ARTICLE

pubs.acs.org/IECR

Improvements in Petroleum Refinery Planning: 1. Formulation of

Process Models
Omar J. Guerra† and Galo A. C. Le Roux*
Department of Chemical Engineering, University of S~ao Paulo, Av. Prof. Luciano Gualberto trav.3, 380, CEP 05508-900,
S~ao Paulo-SP, Brazil

ABSTRACT: Optimization of the production planning is crucial for the economic success of a petroleum refinery. Nevertheless, it is
a difficult task, because of the large scale of the system and the complexity of the processes involved. Part 1 of this series of two papers
addresses the formulation of process models for petroleum refinery planning. First, a generic formulation of nonlinear refinery
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planning model is adopted from the literature. Subsequently, the formulation of nonlinear empirical models for crude distillation
units (CDUs) and a fluid catalytic cracking (FCC) unit is addressed. These empirical models were successfully validated using
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rigorous process simulators. Finally, the results from model validation showed that the accuracy of model predictions is as good as
the current empirical process models reported in the literature, while the empirical process models proposed in this work overcome
the limitations of both linear and nonlinear empirical models for CDUs and FCC units previously developed by other authors. Part 2
[Ind. Eng. Chem. Res. 2011, DOI: 10.1021/ie200304v] involves the implementation of nonlinear empirical process models in the
petroleum refinery planning.

1. INTRODUCTION out in a FCC process simulator from PETROBRAS. Finally, the

For many years, production planning problems in petroleum
refineries have been addressed using the linear programming
(LP) technique.1 This technique is based on delta-base process
models (linearization of nonlinear process behavior at a parti-
cular set of operating conditions). Nevertheless, the linear
process models are not suitable for refinery process modeling,
since refinery processes involve both physical operations (phase
separations, blending operations, etc.) and chemical operations
(cracking reactions, hydrotreating reactions, etc.) that are char-
acterized by their nonlinear nature. Because of this fact, the
results (operating plans) from production planning models
based on the linear programming technique can be unreliable.
Furthermore, the recent advances in computer hardware and
optimization algorithms allow the implementation of nonlinear
process models in the production planning models. Moreover,
Moro et al.2 quantify the impact of the adequate usage of refinery
planning tools based on nonlinear process models in a potential
increase of ∼6 000 000 US$/yr in the profitability for a typical
refinery with operational capacity of 169.8 kbpd/day. Conse-
quently, nowadays, different petroleum companies such as BP,
ECOPETROL, ExxonMobil, and PETROBRAS have decided to
develop their own refinery planning tools (based on nonlinear
process models), instead of using commercial tools (based on the
linear programming technique) such as the Process Industry
Modeling System (PIMS) or the Refinery and Petrochemical
Modeling System (RPMS).
In this paper, nonlinear empirical models for crude distillation
units (CDUs) and fluid catalytic cracking (FCC) units are
proposed and validated. The empirical model for CDUs was
based on the empirical procedure proposed by Watkins,3 using
HYSYS (a rigorous process simulator) for model validation. In
addition, the empirical model for a FCC unit was based
(formulation and validation) on rigorous simulations carried
predictions from the empirical models developed in this work
were compared with those obtained using empirical models from
the literature.
2. REFINERY PLANNING
Being profitable in petroleum refining depends on using
systems and tools that enable the right people/functions to make
the right decisions at the right time.4 These decisions are taken at
different hierarchical levels (advanced control, real-time optimi-
zation, production scheduling, production planning, and strate-
gic planning) and over different time horizons (seconds, minutes,
days, weeks, months, and years), using phenomenological or
empirical process models. The model accuracy, the computa-
tional effort to solve it, and the profit scale for each decision level
can be represented as shown in Figure 1. As can be seen in this
figure, the profit scale is inversely proportional to the model
accuracy and the effort to solve it. In addition, there is an
interaction between each two adjacent hierarchical levels; for
example, the planning model provides the production plan for
the scheduling model, and this provides the production program
and the feasibility of the production plan from the planning level.
According to Kreipl and Pinedo,5 the interaction between the
planning and the scheduling levels may be intricate, because, in
the planning model, the feedstock supply and the final product
demand and production are considered as average values for
the entire time horizon, whereas, in the scheduling model, the
operation is considered to be a sequence of activities and the
Received: February 12, 2011
Accepted: July 22, 2011
Revised: July 8, 2011
Published: July 22, 2011

r 2011 American Chemical Society 13403 dx.doi.org/10.1021/ie200303m | Ind. Eng. Chem. Res. 2011, 50, 13403–13418
Industrial & Engineering Chemistry Research
Figure 1. Hierarchical structure of the decisions in a petroleum refinery.
Figure 2. Process unit structure.2
feedstock supply and the final product demand and production
vary along the time horizon.
Recently, several works have been reported about the integra-
tion between planning and scheduling in order to reduce the dis-
crepancies in the results from these two models.6
8 Moreover, in
order to provide accurate estimation of product yields and pro-
perties in the planning model, it is necessary to ensure an ade-
quate modeling of the refinery process. Several works have been
reported that are related to the implementation of nonlinear
empirical process models in the refinery planning,2,9,10 because
of the limitation of linear models to reproduce the refinery process
behavior under any particular set of operating conditions. Moro
et al.2 presented a general framework for the formulation of
nonlinear refinery planning models, which will be described below.
2.1. Nonlinear Planning Model. According to Moro et al.,2
the topology of a refinery can be defined as a set of process units
interconnected by mixers and splitters; the structure of each
process unit is described in Figure 2. In general, the streams from
one or more units (u0 ∈Uu) that can be sent (at a flow rate Fu0 ,s,u)
as a feed to unit u are defined by the set su = {s1,s2,..,sn}. These
streams are mixed together to obtain the total feed FFu to the unit u.
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The set USu0 ,u contains all streams from the unit u0 that can be
sent as a feed to the unit u; similarly, the set SUs,u contains all
units u0 that can receive (as a feed) the stream s from the unit u.
All streams existing in the entire refinery are characterized by the
set of properties p = {p1,p2,..,pm}, the relevant properties for the
feed to unit u are defined by the set PIu, while the relevant
properties for each product stream s from this unit are defined by
the set POu,s. In addition, the variables PAu,p and PCu,s,p denote
the property values for the feed and each product streams s in the
unit u, respectively. The set SOu contains all product streams
from unit u, the yield and properties for the product stream
s∈SOu can be function of a set of operational variables Ou = {o1,
o2,..,ok}. The value for each operational variable is denoted by the
variable Vo,u. The units that can be fed by external streams (i.e.,
distillation units) are defined by the set Uf, as well as the units that
produce final products are defined by the set Up, these units can
be represented as mixers. For convenience, the feed streams to
each unit u∈Uf are considered to be product streams from a
hypothetical unit r. Based on the sets and variables defined above,
the mathematical model for the refinery planning can be written
as follows:
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Industrial & Engineering Chemistry Research ARTICLE

Table 1. Mixing Rules and Property Indicesa

property or property index notation addition base index correlation reference

cetane index CTI volume

motor octane numberb MON volume
research octane numberb RON volume
specific gravity SPG volume
API gravity API weight
Conradson carbon residue (wt %) CCR weight
sulfur (wt %) SUL weight
pour point index (pp = pour point (F)) PPI volume PPI = 316200 exp{12.5 ln[0.001(PP + 459.67)]} Li et al.11
smoke point index (smp = smoke point (mm)) SPI volume SPI =
362 + [2300/ln(SMP)] Li et al.11
viscosity index (ν = kinematic viscosity (cSt)) VII volume VII = log10(ν)/(3 + log10(ν)) Riazi12
a b
The mixing rules are a volumetric average, if the addition base is volume, or a weight average, if the addition base is weight. The mixing rule for these
properties is a simplification used in this work, usually these properties have a nonlinear mixing rule.

Objective function: unitary product prices, raw material costs, and operating costs
∑ ∑ ∑
respectively. These costs and prices are not necessarily constants.
max Profit ¼ Cpru 3 FF u
Crms 3 Fr, s, u For example, the product prices can be a function of a key
u ∈ Up u ∈ Uf s ∈ USr, u
property (in the case of gasoline, the octane number can be the

∑
u∈U
Copu 3 FF u ð1Þ key property) and the operating costs can be a function of
operational variables (for more details, see Part 2 of this work
subject to [Ind. Eng. Chem. Res. 2011, DOI: 10.1021/ie200304v]). Equa-
∑ ∑
tion 2 denotes the mass balance for the feed mixer in each process
FF u ¼ Fu0 , s, u "u∈U ð2Þ unit. Equation 3 represents the total feed properties as a function
u0 ∈ Uu s ∈ USu0 , u
of the properties and flow rate of each individual feed stream to
the unit. The function fu,p denotes a mixing rule for the property
PAu, p ¼ fu, p ðFu0 , s, u ju0 ∈ Uu ;s ∈ USu0 , u , PCu0 , s, p ju0 ∈ Uu ;s ∈ USu0 , u ;p ∈ PI u Þ p; this mixing rule can be on a volume basis (i.e., density, olefins
" u ∈ U, p ∈ PI u ð3Þ (vol%), etc.) or a weight basis (i.e., sulfur content (wt %),
nitrogen content (ppm), etc.). Nevertheless, many properties
involve highly nonlinear mixing rules (i.e., pour point, flash point,
FPu, s ¼ hu, s ðFF u , PAu, p jp ∈ PIu , Vo, u jo ∈ Ou Þ " u ∈ U, s ∈ SOu
viscosity, etc.); in this case, the linear blending indices (volume-
ð4Þ based or weight-based) can be used, the mixing rules and
property indices used in this paper are described in Table 1.
PCu, s, p ¼ gu, s, p ðPAu, p jp ∈ PI u , Vo, u jo ∈ Ou Þ " u ∈ U, s ∈ Su , p ∈ POu, s Equation 4 represents the flow rate of each product stream as a
function of operational variables Vo,u|o∈Ou and flow rate and
ð5Þ properties of total feed to the unit. Similarly, eq 5 represents the
properties of product streams PCu,p|p∈PIu as a function of
∑
u0 ∈ SUs, u
Fu, s, u0 ¼ FPu, s " u ∈ U, s ∈ SOu ð6Þ operational variables Vo,u|o∈Ou and properties of the total feed
to the unit. Equation 6 denotes the mass balance for each product
stream s from each unit. Inequality 7 denotes the lower bounds
FF u g Demandu " u ∈ Up ð7Þ on product demands for blending units (u∈Up); it will be
assumed that product demand is flexible in the sense that it is
∑
u ∈ Uf
Fr, s, u e Supply s " s ∈ USr, u ð8Þ given by a hard lower bound and a free upper bound. Similarly,
inequality 8 denotes the upper bounds on raw material supply.
Inequality 9 represents the operational capacity for every unit in
the refinery. Inequality 10 denotes the specifications for the
u e FF u e FF u
FF lo "u∈U ð9Þ
up
final product streams (u∈Up), as well as the possible feed
specification for the process units (uˇUp). In addition, inequal-
u, p e PAu, p e PAu, p
PAlo " u ∈ U, p ∈ PI u ð10Þ
up
ity 11 denotes the lower and upper bounds for the operational
variables in each process unit. These limits generally are subject
Vo,lou e Vo, u e Vo,upu " u ∈ U, o ∈ Ou ð11Þ to design conditions. Finally, expression 12 denotes the domain
of the variables used in the formulation of the refinery
FF u , Fu0 , s, u , FPu, s ∈ Rþ ; PAu, p , PCu, s, p , Vo, u ∈ R ð12Þ planning model.
The mathematical model for the refinery planning described
above results in a nonlinear planning model and can be solved
Equation 1 defines the objective function (maximize the total using nonlinear programming (NLP) optimization algorithms
profit (US $/day)) for the refinery planning model in terms of such as sequential linear programming (SLP), generalized re-
sales revenue (blending units, u∈Up), raw material purchase duced gradient (GRG), sequential quadratic programming
costs (units that can process external streams, u∈Uf), and (SQP), and interior point (IP). These algorithms have been
operating costs. The terms Cpru, Crms, and Copu denote the implemented in some NLP solvers, such as CONOPT, IPOPT,
13405 dx.doi.org/10.1021/ie200303m |Ind. Eng. Chem. Res. 2011, 50, 13403–13418
Industrial & Engineering Chemistry Research
Figure 3. Simplified distillation processes.
KNITRO, MINOS, and SNOPT, which are available in many
modeling systems (AIMS, AMPL, GAMS, and MINOPT).
3. CRUDE DISTILLATION UNITS
Crude distillation units (CDUs) are the most important
process units in a refinery, because they perform the separation
of crude oil in many fractions (naphtha, kerosene, diesel oil,
atmospheric residue, vacuum gas oils, etc.) that are processed in
the downstream units (FCC units, delayed coking unit, etc.) or
sent to the blending system to form final products. Conse-
quently, the overall economical performance of a refinery is
directly impacted by the operation of the CDUs.
The crude distillation process occurs in two sections: in the
first one (denoted as atmospheric distillation), the operating pres-
sure is set close to atmospheric pressure. In the second section
(denoted as vacuum distillation), the operating pressure is set to
vacuum pressure (generally in the range of 50
100 mmHg). Prior
to the distillation processes, the crude oil is desalted using water
(to prevent corrosion problems) and heated to provide the ade-
quate conditions for the separation. In Figure 3, a simplified
distillation process is presented. The yields and properties of the
different fractions from the distillation process depend on the type
of crude processed (heavy, medium, or light) and the operating
conditions (heater outlet temperature, reflux ratio, etc.).
3.1. Overview of Empirical Models for Crude Distillation
Units. The empirical models for CDUs reported in the literature
include the swing cut model,13 the adherent recursion model,14
and the Weight Transfer Ratio (WTR) model.15 The swing cut
model is the most commonly used of these models. Normally,
the swing cut model is implemented in commercial planning
tools such as RPMS and PIMS, basically due to its simplicity. On
the other hand, the swing cut model is more inaccurate than the
adherent recursion and WTR models. In the swing-cut model,
the TBP (true boiling point curve) cut point between each two
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adjacent fractions is optimized using a pseudo-cut called a swing
cut (a virtual cut between each two adjacent fractions) with
constant properties. The size of each swing cut is defined as a
certain volume percentage or weight percentage of the overall
crude fed to the CDU (i.e., 5 wt% for the swing cut naphtha/
kerosene, according to Zhang et al.13). Optionally, the size of
each swing cut can be defined as a certain TBP range (i.e., 50 F,
according to Trierwiler14). In the case that more than one crude
oil can be fed to the CDU, the flow rate of each swing cut from all
crude oils are pooled and the resultant stream is distributed
between the corresponding two adjacent fractions. The major
limitation of the swing cut model is that the properties for each
swing cut are considered constants across its TBP range, while
the property distribution across the TBP ranges are known to be
highly nonlinear. Consequently, the swing cut model fails to
represent the highly nonlinear behavior of distillation processes.
The adherent recursion model addresses this limitation, using
an iterative procedure between a LP planning model and a rig-
orous process simulator (HYSYS, PRO/II, etc.). In this proce-
dure, the LP planning model is used to optimize the TBP cut
points and the solution at each iteration (new cut points) is used
by the rigorous process simulator to provide updated yields and
properties for the CDU fractions. The main limitation of the
adherent recursion is the long computational time required for
the convergence of the iterative procedure, because of the use of a
rigorous process simulator.
Finally, in the WTR model, the CDU operating modes are
used to determine the maximum and minimum yield of each
fraction over the TBP curve of the crude oil fed to the CDU;
these values are fixed as upper and lower bounds for the yield of
each fraction from the CDU. In addition, the properties of CDU
fractions are expressed as a nonlinear function of their respective
mid-volume transfer ratio. The TBP cut points are optimized
using the yield of CDU fractions as decision variables constrained
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Industrial & Engineering Chemistry Research
Figure 4. Typical TBP distillation curve.
by the mass balance and the maximum and minimum yields
obtained from the operating modes. Therefore, this model can re-
present the highly nonlinear behavior of distillation processes.
Nevertheless, as in the petroleum industry, it is very usual that the
CDU is able to process more than one crude oil; the implementa-
tion of the WTR model requires additional tedious procedures to
estimate the TBP curve of the crude oil mixture fed to the CDU.
3.2. Empirical Model for CDUs. The necessary characteriza-
tion information of each crude oil must be available in the
refinery (i.e., from laboratory databases) in order to developed
a meaningful empirical model for CDUs. There are two types of
characterization information normally used for crude oil evalua-
tions: the crude oil distillation curve (TBP) and the crude oil
property distribution curves.
The TBP curve is the relationship between the distillate tem-
perature and the cumulative volumetric fraction distilled in a
standard distillation column. The standard test method for the
experimental estimation of the TBP is ASTM D2892 (at atmo-
spheric pressure) for fractions with boiling points below 400 C
and the ASTM D1160 (at reduced or vacuum pressure) for
fractions with boiling points above 400 C. For distillate pro-
ducts, standard method ASTM D86 is generally used. Distillation
curves obtained by the ASTM D1160 and ASTM D86 standard
test methods can be converted into TBP curves using the method
described by Riazi.12 A typical TBP curve is presented in Figure 4.
On the other hand, the properties (API density, sulfur (wt %),
etc.) of distillate products can be expressed using the property
distribution curves, which represent the relationship between the
crude oil properties and the mid-volume transfer ratio (Mid-Vol
(%)) of the fraction distilled.3 A typical sulfur (wt %) distribution
curve is presented in Figure 5.
The TBP curve and the property distribution curves for each
crude oil (available in the refinery) are the necessary character-
ization information for the empirical model developed in this
work. In many cases, the distribution curve for a given property
can be unavailable in the refinery. In that case, the distribution
curve can be predicted from the TBP curve and the distribution
curve for other property (density, viscosity, molecular weight,
etc.) using empirical correlations.12
In addition to the crude oil characterization information, the set
of decision variables is another important aspect to be defined in
the formulation of the empirical model for CDU. This set should
be related to the operating variables that significantly affect the
process behavior for a given feedstock characterization. The TBP
cut points between adjacent fractions are probably the operating
variables that have the greatest impact on the CDU operation.
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Figure 5. Typical sulfur distribution curve.
The definition of the TBP cut point between adjacent fractions
is illustrated in Figure 6. In this figure, the temperature T100 L
represents the final TBP boiling point for the light fraction
(EBPL) and the initial TBP boiling point for the heavy fraction
(IBPH) is represented by the temperature T0H. As can be seen in
Figure 6, the TBP cut points are defined as the average
temperature between the EBPL and IBPH (Tcut = 0.5(T100 L

T0H)). In addition, the degree of separation between two
adjacent fractions is given by the difference between EBPL and
IBPH (T100 L
T0H). This degree of separation depends upon
the efficiency of the distillation column. The detailed procedure
for the estimation of the TBP cut points is presented in Figure 7.
As shown in this figure, the TBP cut points can be estimated from
ASTM D86 100% (the temperature corresponding to the 100
vol % on the ASTM D86 distillation curve) product specifica-
tions and the degree of separation given by the Gap (5
95)
ASTM (the temperature difference between the ASTM 5 vol %
boiling point of the heavier product and the ASTM 95 vol %
boiling point of the adjacent lighter product).
The product yields and properties are strongly affected by
changes in TBP cut points. Furthermore, they are commonly
used in the CDU operation to control the adequate separation
efficiency in the distillation column, as well as the product
specifications. For this reason, the TBP cut points are chosen
as decision variables in the proposed approach.
The ASTM D86 specifications are defined for each refinery,
and the Gap (5
95) can be set by heuristics or estimated using a
rigorous process simulator (HYSYS, PRO/II, etc.). In that case,
many scenarios must be defined by varying the operating con-
ditions and the feedstock characterization in order to evaluate the
variability of each degree of separation; the Gap (5
95) ASTM
between each two adjacent fractions should be reported as the
average value for all of the scenarios. Usual values (recommended
by Watkins3) for the ASTM D86 boiling point range (IBP and
EBP) of CDU fractions and the Gap (5
95) ASTM are
presented in Tables 2 and 3, respectively. In this work, ranges
of 260
275 F and 650
700 F will be considered for the EBP
of gross overhead and heavy distillate, respectively; in other case,
the values from Table 2 will be used.
The volumetric yield of each CDU fraction can be estimated as
a function of the TBP cut points. For example, the volumetric
yield (vol %) of heavy naphtha for a given crude oil is estimated as
the difference between the cumulative volume percent corre-
sponding to the two adjacent TBP cut points (heavy naphtha/
light distillate and gross overhead/heavy naphtha TBP cut
points). In addition, the Mid-Vol (%) value of each fraction is
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Industrial & Engineering Chemistry Research
Figure 6. Definition of TBP cut point between adjacent fractions.3
Figure 7. Procedure for the estimation of TBP cut point between adjacent fractions.3
estimated using its volumetric yield and the actual cumulative
volume percentage.
3.2.1. Mathematical Model. The mathematical formulation of
the empirical model for the CDUs is based on the process unit
structure presented in Figure 2. It is considered that the refinery
has only one CDU, and this is the only unit that processes crude
oil (Uf = {CDU}). Nevertheless, the model can be easily
implemented if there is more than one CDU in the refinery.
The model was formulated on a volumetric basis (volumetric
balances are very common in the petroleum industry), then all of
the flow rates are given in volumetric units. The set USr,CDU =
{s01 ,s0 2,...,s0 k} defines the crude oils (at a flow rate Fr,s0 ,CDU) that
can be fed into the CDU, and the total feed flow rate to the CDU
is represented by the variable FFCDU. The product streams from
this unit are defined by the set SOCDU = {s1,s2,...,sn}. In addition,
the variable FPCDU,s denotes the total flow rate of each product
stream from the CDU, and the contribution of each crude oil to
the total flow rate of each product stream is represented by the
variable FDs,s0 . In general, the product streams from the CDU can
be characterized by the set of properties POCDU = {p1,p2,...,pm},
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ARTICLE
while the relevant properties for each product stream are defined
by the set POCDU,s⊆POCDU. The variables PCCDU,s,p and PDs0 ,s,p
represent the property values of the product streams and the
contribution of each crude oil to the property values of each
product stream from the CDU, respectively. The units that can
process product streams from the CDU are defined by the set
SUs,CDU. The operating variables in the CDU are defined by the
set of TBP cut points between adjacent fractions OCDU =
{Ts1,s2,Ts2,s3,...,Tsn
1sn}. In addition, the variable VTsi,si+1 ,CDU de-
notes the value of each operating variable in the CDU.
The crude oils are characterized by the TBP curve (TBPs0 )
and the property distribution curves (PROp,s,). The variable
VDs0 ,Tsi ,si+1 represents the volume percent vaporized of crude oil s0
for each TBP cut point and the variable Mid_Vols,s0 represents the
mid-volume transfer ratio for product streams from the CDU.
Finally, based on the sets and variables described above, the
mathematical model for the CDUs can be written as follows:
VDs0 , Tsi , siþ1 ¼ TBPs0 ðVTsi , siþ1 , CDU Þ " s0 ∈ USr, CDU , Tsi , siþ1 ∈ OCDU
ð13Þ
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Industrial & Engineering Chemistry Research ARTICLE

Table 2. Suggested ASTM Boiling Ranges for CDU Fractionsa

Operating Mode

product max naphtha max light distillate max heavy distillate

gross overhead (GO) 250
275 F (EBP) 250
275 F (EBP) 250
275 F (EBP)

heavy naphtha (HN) 400 F (EBP) 325 F (EBP) 325 F (EBP)
light distillate (LD) 375
600 F (IBP
EBP) 300
600 F (IBP
EBP) 300
550 F (IBP
EBP)
heavy distillate (HD) 575
675 F (IBP
EBP) 575
675 F (IBP
EBP) 525
675 F (IBP
EBP)
a
Data taken from ref 3.

Table 3. Suggested Gap (5
95) ASTM for Adjacent

Fractionsa
∑
u0 ∈ SU s, CDU
FCDU, s, u0 ¼ FPCDU, s " s ∈ SOCDU ð23Þ

adjacent fractions Gap (5
95) ASTM (F) up

VTlosi , s e VTsi , siþ1 , CDU e VTsi , siþ1 , CDU " Tsi , siþ1 ∈ OCDU
iþ1 , CDU
gross overhead/heavy naphtha (GO/HN) 20
30
heavy naphtha/light distillate (HN/LD) 25
50 ð24Þ
light distillate/heavy distillate (LD/HD) 0
10
" s0 ∈ USr, CDU
up
heavy distillate/bottom residue (HD/BR) 0
10 Fr, s0 , CDU e Fr, s0 , CDU ð25Þ
a
Data taken from ref 3.
FF CDU ¼ ∑
s0 ∈ USr, CDU
Fr, s0 , CDU ð26Þ


1
FDsi , s0 ¼ Fr, s0 , CDU ðVDs0 , Tsi , siþ1
VDs0 , Tsi
1 , si Þ FF loCDU e FF CDU e FF CDU
up
ð27Þ
100
"si jTsi , siþ1 ∈ fTs2 , s3 , Ts4 , s5 , :::, Tsn
2 , sn
1 g, s0 ∈ USr, CDU
FF CDU , Fr, s0 , CDU , VDs0 , Tsi , siþ1 , FDsi , s0 , Midvolsi , s0 , FCDU, s, u0 ,
ð14Þ
FPCDU, s ∈ Rþ ; PDs0 , s, p , PCCDU, s, p , Vo, CDU ∈ R ð28Þ


1 Equation 13 defines the volume percent vaporized (in units of
FDs1 , s0 ¼ Fr, s0 , CDU VDs0 , Ts1 , s2 " s0 ∈ USr, CDU
100 vol %) of each crude oil as a function of the TBP cut points (in

 this work, the TBP curves are represented using a third-order
ð15Þ
1 polynomial function). The contribution of each crude oil to the
FDsn , s0 ¼ Fr, s0 , CDU ð100
VDs0 , Tsn
1 , sn Þ " s0 ∈ USr, CDU total flow rate of each product stream is described by eqs 14, 15,
100
and 16, while the total flow rate for these products is obtained
ð16Þ
using eq 17. In addition, the mid-volume transfer ratio for
product streams can be estimated according to eqs 18, 19, and
FPCDU, s ¼ ∑
s0 ∈ USr, CDU
FDs, s0 " s ∈ SOCDU ð17Þ 20. The contribution of each crude oil to the property values of
each product stream is expressed by eq 21; in this work, the
property distribution curves were represented using a fourth (or
Mid _ Volsi , s0 ¼ VDs0 , Tsi
1 , si þ 0:5ðVDs0 , Tsi , siþ1
VDs0 , Tsi
1 , si Þ less)-order polynomial function. Furthermore, the properties of
ð18Þ product streams are estimated using eq 22 if the mixing rule of
"si jTsi , siþ1 ∈ fTs2 , s3 , Ts3 , s4 ,..., Tsn
2 , sn
1 g, s0 ∈ USr, CDU the property is based on volume. In the case of properties with a
mixing rule based on weight, the flow rate in eq 22 should be
Mid_Vols1 , s0 ¼ 0:5VDs0 , Ts1 , s2 " s0 ∈ USr, CDU ð19Þ given in mass units (the property indices shown in Table 1 can be
used for properties with highly nonlinear mixing rules). Equation
23 denotes the volumetric balance at the product splitters.
Mid_Volsn , s0 ¼ 100
0:5VDs0 , Tsn
1 , sn " s0 ∈ USr, CDU Inequalities 24 and 25 denote the constraints for operating
ð20Þ variables and crude oil supply, respectively. Equation 26 repre-
sents the volumetric balance at the feed mixer (crude oil mixer)
PDs0 , s, p of the CDU. The operating capacity is defined by inequality 27.
Finally, the expression described by eq 28 denotes the domain of
¼ PROp, s0 ðMid_Vols, s0 Þ " s0 ∈ USr, CDU , s ∈ SOCDU , p ∈ POCDU, s the variables used in the formulation of the empirical model
for CDUs.
ð21Þ
3.2.2. Model Validation Using HYSYS. The empirical model
for the CDUs was validated using rigorous process simulations
PCCDU, s, p (based on TBP data and pseudo-components) carried out in
Aspen HYSYS v7.0, using Peng
Robinson as the fluid package.
∑
1
¼ PDs0 , s, p FDs, s0 " s ∈ SOCDU , p ∈ POCDU, s
FPCDU, s s0 ∈ USr, CDU
Three case studies were evaluated using two different crude oils:
Tia Juana Light and Arabian Heavy. The configuration of each
ð22Þ case study is presented in Table 4. The main products from the
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Industrial & Engineering Chemistry Research
Table 4. Case Studies for CDU Model Validation
Feed Flow Rate (kbpd)
crude oil Case A Case B
Tia Juana Light (API = 31.6) 60 70
Arabian Heavy (API = 27.4) 40 30
total 100 100
CDU Feed Properties
Case A Case B
API density 29.65 30.06
molecular weight 234.0 kg/kmol 230.2 kg/kmol
Table 5. Product Specifications
Specification
product ASTM D86, 100% Gap (5
95) ASTM
gross overhead 275 F (135.0 C)
heavy naphtha 325 F (162.8 C)
light distillate 600 F (315.6 C)
heavy distillate 700 F (371.1 C)
bottom residue
CDU are: gross overhead, heavy naphtha, light distillate, heavy
distillate, and bottom residue. The specifications for CDU pro-
ducts and the degree of separation between adjacent fractions are
presented in Table 5. The data shown in Table 5 should be
interpreted as follows: the Gap (5
95) ASTM between gross
overhead and heavy naphtha is equal to 25 F.
The configuration of the CDU in HYSYS includes a preflash
column, a crude oil heater, and a distillation column. The pre-
heated crude oils are mixed and fed to the preflash column at
450 F and 75 psia. In the preflash column, light components are
removed from the crude oil (mixed crude oil) in order to reduce
the energy consumption in the crude oil heater. The heavy
product (bottom product) from the preflash column is fed to the
crude oil heater, where it is heated to the appropriate column
feed temperature. According to Watkins,3 the column feed
temperature should be in the range of 650
700 F in order to
avoid thermal cracking. In this work, the column feed tempera-
ture was set to 700 F. In addition, the distillation column
includes a main column with 29 theoretical stages, three pump-
arounds, three side-strippers, a condenser, and a reboiler (see
Figure 8). The distillation column has 13 degrees of freedom (see
Table 6), while the empirical model developed in this work has
only 8 degrees of freedom (4 ASTM D86 100% and 4 Gap
(5
95) ASTM). This is because the empirical models are more
simplified than the rigorous process models. For example, the
energy balance is not included in the empirical model for CDUs
developed in this work.
The CDU was simulated for all of the case studies using both
the rigorous process simulator model (the HYSYS model) and
the empirical model developed in this work. In the empirical
model, the TBP cut points were estimated using the procedure
described in Figure 7, using the specifications presented in
Table 5. The comparison of product yields is shown in Table 7.
As can be seen in this table, the absolute error in the yield
ARTICLE
predictions using the empirical model was e4.10 vol %. This
absolute error can be reduced to be e0.51 vol % via the addition
of bias factors to the empirical model predictions, as described in
eq 29. These bias factors were calculated as an average of the
Case C
empirical model errors, with respect to the rigorous simulation.
80
20 FPCDU, s ¼ ∑
s0∈ USr, CDU
FDs, s0 þ BiasðsÞ
100
 FF CDU " s ∈ SOCDU ð29Þ
Case C
Equation 29 is a modification of eq 17; the sum of the bias
30.48 factors should be equal to zero, because of the volumetric balance
226.4 kg/kmol in the product splitters. In the work of Li et al.,15 the yield
predictions from the WTR model were compared (using three
case studies) with rigorous simulation carried out in Aspen Plus
version 11.1; the absolute error in the yield predictions was
determined to be less than or equal to 1.3, 3.2, 3.07, 2.67, and
3.06 wt % for the gross overhead (GO), heavy naphtha (HN), light
distillate (LD), heavy distillate (HD), and bottom residue (BR),
respectively. Finally, based on the results from model validation, it
can be concluded that the empirical model for CDU developed in
25 F
this work is adequate for the simulation of the CDUs.
35 F
10 F
4. FLUID CATALYTIC CRACKING (FCC) UNIT
5 F
Fluid catalytic cracking (FCC) is the most important con-
version process in a refinery. In this process, heavy fractions
(atmospheric gas oil, vacuum gas oil, cocker gas oil, etc.) are
converted into light and more-valuable fractions (ethane, ethy-
lene, propylene, butylenes, iso-butane, n-butane, naphtha, etc.).
FCC naphtha becomes a gasoline blending stock. According to
Robinson,16 the FCC units produce more than half of the world’s
gasoline. Light olefins (particularly propylene and butylenes) and
iso-butane are alkylated (in the alkylation unit) to produce high-
octane hydrocarbons for the gasoline pool. In addition, ethane
and ethylene are used as petrochemical feedstock to produce a
variety of products.
The FCC units consist of a riser reactor, a regenerator, and a
product separation system (see Figure 9). In the riser, the fresh
feed is mixed with the regenerated catalyst to provide the nec-
essary conditions for the cracking reactions. In the regenerator,
the combustion air provides the necessary oxygen for the catalyst
regeneration by burning of the coke in the spent catalyst from the
reactor. In addition, the cracked products from the reactor are
obtained separately in the fractionator. The FCC feed composi-
tion has a direct impact in the process behavior. For example, the
reactivity increases according to paraffins > naphthenes > aro-
matics. Therefore, paraffinic feeds produce more naphtha (with
less octane number) than naphthenic and aromatic feeds for the
same set of operating conditions. Olefins are not the preferred
feed to an FCC unit, because they often polymerize to form
undesirable products, such as decanted oil and coke. The typical
olefin content of FCC feed is <5 wt %.17
4.1. Overview of Empirical Models for FCC Units. The
empirical approaches that have been reported in the literature for
modeling FCC units include the delta-base model (commonly
implemented in RPMS and PIMS), the UltraCat model (from
Wollaston et al.18), and the procedure described by Gary and
Handwerk.19 The limitations of delta-base model were pre-
viously described in section 1 of this paper. Contrary to the delta-
base model, the UltraCat model is based on highly nonlinear
13410 dx.doi.org/10.1021/ie200303m |Ind. Eng. Chem. Res. 2011, 50, 13403–13418
Industrial & Engineering Chemistry Research
Figure 8. CDU simulation model in HYSYS.
Table 6. Distillation Column Specifications
specification number of specifications
gap (5
95) ASTM (F) 4 (GO-HN, HN-LD, LD-HD, and HD-BR)
ASTM D86, 100% (F) 4 (GO, HN, LD, and HD)
reflux ratio 1 (condenser)
pump-around flow rate 1 (PA_1)
pump-around heat duty 2 (PA_2 and PA_3)
off-gas flow rate 1 (condenser)
total degrees of freedom 13
empirical correlations for the second-order conversion and the
coke yield. These two empirical correlations (reactor model) are
integrated with two equations that correspond to the heat
balance between the reactor and the regenerator; the yield and
properties for the remaining products are estimated using
simplified empirical correlations. This model was successfully
validated using both pilot- and industrial-plant data. The main
limitation of the UltraCat model is that it is highly nonlinear and
its integration into the entire refinery planning model can lead to
excessive computational cost or difficulties in achieving a local
optimal solution.
The procedure described by Gary and Handwerk19 is a graph-
ical method where product yields and properties are estimated as
a function of the conversion (the operational variable) and two
feed characterization parameters (API gravity and Watson char-
acterization factor). This graphical method can be impractical for
refinery planning, because it is based on charts and figures
that should be converted into mathematical expressions using
13411
ARTICLE
numerical approximations. In addition, the model does not con-
sider the effect of the reactor temperature and the catalyst-to-oil
ratio (two of the most important operating variables in the FCC
process) on product yields and properties, which can be a limitation.
4.2. Empirical Model for a FCC Unit. In the FCC reactor, a
large number of chemical reactions involving a large number of
hydrocarbon compounds take place. Therefore, the modeling of
FCC process results in a large-scale modeling problem. Rigorous
FCC process simulators such as Aspen FCC (AspenTech) and
FCC-SIM (KBC Advanced Technologies) are based on the
lumping technique for feedstock and products characterization,
in order to reduce the inherent problem size. The number of
lumps used for the modeling of FCC process determines the
model structure and applicability. For example, in the 10-lumps
model,20 the reaction rate constants can be considered to be
independent of the feed composition, which is very important for
the simulation of industrial FCC units, because these units can
process both light and heavy feeds. Moreover, when more than
20 lumps are used, all reaction rates can be considered to be
pseudo-first-order21 and the FCC model becomes mostly linear.
However, the higher the number of lumps, the higher is the
number of reaction rate constants to be estimated. For the
regenerator, a rigorous coke burning kinetics (approximately
six reactions) is adopted. Because of the detailed modeling,
rigorous FCC process simulators are suitable for the simulation
of industrial FCC units. Typically, they are used for catalyst
selection, feed selection, delta-base model generation, and other
applications.
The empirical model for a typical FCC unit developed in this
work consists of a set of empirical correlations based on data from
dx.doi.org/10.1021/ie200303m |Ind. Eng. Chem. Res. 2011, 50, 13403–13418
Industrial & Engineering Chemistry Research ARTICLE

Table 7. Comparison of Product Yields

Product Yield (vol %)

HYSYS Simulation Empirical Model Maximum Absolute Error (vol %)

producta Case A Case B Case C Case A Case B Case C without bias with bias bias (vol %)

GO 14.22 14.19 14.17 11.84 12.32 12.80 2.39 0.51 1.87

HN 5.32 5.38 5.46 4.91 4.90 4.89 0.57 0.08 0.49
LD 23.83 24.17 24.51 20.25 20.33 20.41 4.10 0.26 3.84
HD 10.59 10.73 10.86 14.41 14.54 14.67 3.82 0.01
3.81
BR 46.04 45.52 45.01 48.59 47.91 47.23 2.54 0.17
2.39
a
GO = gross overhead; NH = heavy naphtha; LD = light distillate; HD = heavy distillate; and BR = bottom residue.

Figure 9. Simplified fluid catalytic cracking (FCC) unit.

a PETROBRAS FCC process simulator (a rigorous process
simulator). The data consist of a series of simulations, using a set
of independent variables (operating variables and feed proper-
ties). This set of independent variables was defined as the
operating variables and feed properties that more affect the
FCC process behavior. The independent variables and their
respective operating limits (design specifications and operating
constraints) are presented in Table 8. A total of 193 simulations
was used: 135 (70% of total simulations) were used for
parameter estimation, and 58 (30% of total simulations) were
used for model validation. The numerical values for all inde-
pendent variables in each simulation were defined according
to eq 30:
 
up
xi, j ¼ xloi þ randi, j xi
xloi
" i ∈ fAPI ,..., Trxn g, j ∈ f1, 2 ,..., 193g
where xup lo
i is the upper bound for independent variable i, xi the
lower bound for independent variable i, randi,j a random number
between 0 and 1 for independent variable i in simulation j, and xi,j
the value for variable i in simulation j.
4.2.1. Mathematical Model. Similar to the formulation of the
empirical model for CDUs, the formulation (on a volumetric
basis) of the empirical model for the FCC unit is based on the
process unit structure presented in Figure 2. The product yields
and properties were expressed as polynomial functions of
three or less independent variables. The FCC unit can be fed
(at a flow rate Fu0 ,s00 ,FCC) by a set of intermediate streams
USu0 ,FCC = {s001 ,s002 ,...,s00w} from upstream units u0 ∈UFCC (UFCC =
{CDU,...}). The total FCC feed can be characterized by a set of
properties PIFCC = {SPG,API,SUL,CCR}, where SPG, API, SUL,
and CCR denotes the specific gravity, API gravity, sulfur content
(in units of wt %), and Conradson carbon residue (in untis of
wt %), respectively. The operating variables in the FCC unit are
defined by the set OFCC = {Trxn,CO}, where Trxn and CO
represents the reactor temperature and the catalyst-to-oil ratio,
in that order. The numeric values for the reactor temperature and
catalyst-to-oil ratio are represented by the variables VTrxn,FCC and
VCO,FCC, respectively. The product streams from the FCC unit
are defined by the set SOFCC = {C3T,C4T,NAP,LCO,DO,COK},
ð30Þ where C3T, C4T, NAP, LCO, DO, and COK denotes total C3s,
total C4s, naphtha, light cycle oil, decanted oil, and coke respec-
tively. The relevant properties for naphtha, light cycle oil, and
decanted oil are defined by the sets POFCC,NAP = {SPG,API,SUL,
RON,MON}, POFCC,LCO = {SPG,API,SUL,CTI,PPI,VII} and
POFCC,DO = {SPG,API,SUL,VII}, correspondingly. The indices
RON, MON, CTI, PPI, and VII denote research octane number,
motor octane number, cetane index, pour point index, and viscosity
13412 dx.doi.org/10.1021/ie200303m |Ind. Eng. Chem. Res. 2011, 50, 13403–13418
Industrial & Engineering Chemistry Research ARTICLE

index, respectively. The property indices are estimated according to FCLCO ¼ βLCO, 1 þ βLCO, 2 X 0 þ βLCO, 3 X 0 X 0 ð36Þ
Table 1. In addition, there are three auxiliary variables: weight
conversion (X), second-order conversion (X0 ), and weight hourly FCDO ¼ βDO, 1 þ βDO, 2 X 0 þ βDO, 3 X 0 X 0 ð37Þ
space velocity (WHSV).
Finally, based on the sets and variables described above, the FCCOK ¼ βCOK, 1 þ βCOK, 2 PAFCC, CCR
mathematical model for the FCC unit can be written as follows:
þ βCOK, 3 VCO, FCC þ βCOK, 4 WHSV
FF FCC ¼ ∑ ∑
u0 ∈ UFCC s00 ∈ USu, , FCC
Fu0 , s00 , FCC ð31Þ
þ βCOK, 5 PAFCC, CCR VCO, FCC

þ βCOK, 6 PAFCC, CCR WHSV

∑ ∑
1
PAFCC, p ¼ PCu0 , s00 , p Fu0 , s00 , FCC " p ∈ PIFCC
FFFCC u0 ∈ UFCC s00 ∈ USu0 , FCC
þ βCOK, 7 VCO, FCC WHSV ð38Þ
ð32Þ

X ¼ R1 þ R2 PAFCC, API þ R3 VCO, FCC

FCC3T ¼ βC3T, 1 þ βC3T, 2 X 0 þ βC3T, 3 X 0 X 0 ð33Þ
þ R4 VTrxn , FCC þ R5 PAFCC, API VCO, FCC
þ R6 PAFCC, API VTrxn , FCC þ R7 VCO, FCC VTrxn , FCC ð39Þ
FCC4T ¼ βC4T, 1 þ βC4T, 2 X 0 þ βC4T, 3 X 0 X 0 ð34Þ
X
X0 ¼ ð40Þ
FCNAP ¼ βNAP, 1 þ βNAP, 2 PAFCC, API 100
X

þ βNAP, 3 VCO, FCC þ βNAP, 4 X 0 kPAFCC, SPG FF FCC

WHSV ¼ ð41Þ
CatInv
þ βNAP, 5 PAFCC, API VCO, FCC

þ βNAP, 6 PAFCC, API X 0 þ βNAP, 7 VCO, FCC X 0 ð35Þ PCFCC, NAP, API ¼ βNAP, 8 þ βNAP, 9 PAFCC, API

Table 8. Range of Feed Properties and Operating Variables þ βNAP, 10 X ð42Þ

lower upper
variable bound bound PCFCC, NAP, SUL ¼ βNAP, 11 þ βNAP, 12 PAFCC, SUL
API gravity 19 27 þ βNAP, 13 X ð43Þ
total sulfur (wt %) 0.5 3.1
Conradson carbon 2.0 6.0
residue, CCR (wt %)
PCFCC, NAP, RON ¼ βNAP, 14 þ βNAP, 15 PAFCC, API
catalyst-to-oil ratio, C/O 3.85 6.8
þ βNAP, 16 X ð44Þ
weight hourly space 2.8 5.7
velocity, WHSV (h
1)
reaction temperature, Trxn 956 F (513.3 C) 1000 F (537.8 C) PCFCC, NAP, MON ¼ βNAP, 17 þ βNAP, 18 PCFCC, NAP, RON ð45Þ

Figure 10. Parity plots for C3T and C4T yield prediction.

13413 dx.doi.org/10.1021/ie200303m |Ind. Eng. Chem. Res. 2011, 50, 13403–13418

Industrial & Engineering Chemistry Research ARTICLE

Figure 11. Parity plots for naphtha and LCO yield prediction.

Figure 12. Parity plots for DO and coke yield prediction.

PCFCC, LCO, API ¼ βLCO, 4 þ βLCO, 5 PAFCC, API PCFCC, DO, API ¼ βDO, 4 þ βDO, 5 PAFCC, API

þ βLCO, 6 X ð46Þ þ βDO, 6 X ð51Þ

PCFCC, LCO, SUL ¼ βLCO, 7 þ βLCO, 8 PAFCC, SUL PCFCC, DO, SUL ¼ βDO, 7 þ βDO, 8 PAFCC, SUL

þ βLCO, 9 X ð47Þ þ βDO, 9 X ð52Þ

PCFCC, LCO, CTI ¼ βLCO, 10 þ βLCO, 11 PAFCC, API PCFCC, DO, VII ¼ βDO, 10 þ βDO, 11 PAFCC, API

þ βLCO, 12 X ð48Þ þ βDO, 12 X ð53Þ

 !
PCFCC, LCO, PPI ¼ βLCO, 13 þ βLCO, 14 PAFCC, API FPFCC, s ¼ FCs
1 PAFCC, SPG
FF FCC " s ∈ SOFCC
100 PCFCC, s, SPG
þ βLCO, 15 X ð49Þ
ð54Þ
PCFCC, LCO, VII ¼ βLCO, 16 þ βLCO, 17 PAFCC, API

þ βLCO, 18 X ð50Þ
∑
u0 ∈ SU s, FCC
FFCC, s, u0 ¼ FPFCC, s " s ∈ SOFCC ð55Þ

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Industrial & Engineering Chemistry Research ARTICLE

up
FF loFCC e FF FCC e FF FCC
up
PAloFCC, p e PAFCC, p e PAFCC, p " p ∈ PI FCC
up
Vo,loFCC e Vo, FCC e Vo, FCC " o ∈ OFCC
FF FCC , Fu0 , s00 , FCC , FCs , FFCC, s, u0 , FPFCC, s , X, X 0 ,
WHSV ∈ Rþ ; PAFCC, p , PCFCC, s, p , Vo, FCC ∈ R
Equations 31 and 32 calculate the total flow rate and the
relevant properties for the feed to the FCC unit. Equations
33
38 express the product yields (in units of wt %) for the FCC
products, as a function of feed properties and operating variables.
The conversion (in units of wt %), second-order conversion, and
weight hourly space velocity (WHSV) are estimated using eqs 39,
40, and 41, respectively. In eq 41, the scalar k is a conversion factor
(for WHSV) and the parameter CatInv represents the catalyst
inventory in the reactor. Product properties are estimated using
eqs 42
45 for naphtha, eqs 46
50 for LCO, and eqs 51
53 for
DO. The total flow rate for FCC products is estimated using eq 54.
In addition, eq 55 denotes the volumetric balance at the product
splitters. Inequalities 56 and 57 denote the capacity and feed
property constraints for the FCC unit respectively. Inequality 58
denotes the constraints for operating variables. Finally, the expres-
sion described in eq 59 denotes the domain of the variables used in
Figure 13. Parity plot for conversion prediction.
ð56Þ the formulation of the empirical model for the FCC unit. The
parameter in the model are defined by βs,j (parameters for product
yield and property correlations) and Ri (parameter for conversion
ð57Þ correlation), s∈SOFCC, j, and i are numerical identifiers.
4.2.2. Parameter Estimation and Model Validation. The
ð58Þ parameters in the empirical model for the FCC unit (βs,j and
ri) were estimated independently for each product yield and
property via the linear least-squares method (the correlations are
linear in the parameters) using MATLAB version 7.0.4. The
ð59Þ parity plots for product yield predictions (estimation and
validation) are presented in Figures 10
12. In addition, the
parity plot for the conversion is presented in Figure 13. The
coefficient of determination (R2) was found to be g0.950 for
product yields and conversion correlations, and g0.964 for
product property correlations. The maximum and average
absolute errors for product yields and conversion correlations
are presented in Table 9. Table 9 shows that the absolute error
for product yield predictions was e2.09 wt % for parameter
estimation and e1.14 wt % for model validation. Moreover, the
maximum and average absolute error for the coke yield predic-
tion using the same correlation presented in the UltraCat model
and fitting seven parameters (as in eq 38) were found to be
e0.63 wt % and e0.48 wt %, respectively. These values are
greater than those obtained using the empirical correlation
proposed in this work (see Table 9). Similarly, the maximum
and average absolute error for the conversion prediction using
the same correlation presented in the UltraCat model and fitting
seven parameters (as in eq 39) were found to be e2.36 wt % and
e0.41 wt %, respectively. These values are close to those
obtained using the polynomial correlation proposed in this
work (see Table 9). Nevertheless, the polynomial correlations
presented in this work involve less-complex mathematical
expressions than the empirical correlations presented in the
UltraCat model.
Based on the results from parameter estimation and model
validation, it can be concluded that the empirical model for the
FCC unit is accurate and adequate for simulation of FCC
process. Finally, for the implementation of this empirical process
model (including empirical correlation for tail gases (H2S,
methane, ethane, etc.) not presented in this work), product
yield predictions should be normalized in order to ensure the
mass balance across the FCC unit, since mass balance was not
ensured for model prediction during the parameter estimation
phase. It is important to note that we proposed correlations
for LCO yield, DO yield, and conversion. Nevertheless, only
two of them should be used since the conversion is equal to
100
FCLCO
FCDO.

Table 9. Error for Parameter Estimation and Model Validation

Parameter Estimation Model Validation

product maximum absolute error (wt %) average absolute error (wt %) maximum absolute error (wt %) average absolute error (wt %)

C3T 0.25 0.09 0.21 0.07

C4T 0.51 0.15 0.46 0.16
NAP 2.09 0.41 1.14 0.45
LCO 0.58 0.15 0.40 0.15
DO 0.81 0.17 0.55 0.18
COK 0.22 0.08 0.21 0.09

conversion, X (wt %) 3.36 0.38 1.91 0.44

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Industrial & Engineering Chemistry Research ARTICLE

5. CONCLUSIONS Up = units that can produce final products

In this work, empirical models for crude distillation units Uu = units u0 that can sent product streams as a feed to unit u
(CDUs) and a fluid catalytic cracking (FCC) unit were devel- USu0 ,u = product stream from unit u0 that can feed to unit u
oped and successfully validated using rigorous process simula-
Parameters
tors. In these models, product yields and properties are expressed Copu = operating cost for unit u
as nonlinear functions of operating variables and feed properties.
Cpru = price of final product from unit u
The operating variables are the reactor temperature and catalyst-
Crms = cost of raw material s
to-oil ratio for the FCC unit and the TBP cut points between
Demandu = demand for final product from unit u
adjacent fractions for CDUs. Several case studies have shown that
FFlou = lower bound for feed flow rate to unit u
the empirical models developed in this work can reproduce
FFup u = upper bound for feed flow rate to unit u
accurately the nonlinear refinery process behavior for given feed lo
PAu,p = lower bound of property p for the feed to unit u
properties and operating conditions. In addition, the empirical up
PAu,p = upper bound of property p for the feed to unit u
models presented in this work differ from those reported by
Supplys = availability of raw material s
Alhajri et al.22 mainly in two significant ways. First, the CDU
Vloo,u = lower bound for operating variable o of unit u
model was tuned using a rigorous process simulator that is Vup
o,u = upper bound for operating variable o of unit u
typically used in refinery operation for process monitoring.
Second, the FCC model proposed in this work considers more Variables
feed properties (density, sulfur content, and Conradson carbon FFu = feed flow rate to unit u
residue) and operating variables (reactor temperature and cata- FPu,s = flow rate of stream s from unit u
lyst-to-oil ratio) than those (characterization factor as feed Fu0 ,s,u = flow rate of stream s from unit u0 to unit u
property and conversion as operating variable) used by Alhajri PAu,p = property p of the total feed to unit u
et al.,22 which allows evaluation of the effect of some key variables PCu,s,p = property p of product stream s from unit u
on product yields and properties. Finally, the empirical models Vo,u = operating variable o of unit u
presented in this part are used in Part 2 of this work [Ind. Eng.
Chem. Res. 2011, DOI: 10.1021/ie200304v] for the production Empirical Model for CDUs
planning of petroleum refineries.
Indices
’ AUTHOR INFORMATION o = operating variable
p = property
Corresponding Author s = product stream from CDU
*E-mail: galoroux@usp.br. s0 = crude oil fed to the CDU
Tsi,si+1 = TBP cut point
Present Addresses
† r = hypothetical unit
Currently at Colombian Petroleum Research Institute (ICP-
u = unit
ECOPETROL), Colombia E-mails: omar@mail.pqi.ep.usp.br,
omarjo.guerra@ecopetrol.com.co. Sets
OCDU = operating variables for CDU
POCDU = relevant properties for product streams from CDU
’ ACKNOWLEDGMENT
POCDU,s = relevant properties for product stream s from CDU
The authors acknowledge the financial support from CNPq SOCDU = product streams from CDU
(Conselho Nacional de Desenvolvimento Científico e Tec- SUs,CDU = units u0 that can process product stream s from CDU
nologico, Brazil). USr,CDU = crude oils fed to CDU

’ NOMENCLATURE Parameters
Bias(s) = bias factor for the yield of product stream s from CDU
Planning Model (vol %)
FFloCDU = lower bound for feed flow rate to CDU
Indices FFupCDU = upper bound for feed flow rate to CDU
o = operating variable up 0
Fr,s 0
,CDU = availability of crude oil s fed to CDU
p = property lo
VTsi,si+1,CDU = lower bound for operating variable Tsi,si+1 of CDU
s = stream up
u = unit VTsi,si+1,CDU = upper bound for operating variable Tsi,si+1 of
u0 = unit CDU

Sets
Ou = operating variables for unit u
p = stream properties
PIu = relevant properties for the feed to unit u
POu,s = relevant properties for product stream s from unit u
SOu = product streams from unit u
su = potential feed streams to unit u
SUs,u = units u0 that can process product stream s from unit u
Uf = units that can process external streams
Variables
FCDU,s,u = flow rate of product stream s from CDU to unit u0
FDs,s = flow rate of product stream s from crude oil s0
FFCDU = feed flow rate to CDU
FPCDU,s = flow rate of stream s from CDU
Fr,s0 ,CDU = feed flow rate of crude oil s0 to CDU
Mid_Vols,s = midvolume transfer ratio of product stream s from
crude oil s0 (vol %)
PCCDU,s,p = property p of product stream s from CDU

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Industrial & Engineering Chemistry Research
PDs0 ,s,p = property p of product stream s from crude oil s0
VDs0 ,Tsi,si+1 = volume percent vaporized of crude oil s0 at TBP cut
point Tsi,si+1 (vol %)
VTsi,si+1,CDU = operating variable (TBP cut point) Tsi,si+1 for CDU
Empirical Model for an FCC Unit
Indices
i = numeric identifier for parameters in product yields and
properties correlations
j = numeric identifier for parameters in conversion correlation
o = operating variable
p = property
s = product stream from FCC unit
s00 = stream feed to the FCC unit
u0 = unit
Sets
OFCC = operating variables for FCC unit
PIFCC = relevant properties for the feed to FCC unit
POFCC,LCO = relevant properties for light cycle oil from FCC unit
POFCC,NAP = relevant properties for naphtha from FCC unit
POFCC,DO = relevant properties for decanted oil from FCC unit
SOFCC = product streams from FCC unit
SUs,FCC = units u0 that can process product stream s from
FCC unit
UFCC = units u0 that can sent product streams as a feed to
FCC unit
USu0 ,FCC = product stream from unit u0 that can feed to FCC unit
Parameters
Ri = parameter i for conversion (X) correlation
βs,j = parameter j for product yields and properties correlations
CatInv = catalyst inventory in the FCC reactor (lb)
k = conversion factor
FFloFCC = lower bound for feed flow rate to FCC unit
FFup FCC = upper bound for feed flow rate to FCC unit
PAloFCC,p = lower bound of property p for the feed to FCC unit
PAup FCC,p = upper bound of property p for the feed to FCC unit
Vloo,FCC = lower bound for operating variable o of FCC unit
Vup
o,FCC = upper bound for operating variable o of FCC unit
Variables
FCCOK = coke yield in the FCC unit (wt %)
FCC3T = C3s yield in the FCC unit (wt %)
FCC4T = C4s yield in the FCC unit (wt %)
FCDO = decanted oil yield in the FCC unit (wt %)
FCLCO = LCO yield in the FCC unit (wt %)
FCNAP = naphtha yield in the FCC unit (wt %)
FFCC,s,u0 = flow rate of product stream s from FCC unit to unit u0
FFFCC = feed flow rate to FCC unit
FPFCC,s = flow rate of product stream s from FCC unit
Fu0 ,s00 ,FCC = feed flow rate of stream s00 from unit u0 to FCC unit
PAFCC,p = property p of the total feed to FCC unit
PAFCC,SPG = specific gravity of total feed to FCC unit
PCFCC,DO,API = API gravity of decanted oil from FCC unit
PCFCC,DO,SUL = amount of sulfur of decanted oil from FCC unit
(wt %)
PCFCC,DO,VII = viscosity index of decanted oil from FCC unit
PCFCC,LCO,API = API gravity of LCO from FCC unit
PCFCC,LCO,CTI = cetane index of LCO from FCC unit
PCFCC,LCO,PPI = pour point index of LCO from FCC unit
PCFCC,LCO,SUL = amount of sulfur of LCO from FCC unit (wt %)
13417
ARTICLE
PCFCC,LCO,VII = viscosity index of LCO from FCC unit
PCFCC,NAP,API = API gravity of naphtha from FCC unit
PCFCC,NAP,MON = motor octane number of naphtha from
FCC unit
PCFCC,NAP,RON = research octane number of naphtha from
FCC unit
PCFCC,NAP,SUL = amount of sulfur of naphtha from FCC unit
(wt %)
PCFCC,s,SPG = specific gravity of product stream s from FCC unit
PCu0 ,s00 ,p = property p of stream s00 from unit u0 to FCC unit
VCO,FCC = catalyst-to-oil ratio in the FCC unit
VTrxn,FCC = reactor temperature in the FCC unit (F)
WHSV = weight hourly space velocity in the FCC unit (h
1)
X = weight conversion in the FCC unit (wt %)
X0 = second-order conversion in the FCC unit
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