. Only two parameters k0 , and 2 were
Conversion or yield (wt%)

changed appreciably. The final values of the parameters were

50
k0 = 0.0012, E0 = 1540,  = 0.4, and 2 = 13.0. Comparison
of results predicted by present approach and those reported by
40 Theologos and Markatos (1993) is given in Fig. 14. Although
Model gasoline
the model of Theologos and Markatos (1993) is mathemati-
30 cally complex, its yield prediction profiles are similar to the
Plant gasoline
models that use constant values for the gas and solid velocities
20 Model conversion and four to six lumps.
Plant conversion The present model overpredicts the product yields in the first
10 few meters of riser height. This may be attributed to the fact
that in this region the heat and mass transfer resistances are not
0
negligible.
0 5 10 15 20 25 30 35
4. Conclusion
Riser height (m)
A new technique for modeling the FCC riser has been devel-
Fig. 13. Case study 2, comparison with the plant data reported by Derouin
oped. The model incorporated a more realistic kinetic scheme
et al. (1997).
for the cracking reactions, and a new correlation to evaluate
100 Arrhenius type reaction rate constants. The rate constant param-
Theologos and Markatos model prediction
eters can easily be obtained for each combination of feed and
Present model prediction catalyst. Although there is significant variation in the yield pat-
80 tern of different case studies, activation energy parameter (E0 )
Conversion remained same for all cases. However, to account for differ-
Conversion or yields (wt%)

ent characteristics of the feedstock and catalyst, only frequency

factor parameter (k0 ) and feed coking tendency parameter 2
60 were required to be adjusted to compare the yield patterns of
different case studies with the model results.
Gasoline The proposed model is capable of predicting overall conver-
40 sion, products yields, temperature, and catalyst activity along
the riser height. The model results are in close agreement with
Gas+coke the industrial data reported in the literature and the data pre-
dicted by other simulators.
20
The predictions of the FCC riser reactor model are dependent
on the values of cracking reactions’ rate constants, which can
easily be obtained with the help of proposed kinetic model for
0 different characteristics of the feedstock, type of catalyst, ac-
0 10 20 30 40 50 60 tivity of catalyst, and operating parameters. Therefore, it seems
Riser height (m) to be more appropriate to use these rate constant parameters
obtained for a pair of feedstock and catalyst in place of using
Fig. 14. Case study 3, comparison with the simulator data reported by the kinetic constants from the literature which are obtained for
Theologos and Markatos (1993). a different combination of feedstock and catalyst by regression
analysis. Further, this detailed kinetic model can be easily used
The results of simulation with k0 = 0.045, E0 = 1540,  = 0.43, for the other advanced studies (such as control and optimiza-
and 2 = 17.0, are presented in Fig. 13. Model predictions for tion) of FCC modeling.
the gasoline yield along the riser height matches satisfactorily
with the plant data. Notation

3.3. Case study 3 Ar cross-sectional area of riser, m2

Cc coke concentration on catalyst surface, wt%
The objective of this case study is to compare the results Ci,j concentration of ith pseudocomponent in j th
from the present work with other models based on rigor- volume element, kmol/m3
4522 R.K. Gupta et al. / Chemical Engineering Science 62 (2007) 4510 – 4528

Cpcat specific heat of catalyst, kJ/kg cat density of catalyst, kg/m3

Cpi specific heat of ith pseudocomponent, kJ/kg coke density of coke, kg/m3
Cpmix,j specific heat of the gas and solid mixture in j th g,j density of gas phase in j thvolume element
volume element, kJ/kg 1 , 2 tunable parameters
Cpst specific heat of steam, kJ/kg j catalyst activity coefficient
Ei activation energy for cracking of ith pseudocom-
ponent giving kmax,i , kJ/kmol
H coke heat of combustion of coke, kJ/kg Appendix A.
H comb heat of combustion of pseudocomponents, kJ/kg
Hr heat of reaction, kJ/kmol Petroleum fractions are mixtures of innumerable compo-
k0,i frequency factor for cracking of ith pseudocom- nents which are difficult to be identified individually. However,
ponent giving kmax,i m3 /(kg Cat s) Watson characterization factor can be treated as an indicator of
ki,m,n rate constant for the cracking of ith pseudocom- the composition of various groups of compounds (such as paraf-
ponent to produce mth and nth pseudocompo- fin, olefin, naphthene, aromatic, etc.) present in the petroleum
nents, m3 /(kg Cat s) fraction. Watson and Nelson (1933) made a remarkable ob-
1/3
Mcat mass flow rate of catalyst, kg/s servation that the factor KW (=Tb /sg), known as Watson
Mcokej mass flow rate of coke at the outlet of j th volume characterization factor, is closer to 12 for paraffins and olefins,
element, kg/s approximately 10 for aromatics, and between 11 and 12 for
Mst mass flow rate of steam, kg/s naphthenes when the normal boiling point of the component,
MWi molecular weight of ith component, kg/kmol Tb , is in Rankin and sg is the specific gravity at 60◦ /60 ◦ F.
N total number of components, including pure The characterization factor of the mixture of hydrocarbons is
components and pseudocomponents given by KW = MeABP1/3 /sg, where MeABP is the mean av-
NC total number of hypothetical volume elements erage boiling point of the mixture (API Data Book, Chapter 2,
in the riser Characterization of Hydrocarbons, 1976). Using this, Miquel
p pressure, atm and Castells (1993) proposed a method along with a computer
Pi,j molar flow rate of ith component,PCi , through program (Miquel and Castells, 1994) that can represent an oil
j th volume element, kmol/s fraction by an equivalent mixture of small number of hypothet-
ri,m,n rate of disappearance of ith pseudocomponent ical components or pseudocomponents. To use this approach,
giving mth, and nth pseudocomponents, kmol/s atmospheric TBP distillation curve and the entire fraction den-
R gas constant, atm m3 /(kmol K) sity is required. This method assumes that if the difference in
tj residence time of gas phase in j th volume final boiling point (FBP) and initial boiling point (IBP) of a
element, s petroleum oil is not too high (i.e., < 300 K) then the Watson
t Cat j residence time of catalyst in j th volume characterization factor of any narrow-boiling fraction (boiling
element, s range between 15 and 25 K) of this oil remains equal to that of
Tin temperature of reaction mixture in the riser original petroleum oil.
inlet, K In the present case, due to unavailability of TBP curve for
Tj temperature of reaction mixture leaving j th the FCC feed, SD curve reported by Pekediz et al. (1997) was
volume element, K used. The SD curve was first converted to ASTM-D86 curve
u superficial gas velocity, m/s and then to TBP curve by the correlation proposed by Daubert
uc cluster velocity, m/s (1994). The two-step conversion of SD data to TBP data is given
ug actual gas velocity, m/s in Table A1. To generate pseudocomponents, the TBP curve of
the feed was divided into 12 parts, out of which four were of
Subscripts 5 vol% each and eight of 10 vol% each (shown as vertical bars
i, m, n ith, mth, and nth component in Fig. A1 ). These vertical bars represent 12 pseudocompo-
j j th volume element in the riser starting from the nents of the feed. The boiling point of each individual pseudo-
bottom component was determined by area-averaging of the TBP curve
(clearly visible in Fig. A1). Considering constant Watson char-
Greek letters acterization factor, specific gravity of each pseudocomponent
was determined by the equation
i,m,n mass of coke formed when 1 kmol of pseudo-
component PCi cracks to give 1 kmol each of 1/3
PCm and PCn , kg coke/kmol PCi T
sg = 1.21644 b (where Tb is in K). (A.1)
g,j volume fraction of gas in j th volume element KW
 exponent of molecular weight for frequency
factor Molecular weights of these pseudocomponents were then
 exponent of molecular weight for activation calculated by the following equation proposed by Edmister and
energy Lee (1984), which requires knowledge of boiling point and the
 R.K. Gupta et al. / Chemical Engineering Science 62 (2007) 4510 – 4528
Table A1
Distillation data of hydrocarbon feed (Pekediz et al., 1997)
Vol. % distilled (wt%) SD (K)
IBP 532
10 587
30 621
50 650
70 683
90 730
FBP 800
Density of feed (at 15 ◦ C) = 929.20 kg/m3 .
a Estimated using correlation proposed by Daubert (1994).
Fig. A1. Pseudocomponents generated from feed TBP.
specific gravity of a hydrocarbon fraction:
MW = 204.38 · e(0.00218·Tb ) · e(−3.07·sg) · Tb0.118 · sg1.88 . (A.2)
Having known values of the volume fraction, boiling point,
specific gravity, and molecular weight, each individual bars
of Fig. A1 can be treated as a pure component (of course,
hypothetical pure component or pseudocomponent). To make
use of the Eqs. (A.1) and (A.2), an iterative method has to
be adopted as the value of Watson characterization factor is
not known beforehand. Miquel and Castells (1993, 1994) have
explained this iterative approach in detail.
After breaking the FCCU feed into 12 pseudocomponents,
and determining the exact value of Watson characterization fac-
tor, properties of other 31 pseudocomponents were also deter-
mined by using Eqs. (A.1) and (A.2). Boiling points of these
31 pseudocomponents were taken at equal intervals between
the boiling point of n–pentane and the boiling point of first
pseudocomponent of FCCU feed (570 K in the present case).
4523
ASTM-D86a (K) TBPa (K)
585.5 558.9
615.5 604.3
632.8 636.4
652.3 665.3
680.5 700.6
721.4 743.9
756.6 808.1
The lightest seven components were taken as pure components
which are the major constituent of gases. Initially, volume frac-
tion of all these seven pure components and 31 pseudocom-
ponents, which are not present in feed, were taken zero. Thus
total 50 components (seven pure components and 43 pseudo-
components) were considered in the present approach for the
simulation of FCC riser reactor.
After determining normal boiling point, specific gravity,
and molecular weight of all pseudocomponents, heat capac-
ities were determined using the correlations of Kesler and
Lee (1976). Pseudocomponents thus generated are listed in
Table A2.
Predicted concentrations of pseudocomponents in the prod-
uct stream are given in Fig. A2. Also, various product streams,
viz., gas, gasoline, LCO, and residue are marked on the basis
of boiling points.
Appendix B.
The reaction rate constant, k, is normally determined by
Arrhenius equation in terms of frequency factor, k0 , and energy
of activation E. In most of the cases of FCC kinetic model-
ing, these parameters are determined empirically, using exper-
imental data. In the present case, however, all data available in
literature relevant to calculate the rate constants are for lumped
reaction mechanism which, in fact are reaction rate data for
conversion of one lump to other and not for cracking of one
lump giving two other lumps. Due to lack of experimental data,
a purely hypothetical correlation for predicting Arrhenius type
rate constant is being used. The proposed scheme can be per-
fected in future after performing more and more experimental
work (may be in different laboratories).
Hypothetical scheme: It is well observed fact that almost any
physical, thermodynamic, or transport properties of hydrocar-
bons of a particular group have similar behavior, and proper-
ties of these hydrocarbons can be well correlated empirically
(Daubert, 1998). In the present case, we are dealing with pseu-
docomponents, which do not fall under a particular group of
hydrocarbon, but are mixtures of large number of hydrocar-
bons of almost equal boiling point but widely different proper-
ties. In fact, pseudocomponents are neither paraffin, nor olefin,
and not aromatic either. However, the average characteristic
4524 R.K. Gupta et al. / Chemical Engineering Science 62 (2007) 4510 – 4528

Table A2
Properties of pseudocomponents

Component ID Component name Boiling point (K) Molecular weight H comb (kJ/kmol)a

PC1 Methane 111.65 16.043 62764.79

PC2 Ethane 184.50 30.070 58622.94
PC3 Propane 231.09 44.097 51983.86
PC4 Butene 266.90 56.108 50464.83
PC5 Butane 272.65 58.124 49960.31
PC6 Pentene 303.11 70.135 49073.02
PC7 Pentane 309.21 72.150 48952.84
PC8 Pseudocomponent 317.37 88.563 47318.37
PC9 Pseudocomponent 325.54 91.443 47226.62
PC10 Pseudocomponent 333.70 94.402 47137.89
PC11 Pseudocomponent 341.86 97.443 47052.01
PC12 Pseudocomponent 350.03 100.569 46968.81
PC13 Pseudocomponent 358.19 103.781 46888.17
PC14 Pseudocomponent 366.35 107.083 46809.94
PC15 Pseudocomponent 374.52 110.478 46734.00
PC16 Pseudocomponent 382.68 113.969 46660.24
PC17 Pseudocomponent 390.84 117.558 46588.54
PC18 Pseudocomponent 399.01 121.249 46517.73
PC19 Pseudocomponent 407.17 125.045 46445.89
PC20 Pseudocomponent 415.33 128.948 46373.59
PC21 Pseudocomponent 423.50 132.964 46300.89
PC22 Pseudocomponent 431.66 137.094 46227.80
PC23 Pseudocomponent 439.83 141.343 46154.34
PC24 Pseudocomponent 447.99 145.713 46080.57
PC25 Pseudocomponent 456.15 150.210 46006.47
PC26 Pseudocomponent 464.32 154.835 45932.07
PC27 Pseudocomponent 472.48 159.595 45857.39
PC28 Pseudocomponent 480.64 164.491 45782.42
PC29 Pseudocomponent 488.81 169.530 45707.18
PC30 Pseudocomponent 496.97 174.714 45631.67
PC31 Pseudocomponent 505.13 180.049 45555.89
PC32 Pseudocomponent 513.30 185.538 45479.85
PC33 Pseudocomponent 521.46 191.187 45403.53
PC34 Pseudocomponent 529.62 197.000 45326.93
PC35 Pseudocomponent 537.79 202.982 45250.05
PC36 Pseudocomponent 545.95 209.138 45172.88
PC37 Pseudocomponent 554.11 215.474 45095.39
PC38 Pseudocomponent 562.28 221.995 45017.59
PC39 Pseudocomponent 570.44 228.706 44939.46
PC40 Pseudocomponent 593.12 248.399 44720.49
PC41 Pseudocomponent 612.48 266.496 44531.20
PC42 Pseudocomponent 628.50 282.446 44353.16
PC43 Pseudocomponent 643.76 298.497 44187.51
PC44 Pseudocomponent 658.25 314.565 44034.96
PC45 Pseudocomponent 674.30 333.352 43871.15
PC46 Pseudocomponent 691.91 355.231 43697.31
PC47 Pseudocomponent 711.55 381.318 43510.14
PC48 Pseudocomponent 733.25 412.311 43311.36
PC49 Pseudocomponent 760.13 454.185 43075.64
PC50 Pseudocomponent 792.20 509.673 42808.56

PC1 to PC7 are pure components constituting gas; PC8 to PC29 constitute gasoline fraction; PC30 to PC41 constitute light cycle oil fraction; PC42 to PC50
constitute residual fraction whereas feed contains PC39 to PC50 .
a Heat of combustion values are calculated by using Eqs. (12), (13), and (14).

of these mixtures of hydrocarbons with almost equal boiling
point is characterized by Watson characterization factor KW (as
discussed in Appendix A). Therefore it can safely be assumed
that the over all cracking behavior of all pseudocomponents
should follow similar trend, as all the pseudocomponents are
generated with exactly the same value of KW . The Watson char-
acterization factor is an indicator of an average characteristic in
terms of paraffinicity, as well as aromaticity of the hydrocarbon
mixtures (pseudocomponents). Therefore, these pseudocompo-
nents are treated just as pure components with specific char-
acteristics, represented by KW , which helps in determining all
their physico–chemical properties.
 R.K. Gupta et al. / Chemical Engineering Science 62 (2007) 4510 – 4528
800
700 Residue
Feed
Boiling Temperature (K)
600
LC O
500
400 Gasoline
300
Gas
200
100
0 20 40 60
Liquid Volume % (in Product)
Fig. A2. Mass fraction of pseudocomponents in the product.
In the absence of experimental data, the rate constant of a
particular reaction can be considered as the probability of re-
action to take place. A higher probability of the reaction will
correspond to higher cracking rate and hence a higher rate con-
stant. According to the proposed reaction scheme (Eq. (1)) a
pseudocomponent PCi , cracks to give two other pseudocom-
ponents PCm , and PCn and some amount of coke () is also
formed. For the cracking of one specific PCi (i.e., for one fixed
value of i between 1 to N) there are a large number of par-
allel ‘feasible’ reactions taking place through which two com-
ponents PCm and PCn are formed such that m and n can lie
between 1 to i only (Fig. 1). However, the rate constants of all
these feasible reactions (with different values of i, m, and n)
must be different from one another. There are only three possi-
ble ways through which variation in the magnitude of cracking
rate constant of ith pseudocomponent with changing molecu-
lar weight of PCm and PCn can occur, (i) the rate constant of a
cracking reaction is maximum when molecular weights of PCm
and PCn are almost equal (Fig. B1(a)), (ii) the rate constant is
highest when molecular weights of PCm and PCn are widely
apart (Fig. B1(b)), and (iii) the rate constant is almost constant
for all values of m and n. These three possibilities can be ex-
pressed in terms of probability distribution as, (i) probability
of cracking of a pseudocomponent from its middle is highest,
(ii) cracking from its sides is more probable than from the mid-
dle, and (iii) cracking from anywhere is equally probable. It
was later observed that cracking reactions follow the last case
in which rate constant is almost equal for all possible com-
binations of cracking of a particular pseudocomponent. How-
ever, for the pedagogical point of view, following discussion
explains how the present model was developed. First of all we
consider the first case, i.e., when cracking from middle of the
molecule has highest probability. Pitault et al. (1994) has also
supported this assumption. Here it should be noted that ‘middle
of the molecule’ means the molecular weight of PCm and PCn
4525
Fig. B1. Schematic representation of cracking of a pseudocomponent: (a)
cracking from middle of the molecule (without coke formation), (b) cracking
from side of the molecule (without coke formation), (c) cracking from middle
of the molecule (along with coke formation), (d) cracking from side of the
molecule (along with coke formation).
are equal, since there is no differentiation between ring-chain
and straight chain molecules of pseudocomponents.
Thus in this first case, cracking of pseudocomponents from
80 100
the middle has highest probability, therefore, numerical value
of the rate constant should also be highest when molecular
weights of the two product pseudocomponents are equal. It
implies that for the cracking of ith pseudocomponent (PCi )
giving two other pseudocomponents PCm and PCn, the rate
constant (ki,m,n ) is maximum (kmax,i ) when molecular weight
of mth and nth components are equal. In the present scheme,
however, this is possible only when m=n since there are no two
pseudocomponents having equal molecular weight. For cases
when m = n (Fig. B1(b)), a function f (x) is defined to predict
ki,m,n in such a way that the function value approaches kmax,i
when x (=MWm − MWn ) tends to zero, and f (x) is less than
kmax,i for all |x| > 0. This function could be any even function
with a maxima at x = 0. However, in the present case, it is
assumed that the probability of cracking of a pseudocomponent
may follow a normal distribution. Therefore the function f (x),
the normal distribution function in standard form, becomes
1 2 2
f (x) = √ e−x /2 . (B.1)
2
At x = 0, this function has maximum value which corresponds
to the rate constant of the most probable cracking reaction,
kmax,i . Therefore
1
f (0) = √ = kmax,i . (B.2)
2
2 1
Hence 2 = . (B.3)
(kmax,i )2
Substituting Eqs. (B.2) and (B.3) in (B.1) we get the normal
distribution function
f (x) = kmax,i e−x
2 (kmax,i )2
. (B.4)
Here it should be noted that x is the difference in the molecular
weights of the two product components and it is possible that
the value of x is same for different combination of PCm and
PCn .
Another parameter in Eq. (1) is the amount of coke formed
during cracking reaction. The point to ponder is, for a fixed
value of x whether the cracking reaction rate shall increase,
decrease, or remain unchanged when coke formation increases?
4526 R.K. Gupta et al. / Chemical Engineering Science 62 (2007) 4510 – 4528

Table B1
Kinetic data for the cracking reactions reported by Arbel et al. (1995)

Cracking reaction Activation energy (kJ/mol) Frequency factor (h−1 ) Rate at 538 ◦ C (h−1 ) Molecular weight of cracking lump

HFO to LFO 60.7086 1.422 × 107 1760.4 380

HFO to gasoline 23.0274 1.026 × 105 3380.4 380
HFO to coke 73.269 3.704 × 107 712.8 380
LFO to gasoline 23.0274 8.215 × 104 2707.2 255
LFO to coke 73.269 1.852 × 107 356.4 255
Gasoline to coke 41.868 8.555 × 104 172.8 120
HFO: heavy fuel oil; LFO: Light fuel oil.

Table B2
Kinetic data for the cracking reactions reported by Lee et al. (1989)

Cracking reaction Activation energy (kJ/mol) Frequency factor (h−1 ) Rate at 538 ◦ C (h−1 ) Molecular weight of cracking lump

Gas oil to gasoline 68.2495 7.978 × 105 39.364 380

Gas oil to gas 89.2164 4.549 × 106 9.749 380
Gas oil to coke 64.5750 3.765 × 104 6.012 380
Gasoline to gas 52.7184 3.255 × 103 2.470 120
Gasoline to coke 115.4580 7.957 × 101 1.364 120

The formation of coke can be depicted as in Fig. B1(c) and
(d), and the mass of coke formed (in kg), when one kmol of
reactant (PCi ) cracks, can be given by
i,m,n = MWi − (MWm + MWn ).
It appears from Table B.1 and Table B.2 that the rate con-
stant for the conversion of a lump to coke is significantly lower
than the rate constants for the conversion of same lump to other
hydrocarbon lumps. It indicates that the formation of coke is
not favored during the cracking reaction. From this fact an in-
ference can be drawn that the probability (or the rate constant)
of a cracking reaction decreases when coke formation (i,m,n )
is increased. Since we are considering cracking of pseudocom-
ponents, which itself are mixtures of large number of actual
compounds, it seems that the fractional decrease in rate con-
stant with increasing coke formation should be a continuous
function say g(), where  is the amount of coke formation
(i,m,n ). Thus the general correlation for the rate constant can
be expressed as the product of these two functions as
ki,m,n = f (x)g().
In the present work, we hypothesize that the function g() is
an exponential decay function of the form
e−i,m,n − e−MWi
g(i,m,n ) = , (B.7)
1 − e−MWi
such that,
g(i,m,n ) = 1 at i,m,n = 0 (i.e., no coke formation)
and
g(i,m,n ) = 0 at i,m,n = MWi
(i.e., all hydrocarbon mass is converted to coke).
Combining Eqs. (B.4), (B.6) and (B.7), we get
2 2
ki,m,n = kmax,i e− (MWm −MWn ) (kmax,i )
e−(MWi −(MWm +MWn )) − e−MWi
(B.5) × . (B.8)
1 − e−MWi
A schematic three dimensional surface of ki,m,n as functions
of coke formation (i,m,n ) and x (the difference between MWm
and MWn ) for the cracking of a typical pseudocomponent is
shown in Fig. B2. It can be observed that at different values of
coke formation, the grid-line parallel to x-axis follows the nor-
mal distribution function of different curvature, and the func-
tion has a maxima at x = 0.
Up to this point we have considered only hypothetical cor-
relations, without any experimental verification. Eq. (B.8) is
quite rigid to accommodate experimental data as the surface
shown in Fig. B2 can change only by changing kmax,i . There-
fore, at this stage, we introduced two tunable parameters 1 and
2 which can be used to adjust the span (variance) of the normal
distribution function and the curvature of the decay function,
respectively, such that
(B.6)
2
ki,m,n = [kmax,i · e−1 [(MWm −MWn )·kmax,i ] ]
e−(MWi −(MWm +MWn ))/2 − e−MWi
× . (B.9)
1.0 − e−MWi
The parameter 2 is an indicator of coking tendency and its
value will depend on the nature of the feed. Parameter 1 is
an indicator of cracking tendency of pseudocomponents from
middle or from sides.
By increasing 2 decay of exponential function g() is re-
duced. The thick solid line on the grid surface (Fig. B2) is
elevated vertically upward to thick dashed line when 2 is in-
creased. Hence by increasing 2 reaction rate constant can be
increased even with higher coke formation. On the other hand,
 R.K. Gupta et al. / Chemical Engineering Science 62 (2007) 4510 – 4528
Fig. B2. Schematic representation of the probability distribution function f (x)
(on the vertical plane) and the reaction rate constant ki,m,n as a function of
coke formation and the difference in molecular weights of the products.
by decreasing value of 1 the function f (x) (hence the entire
surface of Fig. B2) can be made more flat. If the value of 1
is reduced to zero, the intersection of the surface with ki,m,n –x
plane becomes a straight line. By further decreasing the value
of 1 the surface becomes concave upward. In Fig. B2, the in-
tersection of such surface with ki,m,n –x plane is shown by a
thin dashed line. Thus if 1 is positive, the cracking behavior of
pseudocomponents is as explained for case (i), whereas, nega-
tive value of 1 leads to case(ii), i.e., the rate constant is highest
when molecular weights of PCm and PCn are widely apart. For
the third case, when rate constant is independent of molecu-
lar weights MWm and MWn , 1 is zero. Thus by introducing
these two tuning parameters, 1 and 2 , Eq. (B.9) can be used
to predict rate constant for all possible schemes.
With change in temperature, it is expected that there should
not be any change in the probability distribution for the crack-
ing of a particular pseudocomponent i.e., shape of the normal
distribution curve remains unchanged at all temperatures. At
the same time, the reaction rate constant ki,m,n has to follow
the Arrhenius equation. This is possible only if kmax,i follows
the equation
kmax,i = k0,i e−Ei /RT , (B.10)
where the energy of activation (Ei ) and frequency factor (k0,i )
are the characteristics of ith pseudocomponent (PCi ), therefore
numerical values of these parameters should be different for dif-
ferent pseudocomponents. In other words, Ei and k0,i should
be a function of some characteristic property of ith pseudo-
component. One such property could be the molecular weight
(MWi ). To predict such a relation, data of Tables A1 and A2 can
be used. Although, these Tables represent data for conversion
reaction (not a cracking reaction), even then, a wild guess can
be made from data given in these tables. Overall, it appears that
parameters Ei and k0,i have an increasing trend with increas-
ing molecular weight of reactant lump. These trends may have
4527
the following relationship with molecular weight of cracking
lump:

k0,i = k0 MWi , (B.11)
Ei = E0 MWi . (B.12)
Therefore, the parameter kmax,i used in Eq. (B.9) can be
expressed in terms of the frequency factor (k0,i ) and the energy
of activation (Ei ) with four rate constant parameters k0 , ,
E0 , and . After the sensitivity analysis, as discussed in the
main body of the text, it was observed that the parameter  is
insignificant; therefore it can be eliminated from the list of six
parameters.
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