Modeling, Simulation, Structural Analysis and Feed Characterization of A Fluid Catalytic Cracking Process - 3
Modeling, Simulation, Structural Analysis and Feed Characterization of A Fluid Catalytic Cracking Process - 3
0 대한민국
Disclaimer
공학박사 학위논문
2018년 2월
서울대학교 대학원
화학생물공학부
김성호
Modeling, simulation, structural analysis
and feed characterization of a fluid
catalytic cracking process
지도교수 이종민
이 논문을 공학박사 학위논문으로 제출함
2018년 1월
서울대학교 대학원
화학생물공학부
김성호
김 성 호의 박사 학위논문을 인준함
2018년 1월
위 원 장 이원보 (인)
위 원 남재욱 (인)
위 원 이창준 (인)
위 원 이웅 (인)
Table of Contents
Table of Contents v
1 Introduction 1
1.1 Fluid catalytic cracking process . . . . . . . . . . . . . . . . . . . . . 1
1.2 Structural Analysis of Systems . . . . . . . . . . . . . . . . . . . . . . 3
1.3 FCC feed characterization with plant data . . . . . . . . . . . . . . . 4
1.4 The scope of thesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
v
3.3.1 Structuring the modeling relationships of a system . . . . . . . 44
3.3.2 Attempt to solve the entire modeling relationships simultaneously 45
3.3.3 Finding an output-set assignment . . . . . . . . . . . . . . . . 45
3.3.4 Completing the assignment - Finding optimal place for addi-
tional measurements . . . . . . . . . . . . . . . . . . . . . . . 46
3.4 Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
3.5 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
5 Concluding remarks 75
Appendix A Nomenclature 77
Bibliography 83
vi
List of Figures
vii
3.3 Occurrence matrix of the sample system . . . . . . . . . . . . . . . . 52
3.4 An example of assigning an output to the un-assigned equation . . . 53
3.5 Occurrence matrix of the FCC process . . . . . . . . . . . . . . . . . 53
3.6 Occurrence matrix of the FCC process with 5x5 complete set . . . . . 54
3.7 Fully complete occurrence matrix of the FCC process . . . . . . . . . 54
viii
Abstract
Modeling, simulation and state
observation based on structural
analysis of a fluid catalytic
cracking process
Sungho Kim
School of Chemical and Biological Engineering
The Graduate School
Seoul National University
ix
x
complex petroleum properties were found from literature and interconnected to find
the distribution function. The correlation model was validated by comparing the
reaction results from model with another results from the chemical process simulator.
The comparison showed slightly disagreed expectation result for LPG and LCO. It
is assumed that uncertainties about catalyst in the reactor and process model in the
simulator have caused this difference. Considering that point, we conclude that the
correlation model exhibits an acceptable agreement with the results of Aspen HYSYS
V8.4. The proposed approach provided insights into the FCC process and was found
to be a suitable technique for process design, operation and even more applications
such as optimization.
Keyword: Fluid catalytic cracking, discrete lumped group, process modeling,
structural observability analysis, Feed characterization
Student number: 2013-30984
Chapter 1
Introduction
Fluid catalytic cracking (FCC) is one of the most important refinery processes. It is
used for cracking high molecular weight hydrocarbon feedstocks to smaller molecules
which boil at relatively lower temperatures. In the refinery plant from this study,
heavy vacuum gas oil (HVGO) feed is converted to off-gas, liquefied petroleum gas
(LPG), whole crack naphtha (WCN), light cycle oil(LCO) and clarified oil (CLO).
LPG and WCN are usually the primary products. About 45% of naphtha in the world
is produced by FCC [1]. The existing FCC plant in the refinery consists of a reaction
unit which is followed by the fractionation unit that separates the reactor effluent into
the final products. The reaction unit is composed of the riser and the regenerator.
A simplified process flow diagram of FCC in our study is shown in Fig 1. HVGO is
fed to the bottom of the riser after it is dispersed through a nozzle system. After
dispersion, the feed vaporizes upon contact with the hot catalyst coming from the re-
generator. Dispersion of the feed provides more heat transfer which in turn increases
the efficiency of feed vaporization. Some amount of lift steam is also added to provide
1
2
drag force to catalyst particles. Steam and the vaporized feed lift the catalyst parti-
cles upward through the riser. In the riser, vaporized hydrocarbons crack to smaller
molecules on the catalyst surface. In addition to the cracking reactions, some amount
of coke is deposited on the catalyst surface which reduces the catalysts activity. At
the riser exit, deactivated catalyst particles are separated and transferred back to the
regenerator ‘whereas the vaporized hydrocarbons are sent to the fractionation unit
where they are separated into the end products. In the regenerator, the coke on the
catalyst in burned with air and fresh hot catalyst is transferred back to the riser inlet.
In the riser, hydrocarbon compounds are converted to smaller molecules which boil
such complex mixtures, Quann and Jaffe [2] presented a structure oriented lumping
approach which takes the molecular structure into account. However, industrial ap-
plication of SOL is difficult since the analysis of petroleum fractions at the molecular
level is still limited. Complexity of detailed models has motivated the development of
simpler lumped models. In the discrete lumping approach [3], the mixture is assumed
property such as average Normal Boiling Point (NBP). In the discrete lumping liter-
ature, most studies prefer to use a small number of PCs to facilitate modeling and to
reduce the number of unknown kinetic constants. In early studies [4][5] the reaction
medium is represented by 3 lumps (feed, gasoline and light gases, coke). Limited
some studies, coke and light gases are considered as separate lumps [6][7][8]. Later
studies also include diesel as another lump [9][10][11]. Vargas et al. used a 6-lump
3
model and estimated parameters from refinery data [12]. In some detailed studies
10-lump models are used [13][14][15]. Gupta [3] developed a new kinetic model con-
two other pseudo-components in one single cracking reaction step. They estimate
the kinetic constants using a probability based empirical approach that considers all
feasible reactions.
such as process modeling, control and state estimation. However, measuring all state
state variables based on a finite set of measurements. The notion of system observ-
state of the system. For linear time invariant systems, if the rank of the observability
matrix is equal to the dimension of the state space model, then the system is ob-
servable [16]. For non-linear dynamic systems diverse local observability definitions
can be considered, for example using Lie derivatives [17]. In addition to analyzing
cally determine minimum set of measurements which makes the system observable,
especially for large-scale complex systems. By analyzing the model structure we can
infer the minimum number of measurements and the possible choices to choose.
dition for system observability, and often it may also be sufficient for many complex
chemical systems [17][18]. Structural observability analysis can be done using graph-
disturbances and parameters can be estimated by augmenting the system with them
Structural observability analysis via graph theory offers a visual means to pinpoint
One of the most important tasks in petroleum refining and related chemical pro-
cesses in the reliable values of properties for hydrocarbons and their mixtures of the
oil.[20][21] They are important from the design to operation, optimization and fault
diagnosis. Ideally, these FCC processing would relate feed composition to product
5
yield and qualities for any operating conditions. However, during operation of an
industrial petrochemical plant, crude oil from several reservoir is combined before
process and recycled flows are mixed, making plant operators difficult to know its
properties. Besides, real-time measurement of the process state for the plant is un-
realistic in both cost and time[22]. The industry developed method to correlate feed
There are three major trends in the area of FCC feed characterization. They
models without adding additional knowledge about the effect of each property on the
process [24][25]; 2. lumping models in which different hydrocarbons are lumped into
of the feed which adopt a mechanistic description of catalytic cracking based on the
Parametric models are easily adopted in industrial plant operations as they in-
clude process properties which are able to be easily measured. However, this method
On the other hand, lumping models can provide more insight about how feed
effects the cracking reactions. However, the model require various data which is not
Single-event kinetic modeling is more advanced and make kinetic parameters that
are independent of the feed property. The analysis of the feed is made by liquid
Another approach that using a boiling point test based on distillation analy-
recently.[39] With the boiling point distribution known, the prediction of the com-
plete distributions for various properties of a C7+ fraction is possible using the bulk
In this study we combine the correlations available in the literature for petroleum
description of FCC process feeds from measured process data and find a fraction
This thesis present various research including modeling, simulation, systematic struc-
tural analysis and feed characterization of FCC plant with plant data.
results and dynamic response of the plant to change of process variables are demon-
strated.
we divide the system into partitions based on their functionality and define set of
Chpater 4 represent feed characterization of the FCC plant with the measured
process data. It uses experimental data from literature and thermodynamic correla-
tions to characterize unknown process feed. The expected results are compared with
Finally, in chapter 5, the conclusion and contribution of this research are discussed.
Chapter 2
2.1 Introduction
This chapter presents a dynamic process model for a FCC plant. This model includes
the riser reactor and the catalyst regenerator. These units are modeled individually
In this study, we suggested that when the j-th pseudo-component cracks it can
form all the lighter pseudo-components with different yields. Specifically, a yield
function p(i,j) that specifies the amount of the i-th pseudo-component formed from
cracking of the j-th PC is suggested. The yield function parameters are set from
measured data and it is assumed that the results of yield function approximate the
real distribution. To predict the amounts of the WCN, LCO, CLO, LPG and off-
gas in the feed and the final products, an empirical model is developed by making
use of temperature cut-points (TCPs). This eliminates the need for any rigorous
fractionation unit model to calculate the product distribution. In this way effect of
the riser and the regenerator operating conditions on the product can be predicted.
7
8
The catalyst regenerator is modeled to calculate the heat supplied to the riser
reactor from the combustion reaction. Possible combustion reaction pathways are
suggested. Mass and energy balance equations are built for each elementary reac-
tion. Parameters of the model are estimated by the weighted least-square estimation
method. Steady-state model results and dynamic responses of the model to a step
The riser unit is divided into the feed inlet zone and the reaction zones. Stripper zone
is not considered and spent catalyst is assumed to be completely separated from the
product rapidly.
At the bottom of the reactor the residue feed is mixed with steam and hot catalyst.
The feed is spread in the inlet zone and vaporized by heat from hot catalyst and
steam. Major input and output streams of the feed inlet zone are shown in Fig 2.1.
a small fraction of the riser.[29][30] Therefore, the mixing zone is considered to have
uniform temperature and hydrodynamic features. Also, cracking reaction does not
Under this assumptions, a steady-state energy balance for the feed inlet zone is:
9
Z Tmixzone N Z
X TB,i N
X
M˙cat × Cp,cat dT = Ṁi × Cp,liquid,i dT + ∆Hvap,i
Tregen i=1 THV GO i=1
N Z
(1)
X Tmixzone Z Tmixzone
+ Ṁi × Cp,gas,i dT + Ṁsteam × Cp,steam dT
i=1 TB,i Tsteam
In Equation 1, the left hand side is heat from regenerated catalyst particles. On
the right hand side, the first term is the energy that needed to increase the temper-
ature of the mixture to their boiling points. The second is heat of vaporization of
hydrocarbons. And the third is heating of the mixtures to the zone temperature.
The last term is the energy from the steam. Heat capacity and heat of vaporization
are obtained from literature[20] and Aspen HYSYS, a commercial chemical process
simulator. In this chapter, variation of mixture composition under same API gravity
is not considered and identical physical properties were assumed for identical API
The velocity of the gas leaving the feed inlet zone is calculated from the ideal gas
ṀHV GO × R × Tmixzone
vg = (2)
M W × P × Ariser
In the reaction zone, vaporized hydrocarbon feeds and catalyst particles flow along
the reaction zone where the cracking reactions occur. At the riser exit, deactivated
catalyst particles are separated from the mixture and sent to the catalyst regenerator.
Vapor hydrocarbons are sent to the fractionation unit where they are separated into
10
phase is very small and both phases are assumed to be perfectly mixed. Therefore
Hydrodynamics
The pressure drop in the riser reactor is governed by acceleration of particles and
∂P ∂ 2
= −((1 − ε)ρcat + ερg )g − ((1 − ε)ρcat vcat + ερg vg2 (3)
∂z ∂z
M˙cat
(1 − ε) = (4)
vcat ρcat Ariser
CD is the drag coefficient, Dcat is the average diameter of the catalyst particles,
ρcat and ρg are density of the catalyst and the gas phase. Assuming the same velocity
for gas and catalyst reduces the computational load and would not change the results
significantly.
Mass balance
The cracking reaction rate depends on many factors including feed and catalyst prop-
erties. Bollas defined a feed index to relate paraffinic, olefinic and aromatic content
of the feed to rate constants based on empirical correlations[39]. Ginzel studied the
limited knowledge of chemical composition for complex feed can provide only the
factor Ai and the activation energy Ei are defined as a function of normal boiling
12
point(NBP)[41]. This method can use available boiling point data which is most
Ai = β × N BP µi (6)
Equation (6) is in the form of a power law since materials with higher boiling point
mental data from literatures that activation energy tends to be higher for materials
In the kinetic model from earlier studies each pseudo-component is cracked into
component cracks, it makes all the lighter pseudo-components with different reaction
yield. The yield function p(i, j) represents the amount of the i th pseudo-component
Building a yield function of an operating plant is very difficult since the reactions
are highly dependent on feed content, operating conditions and many other unknown
13
process factors[47]. Besides, refinery data is limited since direct measurement cannot
be performed at the reactor riser which makes the analysis of the intermediate prod-
ucts. Hernandes used a beta distribution function to avoid similar problems[48]. Also,
there are studies which demonstrated that a temperature and composition profile ex-
ists along the riser reactor[31][48][49][50]. The product distributions of paraffinic and
olefinic petroleum feedstocks are presented in Nace’s work[43]. The product distribu-
tion of a specific petroleum cut is also presented in other studies[51]. Thus, starting
from the riser inlet, the yields of cracking reactions to intermediate products should
reaction.
Based on those studies, a yield function was constructed to calculate the products
s
−λ ×N BP
1 λP × N BP j 2(µp ×NPBP j )2 NjBP i (N BP i −(µp ×N BP )2 )
p(i, j) = T e (9)
Pj 2π × N BP 3i
where PjT is the normalization factor of yield functions so that ji=1 p(i, j) = 1:
P
j−1
s
−λ ×N BP
X λP × N BP j 2(µp ×NPBP j )2 NjBP i (N BP i −(µp ×N BP )2 )
PjT = e (10)
i
2π × N BP 3i
p(i, j) for each pseudo-components that have different NBPs are presented in figure.
In the riser reactor, along with cracking reactions, some portion of hydrocarbons
is deposited on the surface of solid catalyst due to coking. Coke deposition on the
catalyst surface causes significant deactivation of catalyst. The amount of coke gener-
ated should be predicted accurately to calculate deactivation of the catalyst and the
reaction rate in both riser reactor and regenerator. In lumped-kinetics method, coke
14
ing conditions, catalyst type and reactor design[52]. In several studies most of the
coke formation occurs early in the riser[53][54]. It is found that catalyst to oil ratio
model. For every cracking reaction, ϕ fraction of the reactant is converted to coke.
laboratory test in which distilled volume fractions of the sample are described as a
function of temperature. [20] Chemical process software such as Aspen HYSYS can
be used as an alternative to plot the curve. In our case, the boiling point of HVGO,
WCN, LCO and CNO are defined as operating temperature of the fractionation unit
which separates the cracked product. It is not possible to sample and perform a
similar analysis on the product output before the fractionation due to safety and
other technical difficulties. Instead, we modeled the fractionation unit with same
operation condition in HYSYS which shows similar separation performance and found
∂(Ṁi ) Ṁi
= −ki × × (1 − ε) × ρcat × Φ
∂z vg
N (11)
X Ṁn
+ p(i, n) × (1 − ϕ) × kn × × (1 − ε) × ρcat × Φ
n>i
vg
where Ṁi is the mass flow rate of i th component; ki is the cracking rate constant
15
(m3 /kg cat h) of i th component and Φ is the catalyst activity coefficient. The first
term in the right hand side means cracking of i th component into smaller components;
the second is the formation of that component from cracking of larger molecules. The
from cracking of the nth component. For each reaction, ϕ fraction of the reacting
The overall mass balance between the inlet and outlet of the riser reactor gives:
N
X
Ṁi + Ċ = ṀHV GO + Ċ0 (12)
i=1
where Ċ0 is the coke flowrate (kg/h) in the catalyst from the regenerator to the
feed inlet zone of reactor. The coke mass flowrate leaving the reactor is
N
X
Ċ = ṀHV GO − Ṁi + Ċ0 (13)
i=1
Catalyst activity depends on the coke fraction on the catalyst surface since coke is
the physical reason for deactivation. An exponential type deactivation model is used
Φ = e−α(Ċ/Ṁcat ) (14)
Ċ
where Ṁcat
is the coke fraction on the catalyst.
Energy balance
where Cp.avg is the average heat capacity of all pseudo-components in the reactor
and δHi is the heat of cracking of i th pseudo-component. The heat of cracking of the
i
X
∆Hi = Hc,coke × ϕ + p(i, j) × (1 − ϕ) × Hc,j − Hc,i (16)
j=1
where Hc.coke is the heat of combustion of coke; Hc,i is the heat of cracking of ith
the plant, we use a power-law type equation to relate heat of combustion to NBP.
As mentioned in above, identical physical properties were assumed for identical API
Hc,i = ac × N BP bi c (17)
Hc.coke is considered to be a function of API gravity of the feed, which is the only
When the temperature cut-point[33] used in the process are known, they can be
used to calculate the amounts of the final products and can be compared to the
amount of product flows in the fractionator process after the reactor. If the model
and the measured data fits, the final products amounts are predicted exactly by the
Let P(NBP) be a polynomial that relates the NBP to the corresponding cumulative
p(N BP h ) = Ṁ (19)
p(N BP l ) = 0 (20)
where Ṁ is the total mass flowrate of the pseudo-components at the riser and
NBPCLO and NBPof f gas are the highest and the lowest boiling point temperatures
4
X i
X
min (P (θi ) − Mi,p )2 (21)
θ
i=1 j=1
P(θi ) is the total mass which boils up to the temperature θi ; Mi,p is the amount of
i )th product from the plant. For instance, θof f gas−LP G is the cut-point temperature
2.3 Regenerator
In the regenerator coke on catalyst surface is burnt to increase the catalyst activity.
The air is fed to the bottom of the regenerator and reacts with the coke and other pol-
lutants on the catalyst. Since combustion reactions are very exothermic, regenerated
catalyst is transferred to the riser reactor, mixed with the feed at a high temperature
and provides heat for the endothermic reactions in the riser reactor.
We assumed that the regenerator has two physical phases: solid dense bed and
The dense bed is the lower part of the regenerator where a higher concentration of
catalyst particles exists. As air flows through the dense bed, coke and other pollutant
react with oxygen in the air. Although there may be a little catalyst concentration
and temperature gradient in the dense bed[35][34], flowing air flow mixes catalyst bed
19
Table 2.1: Catalyst regeneration reactions and rate expression in the regenerator unit
and the gradient become negligible. Therefore, to make our model simpler, we have
modeled the dense bed as a single-phase, well-mixed reactor. Primary reactions, rate
Mcat (kg) is the total catalyst mass holdup in the dense bed. We assume that
the catalyst holdup is kept constant by manipulating the valves on the regenerated
Regen
catalyst circulation. VDensebed is the volume of the dense bed; YCoke is the coke mass
fraction of the catalyst in the dense phase; M Wcoke is the molecular weight of coke.
PCO and PO (bar) are the partial pressures of CO and O2 . CO combustion reaction
occurs through both catalytic and homogeneous paths. The reaction mechanism is not
fully defined due to complex catalyst influence, uncertainty of reaction medium and
values for the reaction orders and kinetic parameters have been proposed[14][34][36].
20
Among the reactions, burning of H2 does not influence the kinetics of the regener-
ator by its concentration because the reaction is so fast that it is assumed to occur
instantenously[37] However, the thermal effects from the reaction are significant be-
cause of its high combustion energy[38]. Expressions for the rate constants are given
as:
ture. [14]
Unlike the riser reactor, the dynamics of the dense bed phase are significant due
to its large catalyst mass holdup. The approximate residence time of the catalyst in
the dense bed is about 5–10 min, which is much longer than 5–10 seconds in the riser
The gaseous species have a residence time about 5 seconds in the dense bed. There-
fore, we have assumed pseudo-steady state for the gaseous phase in the regenerator.
-ṀCO,DenseT oDilute is the molar flowrate of CO that leaves the dense phase. rCO is
calculated from:
regen a1
Mcat Ycoke
rCO = kC,CO ( × ) × (PO2 )a2
VDensebed M W coke
(4)
Mcat a5 a6 a7 a8
−kCO,CO2,c × × (PCO ) × (PO2 ) − kCO,CO2,h × (PCO ) × (PO2 )
VDensebed
From material balance for CO2 ,
where rCO2 is
regen a3
Mcat Ycoke
rCO = kC,CO2 ( × ) × (PO2 )a4
VDensebed M W coke
(6)
Mcat a5 a6 a7 a8
−kCO,CO2 ,c × × (PCO ) × (PO2 ) − kCO,CO2 ,h × (PCO ) × (PO2 )
VDensebed
H2 generated during the reaction is converted to H2 O instantly and leaves the
riser YHriser
ṀH2 O,DensetoDilute = Ṁcat Ycoke 2
(7)
M W H2
where YHcoke
2
is the H2 fraction in coke. Similarly, material balance for O2 is given
by
22
riser YHcoke
ṀO2 ,in − ṀH2 O,DensetoDilute − Ṁcat Ycoke 2
+ rO2 VDensebed = 0 (8)
2M W H2
regen a1 regen a3
Ycoke
Mcat a2 Mcat Ycoke
rO2 = −kC,CO × ( ) × (PO2 ) − kC,CO2 × ( ) × (PO2 )a4
VDensebed M W coke VDensebed M W coke
Mcat
−kC,CO2 ,c × × (PCO )a5 × (PO2 )a6 − kC,CO2 ,h × (PCO )a7 × (PO2 )a8
VDensebed
(9)
MO2 ,in is the molar flow rate of O2 into the dense bed from the fresh air and
ṀO2 ,DenseT oT ilute is the molar flow rate of O2 that leaves the dense bed phase.
d
((Mcat + MO2 + MN2 + MCO + MCO2 + MH2 O ) × Cp,avg × Tregen ) =
dt
(ṀO2 ,in × Cp,O2 × Tair + ṀN2 ,in × Cp,N2 × Tair + Ṁcat × Cp,cat × Triser )
" #
−(ṀO2 ,DensetoDilute × Cp,O2 × Tregen + ṀN2 ,DensetoDilute × Cp,N2 × Tregen
+Ṁcat × Cp,cat × Tregen )
" #
−(ṀCO,DensetoDilute × Cp,CO × Tregen + ṀCO2 ,DensetoDilute × Cp,CO2 × Tregen
+ṀH2 O × Cp,H2 O × Tregen )
riser YHcoke
2
+QR,Densebed VDensebed + Ṁcat Ycoke ∆H H2 ,H2 O
M W H2
(10)
where Tregen is the dense phase temperature, Tair is the air temperature, and
QR,Densebed is the heat released per unit volume from combustion reactions of catalyst
regen a1
Mcat Ycoke
QR,Densebed = kC,CO ( ) (PO2 )a2 ∆H C,CO +
VDensebed M W coke
regen a3
Mcat Ycoke
kC,CO2 ( ) (PO2 )a4 ∆H C,CO2 +
VDensebed M W coke (11)
Mcat
kCO,CO2 ,c (PCO )a5 (PO2 )a6 ∆H CO,CO2 +
VDensebed
Mcat
kCO,CO2 ,h (PCO )a7 (PO2 )a8 ∆H CO,CO2
VDensebed
Contrary to the dense phase, the amount of catalyst particles in the dilute phase is
negligible. Therefore, solid coke nor catalyst does not exist in the dilute phase. The
dilute phase is assumed to be pseudo-steady state since the velocity of the gaseous
phase is very high. The dilute phase is modeled as an one-dimensional adiabatic plug
d
(ṀCO ) = −kCO,CO2 ,h × (PCO )a7 × (PO2 )a8 Aregen (12)
dz
d
(ṀCO2 ) = −kCO,CO2 ,h × (PCO )a7 × (PO2 )a8 Aregen (13)
dz
d 1
(ṀO2 ) = kCO,CO2 ,h × (PCO )a7 × (PO2 )a8 Aregen (14)
dz 2
ṀO2 × Cp,O2 × T + ṀN2 × Cp,N2 × T +
d
− ṀCO × Cp,CO × T + ṀCO × Cp,CO × T +
2 2
dz
(15)
ṀH2 O × Cp,H2 O × T
kCO.CO2 ,h × (PCO )a7 × (PO2 )a8 × ∆H CO.CO2 × Aregen = 0
The parameters of the model were estimated by the weighted least square estimation
method. The weighted sum of squared errors (WSSE) between measured data and
where n is the number of data points, m is the number of measured variables (seven
in this study), yij is the measured value of variable j at time i, and ŷij is the calcu-
lated value of variable j at time i from the model. For the riser reactor, measured
plant variable include the product amount, temperature and pressure of product and
catalyst. Even though we cannot measure the composition of the reactor product
flow, we assume that product flow rate from the main fractionator after the reactor is
same as that of the reactor product flow. For the regenerator, measured variables are
the temperature of dense and dilute phase. The weighting factor, Wij , was defined
to assign more weights to measured variables with less variances and to balance the
1
Wij = (2)
σij λj
25
where σij is the standard deviation of the measurement variables and λj is a scaling
where yijr is the measured variable used as a reference variable and ȳij is the mean
value of the measurement variables. The standard deviation σij is calculated after
The optimization problem to minimize WSSE was solved using the statistics tool
in Matlab.
The constructed model of the FCC was tested for various steady-state operating
condition and feed. The main results which we are interested of the riser reactor are
the flow rate of products and other process variables; the pressure and temperature
at the riser exit. From the regenerator model we can gain expected temperature
of dilute gas phase and dense solid phase. The result was compared to measured
data from an operating FCC plant. The model simulation results and corresponding
plant data are shown in Fig 2.2, Fig 2.3 and Fig 2.4. Although there are little
discrepancies between the simulation results and measured data, it was observed that
the simulation data points have similar trends. Values of R2 of the result are 0.9313,
26
0.8808, 0.9639, 0.8605, 0.8806 for each pseudo-component group and 0.9808, 0.9539,
0.9734, 0.9896, for riser temperature, riser pressure, dilute phase temperature and
Table 2.2 shows the results of parameter estimation of the model. Parameters
which are not listed in table 2.2 are considered to be constant and taken from the
literature.
Due to lack of feed property data in construction of the model, NBP and tem-
perature cut-points are considered as constant values. To solve this problem, further
study about estimating feed property with available process data is required.
Dynamic analysis of the model helps understanding the interactions between the
operation of the riser reactor and the catalyst regenerator. Fig 2.5, Fig 2.6 and Fig
2.7 show dynamic response of the model to an 10% increase of the air flow rate. The
amount of air flow determines the combustion reaction in the regenerator. When
more air is supplied, more combustion reactions occur, and more heat is generated.
Consequently, the temperature of dense and dilute phase in the regenerator increases.
the riser reactor. This high temperature causes more cracking reaction occur in the
riser reactor. The amount of heavier products (CLO and LCO) decreased while the
Next we studied the effect of increased catalyst circulation rate by 10%. When
the catalyst circulation rate is increased, more energy is transferred to the riser re-
actor and the riser temperature is suddenly increased. As the cracking reactions are
27
(a) Off-gas
(b) LPG
(a) WCN
(b) LCO
(a) CLO
endothermic, the cracking reactions occur more often in this condition. However, as
the riser and the regenerator temperature began to decrease, the flow rate of heavier
components became favored. The amounts of the light products increased slightly
because of the increased catalyst flow rate in the riser reactor. The results are shown
All the simulated dynamic responses showed similar trend with plant data.
2.7 Conclusion
Using the discrete lumped group method, The FCC process systems are investigated
to develop a process model for an fluid catalytic cracker. This model predicts the
product yield and other process states under steady-state and dynamic conditions.
32
(a) Off-gas
(b) LPG
Figure 2.7: Dynamic response of the model to a 10% increase of the air flow rate(1)
33
(a) WCN
(b) LCO
Figure 2.8: Dynamic response of the model to a 10% increase of the air flow rate(2)
34
(a) CLO
Figure 2.9: Dynamic response of the model to a 10% increase of the air flow rate(3)
35
Figure 2.10: Dynamic response of the model to a 10% increase of the air flow rate(4)
36
Off-gas (kg/h)
4600
4550
4500
Response
4450
4400
4350
4300
0 5 10 15 20 25 30
Time (min)
(a) Off-gas
1.21
1.2
Response
1.19
1.18
1.17
1.16
1.15
0 5 10 15 20 25 30
Time (min)
(b) LPG
Figure 2.11: Dynamic response of the model to a 10% increase of the catalyst circu-
lation flow rate(1)
37
2.88
2.86
Response
2.84
2.82
2.8
2.78
0 5 10 15 20 25 30
Time (min)
(a) WCN
LCO (kg/h)
4540
4520
4500
4480
4460
Response
4440
4420
4400
4380
4360
4340
0 5 10 15 20 25 30
Time (min)
(b) LCO
Figure 2.12: Dynamic response of the model to a 10% increase of the catalyst circu-
lation flow rate(2)
38
CLO (kg/h)
9750
9700
9650
9600
Response
9550
9500
9450
9400
9350
9300
0 5 10 15 20 25 30
Time (min)
(a) CLO
545
540
Response
535
530
525
520
0 5 10 15 20 25 30
Time (min)
Figure 2.13: Dynamic response of the model to a 10% increase of the catalyst circu-
lation flow rate(3)
39
705
700
695
Response
690
685
680
675
670
0 5 10 15 20 25 30
Time (min)
730
725
720
Response
715
710
705
700
695
690
0 5 10 15 20 25 30
Time (min)
Figure 2.14: Dynamic response of the model to a 10% increase of the catalyst circu-
lation flow rate(4)
40
Empirical correlations that describe the reaction kinetics with model parameters are
built. A yield function for the kinetic model of the riser is constructed and applied to
the model. Also, an approach to estimate the fraction of products using temperature
cut-point is suggested. Using this model, steady-state simulation results and dynamic
3.1 Introduction
based on knowing about current state of the plant. The process disturbance or faults
have a serious impact on process operation, product quality, safety, productivity and
a given set of measurement is adequate to estimate the state of the system. For
linear time-invariant systems, if the rank of the observability matrix is equal to the
dimension of the system, then the system is observable. [57] For nonlinear systems
find the minimum set of measurements which makes the system observable. By
analyzing the model, we can find the minimum set of measurements and the possible
41
42
choices. In this study, we studied our FCC model with graph theory and modeling
relationships to analyze structural observability of the process and find out which
part of the plant is unobservable. Based on the result, we propose optimal place for
3.2 Graph-theory
of vertices, a set E(G) which is a set of edges, disjoint from V(G) and an incidence
connects two nodes vi and vj (vi , vj ∈ V (G)) is denoted by (vi , vj ) and vi and vj are
consisting of an non-empty set V(D) of vertices and a set E(D), which is disjoint from
V(D). Let an edge ei =( vi , vj ) ∈ E, then vi is the initial vertex and vj is the final-
vertex, gives (vi , vj ) ≡ vi → vj . In directed graphs, edges are marked with directed
lines while in undirected graphs it is not. On the other hand, for undirected graphs,
node and a final node. Number of edges in a path is called the length of the path. A
graph is simple if any path in the graph have no loops nor node appearing more than
once. If a path has identical initial and final nodes, it is called a close path.
A cycle is a closed path with no node appearing more than once except the initial
43
and the final nodes. A set of cycles such that no two cycles have any common nodes
are a cycle family. In a cycle family if paths from vi to vj and from vj to vi exits then
rected graph
Our FCC model consists of the riser reactor and the catalyst regenerator. Each
unit can be divided further into three nodes based on their functions. The riser
reactor consists of the feed inlet zone, reaction zone and stripping zone. Although
the stripping zone was not modeled in our study since the catalyst is separated from
the product rapidly and completely, we need process state of the location to find
out accuracy of our model and the results. Meanwhile, the catalyst regenerator is
divided into the dilute gas phase where the spent catalyst are fed and CO is burnt,
surface between dilute/dense phase bed where mass and energy are transferred, and
the dense solid phase bed where the coke on catalyst surface is burnt and the catalyst
returns to the riser reactor. For each functional node, several sensors are installed in
the plant. However, not all kinds of sensors are available for every location, making
A directed graph consisting these nodes is generated and shown in Figure 3.2.
44
ated with input-output relationships, we can analyze the system to find whether the
nodes, connections between the nodes, inputs and outputs of the system and identify
what system variable we can measure. Fig 3.2 is an example of a system with input-
output relationships.
f1 (x1 , x3 ) = 0
f2 (x1 , x2 , x3 ) = 0 (1)
f3 (x2 ) = 0
For these relationships, output-set assignment can be found. From the third
xi can be used as a process state when building occurrence matrix. (x1 ; f1 ) and (x3 ;
These assignments are translated into an occurrence matrix. Functions are placed
at row and state variables are in column. Assignments are marked in the correspond-
multaneously
If all of the modeling relationships or the occurrence matrix could be solved simulta-
Before starting the sequential analysis of the system, we attempted to solve the mod-
the modeling relationships could not be found. Besides, the maximum structural rank
singular matrix and the output-set from the matrix is incomplete. In this case, the
Let us begin searching at a position in the occurrence matrix where the equation
can be solved spontaneously. Check every function in which the solved variable is
included. Than find another function which become solvable with previous result.
Repeat this searching until solve every function. If a solvable function cannot be
found during the process, stop searching and gather complete set into diagonal form.
46
Functions and system variables which found assignment are complete output set,
This results gives answer to the question whether each node of graph model is
observable. If any node, location or process state variable of the system is found to
for a set of modeling relationships, then there exist structural problems with the set
specified or under-specified.
additional measurements
To complete the assignment, we can assume that we know additional variable which
was unassigned and continue the algorithm. In the example, we assume that we
of the current output variable(x3 ). Then we continued with the algorithm until an
3.4 Results
The procedure described above is demonstrated on the FCC plant in this study.
f1 (x1 , x2 , x8 ) = 0
f2 (x2 , x3 ) = 0 (1)
f3 (x3 , x4 , x5 ) = 0
f4 (x5 , x6 , x9 , x11 ) = 0
f6 (x7 , x8 , x9 ) = 0
f7 (x1 , x4 , x9 , x10 ) = 0
f8 (x1 ) = 0 (3)
f9 (x4 ) = 0
For these relationships, output-set assignment was found by constructing the oc-
The assignment could start from both f8 -x1 and f9 -x4 as they have only one
variable related. f8 -x1 was selected for the sake of simplicity. Then the algorithm
was repeated for x2 , x3 and x5 . However, it is found out that for FCC plant system
in this study not every function was solvable with given modeling relationship and
measurements. Assigned nodes and variables are gathered to create the diagonal form
This result shows that five system variables and three nodes are identified to
be observable and controllable. The result is shown in Figure 3.6. Comparing the
48
result to the directed graph it is found that whole nodes and edges in the reactor are
completely observable. However, in the catalyst regenerator, most of edges were not
system variables which was unassigned, x6 -x10 , are assumed to be measured addi-
unmeasured variable. It is found that gas effluent and regenerated catalyst which is
cycled to the feed inlet zone in the reactor are the most optimal location for addi-
tional measurement. Completing output assignment of the entire system with single
3.5 Conclusion
In this chapter, structural analysis of the fluid catalytic cracking process is performed
to find observability of the FCC system. A directed graph was drawn to construct
modeling relationships of the system. The reactor and regenerator unit in this sys-
tem are divided into six nodes based on their functions. The modeling relationships
were built based on nodes and edges of the directed graph. Output-set assignment
relationships. The results of this chapter show that only a part of the system is fully
observable and the states in the regenerator is not observable without measurements.
However, it is also suggested that with additional state measurements, these unob-
servable states can be observed. Optimal locations for additional measurement are
49
Figure 3.6: Occurrence matrix of the FCC process with 5x5 complete set
4.1 Introduction
In this study we combine the correlations available in the literature for petroleum
of FCC process feeds from measured process data and find a fraction distribution of
There are three major trends in the area of FCC feed characterization. They
models without adding additional knowledge about the effect of each property on the
process [24][25]; 2. lumping models in which different hydrocarbons are lumped into
of the feed which adopt a mechanistic description of catalytic cracking based on the
Parametric models are easily adopted in industrial plant operations as they in-
clude process properties which are able to be easily measured. However, this method
55
56
On the other hand, lumping models can provide more insight about how feed
effects the cracking reactions. However, the model require various data which is not
Single-event kinetic modeling is more advanced and make kinetic parameters that
are independent of the feed property. The analysis of the feed is made by liquid
Another approach that using a true boiling point (TBP) test based on distillation
tion recently.[39] With the true boiling point distribution known, the prediction of
the complete distributions for various properties of a C7+ fraction is possible using
fractions
Pure compounds have a single value for the boiling point. However, for mixtures like
crude oil and residue oil in FCC process, the temperature at which vaporization occurs
varies from the boiling point of the most volatile component to the boiling point of
boiling points of the components in the mixture. For a petroleum mixture of unknown
57
vaporized mixture.
The temperature range in this curve is boiling point range. The the lowest boiling
point is initial boiling point and the highest boiling point of the mixture is the final
boiling point. We can assume that compounds in the mixture have boiling point
between them and roughly estimate the number of carbon atoms of hydrocarbons
compounds. The boiling point curve provides a look into the composition of feedstocks
58
and products about petroleum processes. There are several method of measuring and
ASTM–D86 is one of the simplest and oldest method of measuring boiling points of
kerosenes, gas oils and other similar petroleum products. However, this test is not a
matography. This method is much precise and reproducible. Also, this method is
in the mixture. Actual true boiling point(TBP) is the idealized temperature cuts for
of a petroleum mixture using a distillation column with high reflux ratios. However,
terms of both cost and time. In our study, normal boiling point(NBP) and boiling
point curve is used as index for temperature of hydrocarbons in the feed and the
product.
There were several attempt to develop empirical methods for converting ASTM distil-
lations to TPB from the 20th century. [59][60][61][62] These correlations were based
on experimental data from literature. In the 1980s Riazi-Daubert method were de-
veloped analytical method for conversion of distillation curves based on the general
59
correlations for hydrocarbon properties. [63] Another conversion methods were de-
In this study, four ASTM–D86 curve data from an industrial FCC plant is con-
Riazi-Daubert methods are based on the generalized correlation for property estima-
tion of hydrocarbons.
ASTM–D86 to TBP
If distillation data in form of ASTM-D86 is available, we can convert this data into
TBP.
distilled and T (desired) is the desired distillation data for the same vol% distilled.
SG is the specific gravity of fraction at 15.5◦ C. For this particular type of conversion
regarding TBP curve, c becomes zero for all vol%[20] and the equation reduces to
where both TBP and ASTM–D86 temperatures are in kelvin. Constants a and b
at various points along the distillation curve are given in Table 4.1
60
data to TBP. [64]In these methods, first conversion should be made at 50% point and
then the difference between two cutpoints are correlated. In this method, ASTM–
2887 data can be converted to TBP without converting to ASTM–86 as was in Riazi-
Daubert method.
ASTM–D86 to TBP
This equation is used to convert an ASTM–D86 data at 50% point into TBP 50%
Once the 50% point data is calculated, Eqn.() is used to determine the difference
Yi = AXiB (4)
with 50% TBP temperature and add or substract the proper temperature difference
In this study, four available distillation data from an industrial FCC plant is
converted to TBP curve using these two methods. Figure 4.3, Figure 4.4 and Table
tion curve
Unfortunately, real-time measurement of the distillation curve from every feed is un-
realistic. Thus, another method to describe the mixture property is highly demanded.
62
tion(PDF). The PDF can be obtained form a distribution function that describes how
Several distribution functions have been utilized for calculations related to the
petroleum mixture. Among the distribution functions which can be found in the
distributions in the literature is listed in Table 4.4. Well-known but not included in
the list are Turkey-Lambda, Cauchy, and F distributions. They are seldom used to
model empirical data and they lack of a convenient analytical form of the PDF.
• Some of the three-parameter distribution functions can fit distillation data with
63
(a) Data #1
(b) Data #2
Using four-parameter distribution functions is ideal for curve fitting and vali-
dation. However, Since we have only one available measured data (API gravity),
and Γ distribution function are reported to show good accuracy. Three distribution
functions are used respectively in the algorithm and compared to evaluate accuracy.
The population density function in terms of molecular weight for this distribution
65
(a) Data #3
(b) Data #4
model is:
When α < 1, the population density function becomes suitable for gas condensate
increases. However, if the experiment is not available, 1 and 90 for α and η can be
M7+ = η + αβ (2)
The Weibull function with three parameters is defined in forms of PDF and cu-
C
P DF = [(y − A)/B]C−1 exp(−[(y − A)/B]C )
B (3)
C
CDF = 1 − exp(−[(y − A)/B] )
Z ∞
Γ(x) = tx−1 e−t dt (5)
0
The density function given in Eqn. 1 can be reduced to simpler form with the
1 M −η
F (M ) = exp(− ) (6)
M7+ − η M7+ − η
By integrating Eqn 4. between molecular weight boundaries of Mn− and Mn+ , xm,n ,
Mn+ Mn−
η
xm,n = −exp( ) × exp(− ) − exp( ) (7)
M7+ − η M7+ − η M7+ − η
To use this characterization method, API gravity which is measured from the
plant in this study should be transformed to other property such as molecular weight
of C+7 .
141.5
SG = (8)
AP Igravity + 131.5
An extensive analysis was made was made on basic characterization for C+7 frac-
tions of wide range of crude oils were made [67]. In the analysis, following versatile
equation was found to be the most suitable for various properties of crude oils.
1
A 1 (9)
P ∗ = ( ln( ∗ )) B
B x
P −P 0
where P is a any property distribution including specific gravity, P ∗ is P0
, and
1/3
SG∗average = 0.619ASG (10)
Figure 4.4: History of API gravity data from the plant in this study
Figure 4.4 shows history of API data from the industrial plant in this study. Data
points of the steady state among the plenty of the measured data were selected and
used. The time when the data was selected is marked with red boxes.
For measured data from the industrial plant, distribution functions for cumulative
Converted TBP curve data seem to be very similar. That is because the API
gravity data which is measured from the plant is very close to each other since the
operating condition did not change drastically during the operation. Besides, other
fluid properties were not available nor considered in conversion algorithm. Therefore,
we need additional validation of the conversion results using other process data such
as temperature and pressure of the FCC reactor unit to guarantee the reliability of
the results.
69
The reliability of the models with three distribution functions should be validated
with experimental data. However, real-time measurement for the industrial plant is
not available as mentioned in the previous chapter. Instead, the accuracy of the feed
property models were validated by comparing the reaction result using the mathe-
matical model which is built in this study with a steady-state result from a process
The default FCC reactor model in the software is used. The TBP curve data from
oil manager and petroleum assay with same API gravity in Aspen HYSYS is entered
to a feeder block for every 10◦ C. The Peng-Robinson equation of state is employed
for this system. The naphtha hydro-treater unit in this model is deactivated to avoid
unnecessary reactions in the hydro-treater and preserve the distribution curve data
from the feeder block to the FCC block. The unit size, operating conditions and other
specifications at the same time were used for the design of HYSYS FCC model.
Table 4.5 shows that the Weibull distribution function and gamma distribution
function showed similar accuracy while the χ function was a little inaccurate. Hence,
70
the gamma distribution function is selected to be used for the correlation model in
our study since data and assumptions parameters for the gamma distribution is much
available.
Fig 4.7 and Fig 4.8 presents the result of simulation distribution . The comparison
showed slightly disagreed expectation result for LPG and LCO. It is assumed that
uncertainties about catalyst in the reactor have caused this phenomenon. Process
catalyst coefficient can be calculated, but it is not known what kind of the catalyst
it is and kinetic constants in the reaction rate may vary. Considering that point, we
conclude that the correlation model exhibits an acceptable agreement with the results
model constants
In chapter 2, physical properties like heat capacity and heat of combustion are con-
sidered as constant since the model was incapable of identify different mixture com-
position within the feed flow. As the feed is characterized using the measured process
data, the heat capacity and the heat of combustion can be estimated by Lee-Kesler
CPL = a(b + cT )
a = 1.4651 + 0.2302Kw
(1)
b = 0.306469 − 0.16734SG
c = 0.001467 − 0.000551SG
CPL = A1 + A2 + A3 T 2
4.81407 − 0.194833KW
A1 = −4.90383 + (0.099319 + 0.104281SG)KW +
SG
0.27634 (2)
A2 = (7.53624 + 6.2147610KW ) · (1.12172 − ) · 10−4
SG
0.70958
A3 = −(1.35652 + 1.11863KW ) · (2.9027 − ) · 10−7
SG
Aspen Properties and HYSYS software with workbook are used for calculation
of these properties in the modeling and validation. Since the correlated distillation
curve varied little, the heat capacity and heat of combustion are considered to be
almost unchanged.
4.7 Conclusion
and tested with measured data from an industrial plant and to validate the algorithm.
For the estimation, various correlation methods between complex petroleum proper-
ties were found from literature and interconnected to find the distribution function.
The results were validated by being compared with the results from Aspen HYSYS
72
V 8.4 under same operating condition. The proposed approach can provides insights
of complex feed in the petrochemical process without performing costly and time-
consuming experiment. This study can be improved to consider some attributes that
may be important but not available in this study. It is probable that with wide range
of plant data before the our FCC plant, we can improve the prediction performance
(a) Off-gas
(b) LPG
(c) WCN
Figure 4.6: The mathematical model result with correlated TBP compared to Aspen
HYSYS V8.4 (1)
74
(a) LCO
(b) CLO
Figure 4.7: The mathematical model result with correlated TBP compared to Aspen
HYSYS V8.4 (2)
Chapter 5
Concluding remarks
This thesis presents a mathematical approach on modeling the fluid catalytic crack-
ing(FCC) process and its application including systematic analysis and feed charac-
Reaction kinetics should be defined to describe the reactor effluents and thermo-
dynamic phenomena in the reactor. Empirical correlations that describe the reac-
tion kinetics with model parameters are built. Also, an approach to apply the yield
function for the kinetic model of the riser is made. Lastly, hydrodynamics, mass bal-
ance and energy balance should be considered. Steady-state simulation results and
dynamic responses to the change of process variables are simulated by the process
model and compared to the plant data. Then based on the model and process de-
of the system. The reactor and regenerator unit in this system are divided into six
nodes based on their functions and modeling relationships are built based on nodes
on the occurrence matrix to find that only a part of the system is fully observable
and the states in the regenerator is not observable with current measurement sets.
75
76
Optimal locations for additional measurement are suggested by completing the whole
unmeasured properties of feed mixture are suggested and tested to validate the algo-
rithm. Various correlation methods between complex petroleum properties are found
from literature and interconnected to find the distribution function. The proposed
approach can provides insights into the FCC process and will be a suitable technique
for process design, operation and even more applications such as optimization.
Based on this research, some of future works can be considered. First, mode
controllability of the system. In this research, the system is divided into only 6
nodes regarding their functions. However, by defining more detailed system, we can
make use of much more measured data to improve accuracy of our model. Also,
we did not study about control problems of the FCC process. Further systematic
analysis would help this topics. The next is to evaluate more detailed correlation
model for characterizing the feed property. In this study only existing theories were
combined to find any improved correlation between available measurements and the
feed property. However, with more insight with thermodynamics and petrochemicals,
Appendix A
Nomenclature
ṀCO,DensetoDilute = The molar flow rate of CO leaving the dense bed (mol/h)
ṀCO2,DensetoDilute = The molar flow rate of CO2 leaving the dense bed (mol/h)
ṀN 2,AirtoDense = The molar flow rate of N2 from theair to the dense bed (mol/h)
ṀH2O,DensetoDilute = The molar flow rate of H2 O leaving the dense bed (mol/h)
ṀO2,DensetoDilute = The molar flow rate of O2 leaving the dense bed (mol/h)
ṀO2,in = The molar flow rate of O2 from the air to the dense bed (mol/h)
P = Pressure (bar)
QR,Densebed = heat released per volume due to combustionreactions in the dense bed (kJ/m3 )
QR,Dilutebed = heat released per volume due to combustionreactions in the dilute phase (kJ/m3 )
T = Temperature (K)
Riser
Ycoke = the coke weight fraction on catalyst from the riser reactor to regenerator
Regen
Ycoke = the coke weight fraction on catalyst from the regenerator to riser reactor
31(11):2483–2497, 1992.
[3] Raj Kumar Gupta, Vineet Kumar, V.K.Srivastava. A new generic approach for
the modeling of fluid catalytic cracking (FCC) riser reactor. Chemical Engineer-
fixed, moving, and fluid bed reactors. AIChE Journal, 16(3):397–404, 1970.
[6] Liang-Sun Lee, Yu-Wen Chen, Tsung-Nien Huang, Wen-Yen Pan. Four-lump ki-
netic model for fluid catalytic cracking process. The canadian journal of chemical
83
84
[8] Chunyang Jia, Sohrab Rohani, Arthur Jutan. FCC unit modeling, identification
[9] Raluca Roman, Zoltan K.Nagy, Mircea V.Cristea, Serban P.Agachi. Dynamic
with selective catalyst deactivation for the prediction of the product selectivity
lumping and reaction scheme for catalytic cracking. AIChE Journal, 22(4):701-
713, 196.
85
[14] Arnon Arbel, Zupeng Huang, Irven H. Rinard, Reuel Shinnar, Ajit V. Sapre.
1243, 1995.
[15] Sanjay Kumar, Ajay Chadha, Rajan Gupta, Raj Sharma. CATCRAK: A Process
[16] Dan Simon. Optimal State Estimation: Kalman, H Infinity, and Nonlinear Ap-
[17] Liu, Y.-Y., Slotine, J.-J., Barabasi, A.-L. Observability of complex systems.
Verlag, 1988
[19] M. Anushka, S. Perera, Bernt Lie, Carlos Fernando Pfeiffer. Parameter and
international, 2005.
[21] Sriram Satya, Richard M. Roehner, Milind D. Deo, Francis V. Hanson. Estima-
[23] Nace, D. M., Voltz. S. E., Weekman, V. W. Application of a kinetic model for
Research,10(4):530–538, 1971.
4640, 1998.
[25] Castiglioni, B.P. How to predict FCC yields. Hydrocarbon Process,62(2), 1983.
engineering,17(10):837-844, 1997.
model in the simulation of an industrial riser reactor for the catalytic cracking
[29] Hany Ali, Sohrab Rohani. Dynamic modeling and simulation of a riser-type fluid
science,47(9-11):2319-2324, 1992.
[32] Todd S.Pugsley, Franco Berruti. A predictive hydrodynamic model for circulating
[33] Wenkai Li, Chi-Wai Hui, AnXue Li. Integrating CDU, FCC and product blending
2028, 2005.
1904, 2007.
[35] Yongmin Zhang, Chunxi Lu, Tingwen Li. A practical countercurrent fluid cat-
[36] Joana L. Fernandes, Carla I. C. Pinheiro, Nuno M.C. Oliveria, Ana I. Neto,
Fernando Ramoa Ribeiro. Steady state multiplicity in an UOP FCC unit with
2007.
88
43(13):3270–3281, 2004.
[40] Ginzel, W. How feed qualify effects FCC performance. Erdoel und Kohle, Erdgas,
[41] Powell R. T., Yu, C. -Y. Refinery reaction modeling trends. Hydrocarbon Engi-
[43] D.M. Nace. Catalytic cracking over crystalline aluminosilicates. II. Application
[44] D.K. Liguras, D.T.Allen. Structural models for catalytic cracking. Industrial &
FCC catalyst and various commercial cracking catalysts using TGA. Ther-
[46] J. Corella. On the modeling of the kinetics of the selective deactivation of cata-
lysts. Application to the fluidized catalytic cracking process. Industrial & Engi-
2004.
[49] In-Su Han, Chang-Bock Chung. Dynamic modeling and simulation of a fluidized
catalytic cracking process. Part II: property estimation and simulation. Chemical
142, 2009.
actor Study of Gas Oil Cracking. Industrial & Engineering Chemistry Product
[55] V. Van Speybroeck. Modeling elementary reactions in coke formation from first
[56] M.Anushka S. Perera, Bernt Lie, Carlos Fernando Pfeiffer. Structural observ-
ability analysis of large scale systems using Modelica and Python. Modeling,
[57] Chi-Tsong Chen Linear system theory and design Oxford university press, 2009.
[60] Angel Nedelchev, Dicho Stratiev, Atanas Ivanov, Georgy Stoilov. A True Boil-
[61] Nelson, W. L., Hansburg, M. Relation of ASTM and True Boiling Point Distil-
[62] Edmister, W. C., Pllock, D. H. Phase relations for Petroleum Fractions. Chemical
2000.
36:4299–4307, 1997.