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pubs.acs.org/IECR
Institute for Biotechnology and Bioengineering (IBB), Department of Chemical Engineering, Instituto Superior Tecnico/Universidade
Tecnica de Lisboa, Av. Rovisco Pais 1, 1049-001 Lisboa, Portugal
Process Design and Modeling Division, IFP Energies Nouvelles Lyon, Rond-point de lechangeur de Solaize, B.P. 3,
69360 Solaize, France
Centre for Chemical Processes Engineering and Forest Products (CIEPQPF), Department of Chemical Engineering,
Universidade de Coimbra, R. Slvio Lima Polo II, 3030-790 Coimbra, Portugal
#
ATP Engenharia, Rua S~ao Jose 90/2201-C, 20010-020 Centro, Rio de Janeiro, RJ, Brazil
ABSTRACT: This paper focuses on the uid catalytic cracking (FCC) process and reviews recent developments in its modeling,
monitoring, control, and optimization. This challenging process exhibits complex behavior, requiring detailed models to express the
nonlinear eects and extensive interactions between input and control variables that are observed in industrial practice. The FCC
models currently available dier enormously in terms of their scope, level of detail, modeling hypothesis, and solution approaches
used. Nevertheless, signicant benets from their eective use in various routine tasks are starting to be widely recognized by the
industry. To help improve the existing modeling approaches, this review describes and compares the dierent mathematical
frameworks that have been applied in the modeling, simulation, control, and optimization of this key downstream unit. Given the
eects that perturbations in the feedstock quality and other unit disturbances might have, especially when associated with frequent
changes in market demand, this paper also demonstrates the importance of understanding the nonlinear behavior of the FCC
process. The incentives associated with the use of advanced model-based supervision strategies, such as nonlinear model predictive
control and real-time optimization techniques, are also presented and discussed.
1. INTRODUCTION
Growing demand for renery products combined with the
decreasing quality of crude oils and tighter product specications
due to environmental constraints is forcing reners to make
signicant investments. In fact, during the past decades, new
hydroprocessing units have been built, together with the revamping of old rening processes to meet market demands.1 In this
context, the use of advanced process engineering tools has become
essential for reners, not only for design but also in the tasks of
process control, optimization, scheduling, and planning. Besides
the application to specic process units, these techniques are also
being used for the entire renery supply chain.2
Fluid catalytic cracking (FCC) remains a key unit in many
reneries; it consists of a three-step process: reaction, product
separation, and regeneration. In this cyclic process, gas oils from
vacuum distillation towers and/or residues from atmospheric
distillation towers are converted into lighter and more valuable
products. One of the most desired products is cracked naphtha,
which is the major constituent of the gasoline pool.3 Operating
conditions comprise high reaction temperatures in the range of
750800 K and pressures close to atmospheric conditions. FCC
is able to process a wide variety of feedstocks and is suitable to
operate in special campaigns46 that may also soon include
coprocessing of renewable feedstocks.79 Nowadays, more than
400 FCC units are operated worldwide.10
A multicomponent catalyst that usually contains an acid USHY
zeolite, an active alumina matrix, an inert matrix (kaolin), and a
r 2011 American Chemical Society
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Figure 1. Scheme of some FCC unit designs: (a) UOP stacked unit; (b) model IV; (c) Exxon Flexicracking unit; (d) R2R residue unit (adapted from
Montgomery32).
catalyst is frequently required. Moreover, for FCC units processing feedstocks with high levels of metals,2527 it is also common
to replace a portion of the inventory by fresh catalyst, to keep the
amount of contaminant metals at an acceptable level. This
regular addition of fresh catalyst makes the FCC process one
of the most important markets for catalysts.12,21 As a result, the
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2. MATHEMATICAL MODELING
The implementation and maintenance of model-based engineering tools are currently limited by the lack of experienced
manpower in the reneries.38 Consequently, it has become
common practice for reners to request costly hand-in-hand
solutions from companies specialized in the development of
these engineering tools. Model development and process identication are probably the most time-consuming steps in the
implementation of many advanced process engineering strategies at the industrial level. Advanced control strategies usually
rely on linear black box models from step identication tests
carried out on the unit. Although these models are faster to
develop, they are valid only in the operating region where they
were obtained, and they do not usually capture the nonlinearities
of the industrial process. In addition, it is dicult to use
simultaneously these models for plant optimization, which
requires accurate and rigorous models for a wider range of
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gas oil (VGO) feeds70,71 and for coke formation,72 based on the
single-event approach. This modeling technique aims at retaining
the full detail of the reaction pathways of all individual feed
components and reaction intermediates, by describing the reaction network in terms of elementary steps.73 Therefore, this
requires a very detailed characterization of feeds and products,
which is generally not available in industry, and is computationally more demanding than the lumped models.
Semilumped models that consider the dierent reaction types
occurring in catalytic cracking have also been proposed, in which
the products and reactants are grouped by common characteristics such as the carbon number and types of molecules such as
parans and olens.74,75 Unfortunately, studies concerning this
type of model have been carried out mainly for model molecules
and, like the single-event models, require a good characterization
of the reactants and products.
In the case of very complex feeds containing several chemical
species, such as the FCC feedstock, a detailed composition can be
obtained from partial analytical data through molecular reconstruction techniques. The so-called feedstock reconstruction
method was proposed by Verstraete et al.76 by means of an
algorithm that generates a complex mixture of molecules based
on standard petroleum analysis, which was validated for FCC
gasolines,76 VGO,77 LCO,78 and VR.79 It consists of a two-step
approach; in the rst step, called stochastic reconstruction, a
large representative set of molecules is created. It is initially assumed
that the oil mixtures can be described by distributions of structural
blocks (polycyclic cores, rings, chains, etc.), the transformation
from a set of distributions into an equimolar mixture of molecules being performed by Monte Carlo sampling. The properties
of the mixture are then optimized using a genetic algorithm to
minimize the dierence between calculated properties and
experimental data. The second step, named reconstruction by
entropy maximization, further improves the representativeness of the set of constructed molecules by adjusting their molar
fractions.
The choice of the kinetic model used should be supported by
the level of detail desired, which normally depends on the type of
usage that the FCC model will have. It is also important to keep
in mind that it is not realistic to attempt to dene a detailed
microkinetic model for gas oil industrial cracking, because it
would involve hundreds of elementary steps, for which kinetic
parameters would need to be determined.70,80 Nevertheless, if
one intends to predict the behavior of FCC industrial units, it is
necessary to choose a kinetic model with a reasonably detailed
product distribution.75
2.2. Deactivation. In addition to the already mentioned difficulties in modeling the catalytic cracking kinetics, other important
aspects are the ad/desorption steps of reactants and products on the
catalyst surface8184 and the very fast deactivation of the catalyst that
complicates the independent determination of the kinetic reaction
rates and the catalyst deactivation.58,65,85,86 Indeed, the main cause of
FCC catalyst deactivation is the coke formation and deposition on
the surface of the catalyst.22,32,39,42,84,87 The first efforts in modeling
coke formation were made by Voorhies:88 he proposed an empirical
correlation for coking in the catalytic cracking of gas oil that depends
on the catalyst residence time.
Two fundamentally dierent approaches to modeling catalyst
deactivation have been used: the time-on-stream and the coke-oncatalyst functions. Nam and Kittrell89 addressed this issue and
concluded that time-on-stream functions exhibit the advantages of simultaneously allowing the deactivation mechanisms
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which means that the gas and solid velocities are practically
coincident.121 This disagrees with typical slip factors, close to 2,
that are usually reported in the riser by many other authors.50,117,122
High slip factors, up to 4, have been experimentally observed and
can be related to the formation of clusters along the riser
reactor.122,123 A cluster is an aggregate of particles moving together
with the same velocity (Figure 2). It has a higher free falling
velocity than the terminal velocity of the individual particles.
Hence, when the amount of clusters increases, the slip factor
between gas and catalyst will also increase. The reported size of
FCC catalyst clusters is between 2 and 15 mm.124 However, in the
dilute region of the riser the probability of cluster formation is
smaller due to the higher velocities, and the slip factor decreases
signicantly in that region. Subbarao125 has recently presented a
model for the structure uidsolid in a riser, which includes an
equation developed for estimating cluster size.
Although there are studies that experimentally demonstrate
the formation of clusters in the riser reactor,122,124,126 this factor
is not usually considered in modeling these sections.52,117 The
studies that consider the formation of hydrodynamic clusters in
1-D simulations give comparable results to 3-D simulations for
product yield and conversion, if an eective cluster diameter is
used instead of the catalyst single-particle diameter.52,117 Nevertheless, the 3-D simulations describe better the gassolid slip in
the riser, considering a larger range of operating conditions and
model parameters.
Computational uid dynamics (CFD) simulations with a
EulerianEulerian two-uid modeling approach of gassolid
ow in the riser have been widely conducted to predict hydrodynamics in circulating uidized bed risers, by including cluster
diameter correlations used within the framework of the energy
minimization multiscale model.127129
The behavior of catalytic cracking reactions of particle cluster
in uid catalytic cracking risers was recently numerically analyzed
using a hydrodynamics model coupled with a four-lump mathematical model.130 The eects of the cluster porosity, inlet gas
velocity, and cluster formation on cracking reactions were
investigated. Distributions of temperature, gases, and gasoline
from both the catalyst particle cluster and an isolated catalyst
particle are presented. Simulated results show that the reactions
from VGO to gasoline, gas, and coke of individual particles in
the cluster are slower than those of the isolated particles, but
faster for the reaction from gasoline to gas and coke. Particle
clustering will reduce the reaction rates from VGO to gasoline,
gas, and coke and increase the reaction rates from gasoline to gas
and coke.130
2.4. Stripper/Disengager Models. In contrast to that on the
riser, research on stripper/disengager vessels published in the
open literature is scarce.131 There are, nevertheless, some studies
in cold-flow units (in the absence of reactions) using CFD for
detailed modeling of the hydrodynamics of the stripper/disengager vessels in the FCC unit. The main objective of these studies
is to improve the design of the internal hardware in this section,
such as the riser termination device, the cyclones system, and
stripper baffles132136
Besides cold-ow modeling, only the authors that proposed
models for the integrated reactorregenerator system have
described the stripper/disengager vessel as a component in their
models. This is particularly important in the dynamic models,
because in modern units the catalyst holdup in this vessel is high
and contributes signicantly to the transient behavior of the FCC
unit. Moreover, it is important to predict the percentage of
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O2 g f
COg
CHx s
2 1
4
1
1
x
CO2 g H2 Og
2
1
2
2COg O2 g f 2CO2 g
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y hx
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0 f x;uss
y hxss
has more than one solution. This can be caused by the presence
of state multiplicities, particularly when y corresponds mostly to a
subset of the state vector.
Because output multiplicities are easier to study and validate
than state multiplicities, their identication is much more often
carried out in practice. A common way of determining output
multiplicity in chemical systems is to plot the curves that refer to
removed and generated heat. The intersections of these two
curves represent the steady-state points of the system.183185
The identication of output multiplicities is important, from an
operational point of view, mainly due to two reasons:186 (1)
Having several steady states in feasible operating regions may
result in very distinct economical returns. (2) Operating conditions can be changed in such a way that a stable steady state is lost.
In this case, the unit may wind down to the cold steady state
(which can be physically infeasible and imply the shutdown of the
unit) or else reach an unstable steady state that needs further
stabilization by the online control system.
Steady-state multiplicity is an important feature of FCC units
and has been analyzed in various references.140,168170,177,186189
The rst author to study this phenomenon was Iscol,188 in 1970. Lee
and Kugelman169 claimed that in a typical open-loop FCC there is
only a unique steady state at xed feed rate, catalyst circulation rate
(Fc), and air ow rate (Fair). However, their concept of uniqueness is
restricted to an operation region of practical interest. Oliveira189 also
studied state multiplicity in FCC units, using the same model as Lee
and Kugelman,169 and reached the same conclusion.
Other authors have used the term multiplicity of steady
states in the sense of input multiplicity. In their studies, they
searched for multiple steady states by xing process variables
such as the feed ow rate, feed temperature, and combustion air
rate, while the catalyst circulation rate was allowed to vary to keep
the riser reactor temperature constant.170,187 Under these conditions, two steady states were obtained. A system with input
multiplicities can be dicult to control because there exist more
than one set of steady-state values for the manipulated variables
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Figure 4. Eect of operating conditions in the heat generation and heat removal lines in an industrial UOP FCC unit with a high-eciency
regenerator:186 regenerator pressure (a), combustion air temperature (b), and feed preheat temperatures (c).
combustion air inside the regenerator. Changing the feed temperature (Figure 4c) aects both the heat-removed and heatgenerated curves. The heat-removed curve changes position,
because the requirements to heat and vaporize the feed ow rate
also change. On the other hand, the feed temperature directly
aects the temperature in the riser and subsequently aects the
formation of coke and the heat-generated curve. Furthermore,
panels b and c of Figure 4 show that low feed and air temperatures can even result in the loss of the intermediate and upper
steady states. This situation would result in a set of nonpermissible operating conditions, because the only steady state available
would be the cold point.186 These dierent heat curves and
consequently the multiple steady states can be very close to each
other, so in industrial operation the behavior can shift from one
steady state to another, and this is an incentive for choosing a
robust control system.
Therefore, from a control point of view, particular care is
required in the choice of manipulated variables that will allow
correct operation of the unit in the region of ve steady states.
Depending on the choice of the control structure, input multiplicities can also cause stability problems. An important consequence of the input multiplicity is that there are usually points in
the operating region where the steady-state gain matrix becomes
singular.192 This means that changes in the sign of the steady-state
gains are possible, which poses additional diculties, especially
for linear control actions, because if the controller gains are
maintained constant, positive feedback will be introduced in the
system.189 Hence, for processes with such characteristics, nonlinear control strategies can be the only feasible approaches for
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controlled variables, y
partial
[Fc, Fair]T
[TRT, TRG]T
Kurihara
partial
[Fc, Fair]
[TRG, TRG]T
alternative Kurihara
partial
[Fc, Fair]T
[TRG, TCY]T
Hicks
Partial
[Fc, Fair]T
[TRT, TCY]T
riserregenerator
partial
[Fc, Fair]T
[TRT, TRG]T
conventional
complete
[Fc, Fair]T
[TRT, yO2,RG]T
Kurihara
complete
[Fc, Fair]T
[TRG, yO2,RG]T
riserregenerator
complete
[Fc, Fair]T
[TRT, TRG]T
control structure
conventional
combustion mode
observations
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controlled variables
Wr, TRG, TRT
manipulated variables
FRC, FSC, FPF
S2: 3 3
FRC, FSC, FS
S3: 3 3
FRC, FSC, FV
S4: 3 3
FRC, FSC, FV
S5: 4 4
S6: 4 4
S7: 4 4
S8: 5 5
S9: 5 5
S10: 5 5
S11: 5 5
S12: 5 6
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Figure 6. Schemes of (a) two-layer approach, (b) one-layer approach, and (c) two-layer approach with two-stage MPC (adapted from Ying et al.261 and
Tatjewski262).
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year
approach
description
1989
two-layer
1989
two-layer
Grosdidier253
1993
two-layer
1995
two-layer
1995
two-layer
1996
one-layer
Yang et al.194,256
Lid and Strand257
1996, 1998
1997
one-layer
one-layer
nodel from real plant step test; transfer function matrix; MPC
industrial application at Statoil Montgomery Plant; model
Ellis et al.266
1998
two-layer
1999
one-layer
Zanin254
2001
one-layer
2000
one-layer
Zanin et al.250
2005
two-layer
Souza et al.260
2010
one-layer
from unit operational data and step tests; SQP optimizer; MPC
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6. FINAL REMARKS
Historically, the uid catalytic cracking unit has expanded its
role from a gasoline machine to a LPG and propene producer and
a residue upgrader. FCC technology advances played an essential
part in renery prot. Recent FCC challenges are related to
environmental regulations and the drive to produce cleaner fuels.
It also seems that in the coming decades the FCC will take on two
additional roles: it may (partially) use feeds from renewable
sources and be combined with a CO2 capture process to alleviate
growing concerns over energy consumption and global warming.
With combined eorts by reners and technology developers,
the process will continue to demonstrate superior adaptability to
the changing market requirements.
The importance of catalyst formulations (e.g., additives, new
or modied zeolites, functional ingredients) will continue to be a
major aspect. Process congurations and hardware improvements such as feed injectors, riser and stripper internals, and
termination devices will continue to be developed. These modications, combined with advanced control techniques, are
essential to sustain both the yield and the quality of FCC gasoline
with the future feedstock scenario. Reneries equipped to process
heavy crudes have, so far, reported better rening margins because
they can take advantage of less expensive opportunity crudes.
Residue uid catalytic cracking is an important component in the
upgrading of such crudes, with unit protability depending upon
the extent to which heavy hydrocarbons in the feed are cracked into
valuable products. Technology advances in catalysts, hardware,
and monitoring will improve residue FCC operations. Although
the coprocessing of renewable feeds with FCC gas oils can be
performed in the existent FCC infrastructures with minimal
changes, the use of renewable feeds alone may require signicant
modications in the FCC unit.
Feed characterization is a key area for improvement. Predicting unit dynamics caused by feed changes is important in
optimizing unit operation, especially for atmospheric distillation
residues. Product recycles and multiple reaction sections seem to
be the most prevalent technology trends. Improving feed injectors, riser termination and catalyst separation devices, strippers, and regenerator components are good revamp options
for existing units. As feeds get heavier, the trend toward a higher
stripper residence time and, thus, increased mass transfer between
entrained hydrocarbons and steam will continue. Moreover, the
role of the regenerator is expected to evolve because of CO2
emission reduction requirements.
Several of todays FCC units were built in the 1970s, when
ecient energy use was not of primary concern. These units have
been revamped to improve energy performance. The coke yield
of a FCC unit is dictated by the energy needs of the unit. The heat
of reaction from catalyst coke combusted in the regenerator is
used to heat and vaporize fresh and recycled feed, heat atomizing
steam, provide the heat required for endothermic cracking
reactions, heat the combustion air to regenerator ue gas
temperature, make up for heat lost to the surroundings, and
produce stripping steam. Because the FCC unit operates in heat
AUTHOR INFORMATION
Corresponding Author
*Tel: +351 218 417 887. Fax.: +351 218 419 198. E-mail: carla.
pinheiro@ist.utl.pt.
ACKNOWLEDGMENT
L.D., A.J.S.C., and I.G. thank the Fundac-~ao para a Ci^encia e
Tecnologia (FCT) for nancial support (ref SFRH/BD/60668/
2009, ref PTDC/EQU-ESI/73458/2006, and ref SFRH/BPD/
74457/2010, respectively).
DEDICATION
4
In memory of Prof. Fernando Ram^oa Ribeiro, recently deceased.
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ABBREVIATIONS
ADMC adaptative dynamic multivariable controllers
ANN
articial neural networks
API
American Petroleum Institute
ASTM American Society for Testing and Materials
CFD
computational uid dynamics
CPERI Chemical Process Engineering Research Institute
CST
continuous stirred tank
CSTR continuous stirred tank reactor
CTO
catalyst-to-oil
DCS
distributed control system
DMC dynamic matrix control
DO
decanted oil
e-cat
equilibrium catalyst
EKF
extended Kalman lter
F
ow rate
FCC
uid catalytic cracking
FCCU uid catalytic cracking unit
FLC
fuzzy logic control
GMC generic model control
HCO heavy cycle oil
HEKF heuristic extended Kalman lter
IFP
Institut Franc-ais du Petrole
IFPEN Institut Franc-ais du Petrole Energies Nouvelles
IMC
internal model control
IRV
ideal resting values
ISE
integral of the square error
LCO
light cycle oil
LMPC linear model predictive control
LP
linear programming
LPG
liqueed petroleum gases
MIMC multivariable internal model control
MIMO multi-inputmulti-output
MPC
model predictive control
N4SID numerical algorithms for subspace state space system
identication
NMPC nonlinear model predictive control
NLP
nonlinear programming
PCA
principal component analysis
PFR
plug ow reactor
PI
proportiona-integral
PID
proportionalintegralderivative
PMBC process model-based constraint control
PRBS pseudo-random binary sequences
QP
quadratic programming
RFCC residue uid catalytic cracking
RGA
relative gain array
RHP
right half-plane
RTO
real-time optimization
RVP
Reid vapor pressure
SCP
sequential linear programming
SEMK single-event microkinetic
SISO
single-inputsingle-output
SLP
sequential linear programming
SMPC simplied model predictive control
SOD
Standard Oil Development Co.
SOL
structure-oriented lumping
SQP
sequential quadratic programming
SRTO simplied real-time optimization
SSM
steady state models
T
temperature
U
manipulated variable matrix
VGO
VR
W
Y
ZN
air
c
CY
Feed
MF
PF
r
RC
RG
RT
S
SC
SS
V
wt
air to regenerator
catalyst
cyclones
feed stream
main fractionators (top)
preheating furnace fuel
stripper (historically reactor)
regenerated catalyst
regenerator
reactor section (riser + disengager + stripper)
stack gas
spent catalyst
steady state
regenerator air nypass
weighting matrix
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