Printed
Comput.
Modelling
1993 Copyright@
in Great Britain.
Comparison Between Different Mathematical Models for the Simulation of Industrial Fluid Catalytic Cracking (FCC) Units
S. Chemical S. E. P.O. S. Department S. H. ELNASHAIE* King Saud Arabia University Engineering Riyadh, Department, ELSHISHINI* University
of Chemistry, College of Science, King Saud Riyadh, P.O. Box 22452, Saudi Arabia
Abstracth&t of the work dealing with the modelling of industrial fluid catalytic cracking units is based upon a highly empirical approach that helps in building units and operating them, but does not help to elucidate the main features and characteristics of these units for better design, control, and optimization. It is shown in this paper that a better insight into the behaviour of these units can be achieved through the use of less empirical mathematical models coupled with industrial verifications. The present paper emphasizes the bifurcation behaviour of these industrial units.
NOMENCLATURE
A
Dimensionless velocity constant for overall cracking reactions (Equations (32), (34)) Frequency factor in Arrhenius equation for coke burning reaction Overall frequency cracking Frequency factor for
CA,,CA,
CA,f,
AC A CT Ad Ai
Weight % of catalytic carbon, carbon on spent catalyst, and carbon on regenerated catalyst Weight ratio of coke necessary for complete deactivation of catalyst Cpa,
Cpf, Cplr cps
Frequency factor in Arrhenius equation for cracking reactions, i = 1 for cracking to gasoline and i = 2,3 for cracking to coke Area of bed occupied by bubbles in reactor and regenerator, respectively; m2 Area of bed outside bubbles (dense phase) in reactor and regenerator, respectively; m2 Constants for catalytic carbon, additive carbon, and strippable hydrocarbons Space velocities regenerator in reactor and
Heat capacities of air, liquid feed, vaporized feed, and solids; J/kg K Heat capacity of gases in reactor and regenerator; J/mol K Weight ratio of coke to catalyst reactor and regenerator; kg/kg Weight fraction Concentration of coke in feed of oxygen; mol/m3 in
c PRI CpG
&B> AGB
CR,
CG
ARD,
AGD
cf
co Ec, Ei
act , aad,
ashc
Activation energies for coke combustion and cracking reaction, i = 1 for cracking to gasoline, i = 2,3 for cracking to coke; J/mol
BR,
BG
Author to whom all correspondence should be addressed. *On leave from the Chemical Engineering Department, Cairo University,
91
S. S. E. H. ELNASHAIE.
S. S. ELSHISHINI
energy for
Rate of coke formation; Overall rate of cracking; Liquid space velocity; Time; s Catalyst residence
Ed
FAG
t tc
TGFYTAF
FC FD
= FGF (In the model of IscolFigure la, FD = FGF in lb/hr) Fresh feed, mixed feed, and air feed flowrates; kg/s
TR,TG
F,r
Coke formation factor of total feed; kg Coke/m3 oil Volumetric feed flowrate for gas oil and air; m3/s Volumetric regenerator gas flowrate in bubble phase, dense phase, and overall; m3/s Volumetric reactor gas flowrate in bubble phase, dense phase, and overall; m3/s
GGFIGAF
Molar gas flow rates of feed, reactor gases, regenerator gases, and air; mol/s Weight fraction gases) of coke to (coke +
W.
HR,HG
Height of fluidized bed in resctor and regenerator; m Total inventory of catalyst; kg Reaction velocity constant for coke combustion and cracking reactions, i = 1 for cracking to gasoline, i = 2,3 for cracking to coke
Dimensionless concentrations of component i in the bubble phase, dense phase, output, and feed, i = 1 for gas oil, i = 2 for gasoline Coke on catalyst in reactor regenerator; mol/kg cat Mole fraction of component unit and in feed Mole fraction and in feed and i in
XR,XG
Yi,YiF
Kc,
for
YOrYOF
of oxygen in unit
kn,f
determined coefficient
YRB,YRD,YR
Dimensionless temperature in bubble phase, dense phase, and output of reactor = T/T,f Dimensionless temperature in bubble phase, dense phase, and output of regenerator = T/T,f Dimensionless feed temperature gas oil and air Dimensionless temperature feed vaporization of
YGB,YGD,YG
Molecular weights of gas oil, gasoline, gases, coke, and air Catalyst hold up in reactor and regenerator; kg
NR,NG YGF>YAF
Gas hold up in reactor and regenerator; mol Volume percent of oxygen in flue gases Partial pressure of hydrocarbons in stripper; Pa Pressure tor; Pa in reactor and regeneraby
Ofi4
Greek Symbols
a,0 PC A ri
Coke oxygen stoichiometric Exothermicity Endothermicity Dimensionless EiIR. factor factor activation
ratio
91c
&>pG
energies
Trr
coke combustion and reactions, i = 1 for to gasoline, i = 2,3 for to coke; J/kg and heat
AH,, AH,
Heat supplied by combustion and heat removed from system; J/s Mass transfer interphase coefficient for reactor and regenerator; l/s Heat loss for unit; J/s Universal gas constant kg/s Rate of coke combustion;
QL R Rc
Dimensionless heat losses from reactor and regenerator Dimensionless heat of cracking and vaporization Porosity of fluidized bed
Simulation of Industrial FCC Units Conversion of gas oil cracking; wt. fraction Dimensionless decay velocity constant (Equations (32), (33)) PI I Pf Density of liquid feed, vaporized feed, and air; Kg/m3 Catalyst activity in reactor and regenerator
93
EC
I Pa
bR, $G
INTRODUCTION
Multiplicity phenomenon in chemically reactive systems has been first observed as far back as 1918 [l], and in the Russian literature as far back as 1940 [2], especially in relation to the explosion theory. However, it was not until the 1950s that the great interest in the investigation of this phenomenon started, inspired by the Minnesota school of Amundson and Aris [351 and their students [691. The Prague school also had a notable contribution to the field [lo121. Since then, this phenomenon has been high in the agenda of chemical engineering research in general, and chemical reaction engineering research in particular. The fascination with this phenomenon has also spread very widely in the biological and biochemical engineering literature where it is referred to as short term memory [13,14]. In the mathematical literature, this phenomenon is treated in more general and abstract terms under bifurcation theory [15]. A major breakthrough with regard to the understanding of this phenomenon in the field of chemical reaction engineering was achieved by Ray and coworkers [16,17] when in one stroke they uncovered a large variety of possible bifurcation behaviours in nonadiabatic continuous stirred tank reactors. In addition to the usual hysteresis type bifurcation, Uppal et al. [17] uncovered different types of bifurcation diagrams, the most important of which is the isola which is a closed curve on the bifurcation diagram, disconnected from the rest of the continuum of steady states. Isolas were also found by Elnashaie et al. [18201 for enzyme systems where the rate of reaction depends nonmonotonically upon two of the systems state variables (substrate concentration and pH), a situation which was shown to be applicable to the acetylcholinesterase enzyme systems. Later development in the singularity theory, especially the pioneering work of Golubitsky and Schaeffer [15], provided a very powerful tool for the analysis of bifurcation behaviour of chemically reactive systems. These techniques have been used extensively, elegantly, and successfully by Luss and his coworkers [7,8,21231 to uncover a large number of possible types of bifurcation. The Fluid Catalytic Cracking unit for the conversion of heavy gas oil is one of the most important conversion processes in the petroleum refining industry. Despite the great industrial importance of this unit and the complexity of its rather interesting steady state and dynamic behaviour, it has been the subject of very few modelling and simulation investigations [24271. Most of these investigations are based on highly empirical models and give conflicting conclusions. In addition to that, most of these investigations concentrate on the thermal characteristics of the unit and do not involve any reaction network that allows relating the performance of the unit as a gasoline (and sometimes olefins) producer to its thermal characteristics. A serious limitation in these models is the fact that they ignore completely the twophase nature of the fluidized beds in both reactor and regenerator. The models of Elnashaie and ElHennawi [28,29] and Elshishini and Elnashaie [30331 involve a reaction network and recognize the twophase nature of the reactor and regenerator. These models take into consideration the main processes taking place within the boundaries of the system in a rational, albeit simplified form. The present paper is mainly concerned with the mathematical modelling of industrial fluid catalytic cracking units with special emphasis on their bifurcation behaviour.
94
S. S. E. H. ELNASHAIE, S. S. ELSHISHINI
engineering
literature
of chaotic behaviour,
interest
Physical Explanation of Bifurcation Multiplicity of the steady states, which is a phenomenon associated with open systems only,
means that such a system will have more than one stationary nonequilibrium state. The open system may have multiplicity of the steady states for a certain region of its physicochemical parameters if and only if there is at least one process that is taking place within the boundaries of the system which is a nonmonotonic function of at least one state variable of the system. This is a necessary condition for the existence of multiple steady states, but it is not a sufficient condition. To discuss the sufficient conditions for the existence of multiple steady states, we must make it clear that there are certain even when the nonmonotonic flow reactor, where no mixing systems that will never show multiplicity conditon is satisfied, of the steady tubular that states plug will dependence between e.g., the adiabatic
have multiple steady states if the nonmonotonic dependence condition is satisfied, but only for a certain range of parameters (physicochemical, operating, and design parameters). No system will exhibit multiplicity of the steady states for all values of the parameters. The plug flow adiabatic reactor does not show any multiplicity of the steady states because the plug flow system does not have any diffusion or mixing. In other words, what is happening upstream is completely independent of what is happening downstream. This gives a second necessary conditon for multiplicity, which is the existence of some kind of diffusion or mixing mechanism that creates what might be called a feedback of information, or in simpler terms, makes what is happening upstream depend on what is happening downstream. Thus, for the above plug flow reactor with the nonmonotonic dependence condtions satisfied, the existence of a recycle stream from the output of the reactor to the input creates the possibility for multiplicity of the steady states. In the case of a nonisothermal plug flow reactor, where an exothermic reaction is taking place, the reactor will never give multiplicity of the steady states if it is provided with cocurrent cooling. However, if the cooling is countercurrent, multiplicity of the steady states is possible. From a mathematical point of view, the simplest bifurcation problem involves treatment of the local bifurcation problem with one state variable,
where x is a state variable and X the bifurcation parameter. Many chemical engineering problems can be reduced to the form of equation (1). Evidence for the existence of multiple steady states for the industrial FCC units discussed in this paper are shown in Figures 13.
Simulation
2 0.013 5 xc! 2 z 0.014 22
,u.0
of Industrial
FCC Units
95
0.011
urn _.I 560 P. 2 ; P d c 340 630 640 650 FD, LBlHR 660 950
51 (L I 2 _A 50 m U d 49 E
0.2 0.0 0
1 gy__;;;:_,:,
=,9( j ,y
4.8 5.4 6.0 6.6 7.2 Temp.10 Regenerator
670
1f
0.6
+q
\.*
1.8
1.4
3.0 Air
3.6 Fe&
4.3
YAF Dimensionless
(a) Iscol (241 (bifurcation diagram with gas oil feed flow rate as the bifurcation parameter). 200
(b) Elnashaie and ElHennawi [28] (bifurcation diagrams at different gas oil flow rates with air feed temperature as the bifurcation parameter).
19c
18C Q. megaJlrec
1JC
la
Partial Comburtion
TOlOl Combv,lion
163
150
j

  
Heat Heit
Generation
Removal
500
925
550
975
1000
1025
Regenerator
Bed Temperature.
(c) Edwards and Kim [27] (Van Heerden diagramheat removal diagramfor one set of parameters showing steady states). Figure 1. Examples trial Fluid Catalytic of diagrams showing multiplicity Cracking units (FCC) obtained

75/.
COMPLETE
COMBUSTION
0.00
0.40
Catalyst
0.80
Circulation
1.20
Rate Fcl Fcr,t
Dimensionless
Figure reactor
2. Effect of degree of coke combustion to CO2 on bifurcation temperature vs. catalyst circulation rate [30].
diagrams
for
96
S. S. E. H. ELNASHAIE,S. S. ELSHISHINI
fluidization regimes beyond the bubbling regimes. One of the most complicated problems is that associated with riserreaction type units because of the complex flow patterns in the riser. Recent research in fast fluidization regime and circulating fluidized beds helps to elucidate the complex nature of the flow in these risers [34371. Grace [38,39] argues that it is not difficult to revise twophase fluid bed reactor models, originally intended for bubbling bed regime, to be applied to other regimes of fluidization.
4.0 z 2 INDUSTRIAL INDUSTRIAL UNIT UNIT 1 i
1. 00
___I:IDUSTRIAL lNDUSTRlAL UNIT UNIT 1 2
2.0 
temp.
_I
0.00
1.00
2.00
Reactor
3.00
( YR )
4.00
Dimensionless
Temperature
(b) Conversion and gasoline yield for units 1 and 2 1291. Figure 3.
in this paper. The models differ from each other in some basic characteristics as well as in their structure. The degree of empiricism in expressing the rates of the different processes also differ from one model to the other. Table 1 shows a summary of the basic characteristics of the seven models discussed.
Table 1. Summary of some of the basic characteristics industrial Fluid Catalytic Cracking (FCC) units. Characteristics TwoPhase Models Model L & L [40] K No Kinetics of Gasoline Formation Yes Kinetics of Carbon Formation Yes Yes Yes Yes Yes Yes Yes of the models used to simulate
Kinetics of Carbon Burning Yes Yes Yes Yes Yes Yes Yes
Predicts Multiplicity
1251
No
No No Yes No Yes
No
No No Yes No Yes
I ]241 L & K [26] E & E [28] E & K [27] E & E modified [30]
LUYBEN
AND
LAMB
MODEL
(L & L MODEL)
Luyben and Lamb model [40] was described by Douglas [41] as being a crude model that predicts the direction of change of the most important dependent variables and at least gives an order of magnitude estimate of the response time of these variables.
97
The authors
assume
reaction
products,
and m is an empirical
stoichiometric of
coefficient depending upon the degree of completion of carbon combustion hydrogen in coke. The model is also based on the following assumptions: 1. The reactor and the regenerator are perfectly mixed.
2. The heat capacities are independent of composition and temperature. 3. The catalyst holdup remains constant in each vessel. 4. The reaction rates are first order and the rate of coke combustion is independent amount of coke. 5. The reaction network in the reactor is formed of one reaction. The material
REACTOR. dNR 
of the
and energy
balance
equations
as follows:
dt dNRys = VGFy2~  VR y2 + NR (1  ~2) Al eFEIIRTR, dt dXR = Fc XG  Fc XR + 0.1 Nn (1  yz) Al eE1RTR, MR dt C&k% = &RVGFTGF
 (AHr) +c,sFcT~  C~RVRTR  C,,FCTR
= VGF 1/R,
c4
(3) (4)
Nn (1  ~2) A1 eeEIIRTR.
(5)
REGENERATOR.
(6) (7)
(8)
TG C,,FCTG (9)
 (AH2) NG yo A, emEciRTG+ Q. Using the ideal gas law and simplifying the equations, of six coupled, nonlinear, ordinary differential equations Evaluation of the Model
the authors reduced the model to a set which can be solved numerically.
The model was not tested experimentally, and using such a simplified model for estimating the dynamic characteristics of the system may give misleading results. However, by introducing some modifications on the kinetic scheme used for the cracking reactions and on the rate of carbon burning, it can provide a starting point for developing an approximate model.
98
S. S. E. H. ELNASHAIE, S. S. ELSHISHINI
KURIHARA
MODEL (K MODEL)
Denn, in his recent book [42], considers Kurihara model [25,43] to be the best model available in the open literature. The model considers two different carbon species. The carbon that is deposited on the catalyst during the course of the cracking reaction is denoted catalytic carbon (C,,,). The remaining (additive) carbon is generally present in gas oil and is deposited without reaction. Carbon that has passed into or through the regenerator on the spent or regenerated catalyst has a different chemical activity from the catalytic carbon. This species is identified as C,, or C,,, depending on whether the catalyst has been regenerated or spent. The msss balance on total carbon on the spent catalyst in the reactor by: is given in this model
(10) = Fc (Cm  Cs,) + R,f. dt The term Fc C,, is simply the rate at which catalytic carbon leaves the reactor, while FC C,, is the rate at which carbon remaining on the regenerated catalyst is supplied to the reactor through the catalyst circulation stream. The specific rate of carbon formation is described by:
MR
dcs,
+ptrG~F,
(11)
exp[&/RTn].
(12)
The first term in (11) represents the rate of production of catalytic carbon from the cracking reaction, and the second term represents the rate of formation of additive carbon, which is proportional to the feed rate GGF. The remaining reactor mass balance is written weight %) obtained from the cracking reaction, for C&t, which is the catalytic carbon (in
equation
dC,,t MR= Fc &at + MRPRK~. dt for the reactor is written as:
GFTR)+(AHv)P~GGF+(AH~~)R~~.
(13)
= C,,FC(TGTR)+C~~P~GGF(T
(14)
The term containing the enthalpy of vaporization accounts for the fact that the gas oil enters as a liquid and is vaporized inside the system. The overall specific rate of cracking reaction R,, is given by:
Rcr =
MRPRP~Kc, 1 +MR&&@GF'
and
(15) (16)
The regenerator
A~,,,, exp[&/RT]. cat CT mass and energy balance equations are given by: MG
K,, = c
Gc
dt
= Fc (Cs,  Cr,)  R,, = C,, Fc (TR  TG) + Cpa FAF (TAF  TG) + (AHc)
Rc.
(17)
(18)
1oocr
MGPG/FAF
(19)
where
Of' = 21 exp
(104/3.15 Fx,)
+ (100/C,,
A, exp(&/RTG))
(20)
Cr is a stoichiometric coefficient that and CO products, and (21  Or,)/100 air feed is 0.21.
reflects the selectivity of the combustion reaction to CO2 is the oxygen conversion, since the volume fraction in the
SimulationIndustrial Units of FCC Evaluation of Kurihara Model from other models by the fact that it differentiates between catalytic
99
carbon which deposits on the catalyst due to catalytic cracking, and noncatalytic is generally present in gas oil and is deposited without reaction. In the solution Kurihara Other assumes additive carbon to be zero (Ftf = 0). than that, the model is, in principle, very similar to the model
[26] discussed later, especially with regard to the model structure and the involved in the different generation, and consumption functions inserted in the twophase nature (bubble and dense phases)
the model equations. Kurihara model [25,43] does not recognize of the two fluidized beds in the reactor dense phase can be considered dense or emulsionphase),
Although
(pseudohomogeneous
the differentiation
as a whole, in such bubbling or turbulent fluidized beds, can be quite important for accurate mass and heat balance formulation of the system. Kurihara [25,43] uses a very simplified kinetic scheme given by the following equation: Cracking Gas oilProduct gas+Coke (additive + catalytic).
This network is similar to that used by Luyben and Lamb [40] and has the disadvantage of lumping gasoline, coke, and light hydrocarbons. Consequently, there is no way to obtain the gasoline yield which is the most important design variable. The most serious limitation in this model is that the constants AZ (for the rate of catalytic carbon formation) and A1 (for the rate of catalytic cracking) have been fitted for a certain assumed steady state. Kurihara [25,43] assumes that the reactor is operated at a certain probable steady state condition (e.g., Mn = 54432 kg, PR = 275 kPa, tn = 499C, GGF = 0.184 m3/s, conversion on fresh feed = 0.6), together with a certain probable steady state condition of the regenerator, and he evaluates AZ and Al by setting the time derivatives to zero and solving the steady state mass balance equations. This was justified for optimal control, since the investigation was concentrating on the problem of small disturbances around the steady state condition, as Kurihara puts it in his thesis: %ince it is not only dificult but also uesless for our purpose of simulation to estimate accurately these constants by purely chemical analysis of feed composition and catalyst condition, this kind of closedloop method was used [25]. However, these rate equations are not valid at any other conditions away from the assumed steady state (simple calculations show that for a reactor temperature of 593C, the percent carbon formed is much higher than 100%). Consequently, they cannot be used to investigate multiplicity of the steady states, since the model will always give one steady state (the assumed steady state).
ISCOL
MODEL
(I MODEL)
Iscol [24] carried out his modelling exercise to investigate the steady state and dynamic characteristics of Model IV Fluid Catalytic Crackers with special emphasis on trying to explain the continuous drift of a commercial unit away from its operating point at high gasoline yield. Iscol model consists of the following mass and energy balance equations together with the necessary generation and consumption functions. REACTOR ENTHALPY BALANCE.
x
= Fc C,, (TG  TR)  FGF (335oT~  814100)  8141000 R,f  2.93 ENTHALPY dt
x
106.
(21)
dTG = 3.02
107.
(22)
(23)
dk
dt
=Fc(&CG)%.
(24)
Z&f = FGF [0.0754 + 2.297 x 10e6 x (7'~ 772)3]. COKE BURN RATE CORRELATION & = 6.45 [l eXp[CG
(25)
(REGENERATOR).
(747 + 14.94 (??G 894) + 0.107 (TG 894)2)]]. (26)
The coke make and burn rates are given by empirical correlations, which as Iscol states in it should be noted that equation (26) will vary among conjunction to the coke burning rate: different FCC units and depends upon catalyst type, chemical composition of the coke and actual catalyst flow pattern, and thus vessel geometry. Evaluation of Iscol Model
The empirical nature of the coke forming, coke burning, and heat losses from the vessels is apparent. Also, the coke make rate is expressed in terms of the input variable FGF (gas oil feed flow rate) which is not very rigorous, since all processes in a physical model should be expressed in terms of state variables in the model formulation. As for the rate of coke burning, although it is expressed in a semiempirical form, it is actually expressed as a function of the regenerators state variables CG and TG, with no input variables appearing in the equations. The Iscol model does not involve any reaction network entailing all the consequences discussed earlier, and it also does not recognize the twophase nature of the fluidized beds in the reactor and the regenerator. Iscol [24] investigated the steady state characteristics of his model and showed that multiplicity of the steady states (bifurcation behaviour) does exist over a relatively wide range of parameters (Figure la). He also concluded that the operating steady state is the middle unstable steady state, and that the instability of the system manifests itself as a slow drift from this unstable steady state due to the very high heat capacity of the system.
LEE AND
KUGELMAN
MODEL
(L & K MODEL)
The model of Lee and Kugelman [26] was published three years after Iscol model to reinvestigate the problem of multiplicity of the steady states in fluid catalytic cracking units. The model consists of the following equations: REACTOR CARBON BALANCE. d(MRCR) dt REACTORENERGY ~(MRC,,TR) dt BALANCE, = FC CPS (TG  TR) + FGM C,l (TGF  TR)  FGM (AH + tc AH,,). (28) = Fc(CG  cR)+%f. (27)
101
dt
REGENERATOR ENERGY BALANCE. d(MG c,s TG)
Fc (CR  c,)
R,.
dt
(30)
The carbon formation in the reactor is given by Lee and Kugelman [26] as:
(31)
Lee and Kugelman [26] state that the first term on the right hand side of (31) corresponds to the cracking reaction and is based on the assumption that coke formation follows the socalled Voorhies relationship [44], in which the weight fraction of coke on catalyst is proportional to the nth power of the catalyst residence time in the reactor. The coke formation rate constant ucc is taken by Lee and Kugelman [26] to be a function of feedstock and catalyst. Lee and Kugelman [26] determine ucc, Ez, and n experimentally to fit laboratory and plant data, and therefore their values strongly depend upon catalyst, feedstock, and the characteristics of the particular FCC unit. In addition to catalytic coke, Lee and Kugelman consider additive coke (e.g., Conradsontype coke) which is included in the second term of (31). They also take into consideration the efficiency of the stripper by adding a term which depends upon the fact that the hydrocarbons interspersed among the catalyst particles are to be completely stripped by countercurrently flowing steam. However, due to the poor efficiency of the stripper, some fraction of the strippable hydrocarbons remains and is carried over to the regenerator. This effect is included in the last term of (31), the amount of strippable hydrocarbons to be burned being proportional to an lth power of catalyst circulation rate. In fact, this term should not be included in the carbon formation equation, for it does not affect the catalyst activity the same way carbon does. It should be accounted for in the heat balance of the regenerator, for, in actual fact, it gets burned in the regenerator and contributes to the amount of heat released in the regenerator. The gas oil overall cracking conversion cc is given by the model as: A (1  emX) EC=X+A(leX) where X = t, Ad edEdIRTR, (33)
A _ f pf ACr ,&IRTR (34) PI S and Ad, A,,, E,,, Ed are experimentally determined parameters characterizing the combination of the particular catalyst and feedstocks. The coke burning rate is given by Rc = FAG Mc (21 Of,), 100 (Y,OMA (35)
where Of, is the oxygen mole fraction at the exit of the regenerator which is computed from the relation: A, e Eel RT~ CG I6f~ MG CY,O Of, = 21 exp 0.21 FAG MC Lee and Kugelman [26] used this model to investigate the steady state characteristics of the system, and they reached an opposite conclusion to that of Iscol [24] with regard to multiplicity. Lee and Kugelman [26] attributed the multiplicity results obtained by Iscol [24] to the cubic temperature dependence in the expression for R,f used. Denn [42] comments on this contradiction by emphasizing the need to study the sensitivity of the model predictions to structural as well as parametric changes.
I*
102
Evaluation of Lee and Kugelman Model The model does not consider the twophase nature of the two fluidized beds which is similar to previous models. However, it distinguishes between catalytic carbon and additive carbon, for which is in principle comparable to Kurihara model [25,43]. The model takes into consideration the stripping efficiency, which accounts for what is known as cattooil coke. This is a measure of unstripped, but potentially strippable, hydrocarbons that are carried out to the regenerator [45] because of the nonideal stripping in the commercial process, and they are also burned in the regenerator. Obviously, this is not really coke. The inclusion of this stripping efficiency is an advantage to the model building; however, the authors include this term with the carbon formation rate in the reactor (equation (31))! This causes some errors in the carbon balance in the reactor which affect the computation of the catalyst activity and the heat produced in the regenerator. The first term in (31), which is supposed to be the term for the formation of catalytic carbon, has a dependence over t,, which is the catalyst residence time in the reactor. This dependence can be justified by Voorhies work [44] and also by the derivations of Kurihara [25] and Denn [42], who have shown that under certain assumptions and when vapors are flowing isothermally in plug flow, such a dependence can be obtained. However, as shown in (31), the term is made also dependent on the catalyst circulation rate (F,), which is not a state variable and cannot be directly related to the rate of catalytic carbon formation. The inclusion of such an input variable in such a manner affects negatively the logical structure of the model and will, therefore, affect the consistency and the conclusions obtained using this model. The model also represents E, (the conversion) in a manner which is, to a great extent, independent of the rate of formation of catalytic carbon. In fact, the rate of formation of catalytic carbon and the conversion are strongly interlinked. The model is not expected to show any multiplicity of the steady states, since the authors use Kurihara rate equations for which the constants are fitted to a specific steady state. As explained earlier, these rates are not valid at any other steady state, and the solution of the steady state model will always give the assumed steady state.
ELNASHAIE
AND
ELHENNAWI
MODEL
(E & E MODEL)
Elnashaie and ElHennawi [28] developed a model that overcomes some of the limitations of the previous models in order to check the contradictory results reported in the literature, specifically the opposite conclusions of Iscol [24] on one hand, and Lee and Kugelman [26] on the other hand. The model of Elnashaie and ElHennawi takes into consideration the twophase nature of the fluidized beds in the reactor and the regenerator, albeit in a simple form. Elnashaie and ElHennawi used the three pseudocomponents kinetic model of Weekman [46,47]: Gas Oil (Al> 3 Gasoline K3 The rates of reactions for this consecutiveparallel network are given by Weekman and Nate [48] a% RATE OF DISAPPEARANCE OF GAS OIL. (AZ) 3 Coke + Gases i< (As)
(36)
RATE OF APPEARANCE OF GASOLINE. (37)
103
R3 (1 RE) ps (K&i, = In this simple coke burning model, the gaseous throughout the particle at constant concentration solid reactant (coke deposit) according
+K3C&).
(38)
For the coke burning in the regenerator, Elnashaie and ElHennawi model for solids of unchanging size presented by Kunii and Levenspiel
reactant (oxygen) is assumed to be present (no diffusional resistance) and reacts with
REACTOR DENSE PHASE EQUATIONS. Gas oil balance: BR (Zlf  $lD)  ?,!&& Gasoline balance: 01 eY1YRD + (Y3eY31YRD = 0. >
(40)
BR
Coke balance:
(Xzf  X~D)
?,!JG CY~X~D~T~~'~~~
(Y~X~D~"'~~~
>
0.
(41) (42)
Heat balance: al (YGD  YRD) + BR (Yv  YRD) + ~2 (YGF  K)  (AR + ARLR) + ABcr = 0. REACTOR BUBBLE PHASE EQUATIONS. Gas oil balance: (X1B  X1D) = (xlf  51~) emaR HR. Gasoline balance: (ZZB  22~) = (x2f  521)) eeaR HR. Heat balance:
(YRB  YRD) = (K  YRD) eREGENERATOR DENSE PHASE EQUATIONS. Coke balance:
(43)
(44
(45)
a~ HR .
(46)
(47)
Heat balance: BG
(YAF YGD)+~~(~RD YGD) ARLG+A
R, =O.
(48)
(4%
104
S. S. E. H. ELNASHAIE, S. S. ELSHISHINI
where
al =
Fc
C
?H~Cpfpf, ARI aR = QER
a2 = FGM 
CPlH~C~fpf,
aG =QEGGGD'
ARI
as=FcsH~Cn~P~,
AGI
(50) (51)
in dimensionless
variables
R, = a, erciYG (1  $Q), where (Y, =A,Co(l and the exothermicity E), & ^( = RTrf reaction is given by:
(AH4
(53)
(54)
The endothermicity
factors
reactions
k=cA,f~m~~f, rf pf
heat of cracking
This model has been used by Elnsshaie and ElHennawi to investigate the multiplicity phenomenon in fluid catalytic cracking units. Since the model involves a reaction kinetic network, they were able to investigate the gasoline yield of the system. The investigation of Elnashaie and ElHennawi [28], using this relatively more rigorous model, confirmed the conclusions of Iscol [24] and contradicted the conclusions of Lee and Kugelman [26]. Elnashaie and ElHennawi found that the multiplicity region covers a very wide range of operating conditions (Figure lb). They also found that the maximum gasoline yield corresponds to the middle unstable branch of the bifurcation digaram, and that operation outside this unstable branch, at any of the other stable steady states, gives very low gasoline yield.
105
Model
The model of Elnashaie and ElHennawi recognizes the twophase nature of the fluidized beds in both the reactor and the regenerator, albeit in a simple manner. The model uses a reaction network that relates the different steps of the cracking reactions to each other and to the reactor model. From a hydrodynamics point of view, a simplified twophase model is used and many assumptions were introduced to simplify the overall model of the system. With regard to the kinetics of the cracking reaction, although the approach adopted, based on lumping hundreds of components into three pseudocomponents, is reasonably sound for the purpose of investigating bifurcation behaviour and gasoline yield, the network used has a strong deficiency in the lumping of coke with light hydrocarbons in one component while they have completely different roles. A fourcomponent network [50] may improve the reliability of the model. However, a much more detailed network is needed for computing product distribution and gasoline octane number [51]. It is also important to notice that the activation energies of the kinetic reaction network are obtained from the work of Weekman [46,47] and Weekman and Nate [48], which gives the rate constants at only two temperatures. Therefore, the reliability of these activation energies is not high, and more experimental work is required to accurately determine the activation energies and rate constants for different gas oil feedstocks. Another weakness with regard to this model is the fact that it has not been systematically checked against the performance of commercial, or even pilot plant, FCC units.
EDWARDS
AND
KIM MODEL
(E & K MODEL)
The model used by Edwards and Kim [27] is proprietary; however, the authors give a brief summary of the concepts and relations employed by them in the use of the model to investigate the multiplicity phenomenon. The model consists of an overall carbon balance for the whole unit (reactor + regenerator) in the following form:
(57)
In this model, the capacity of the reactor is considered negligible in comparison to the capacity of the regenerator. This is justified by Edwards and Kim [27] by the fact that modernday FCC units reactor normally amounts to less than 1% of the total catalyst in the system. The energy balance of the system is given as:
(58)
where the heat capacity of the reactor has been assumed negligible as compared to the heat capacity of the regenerator
Qr = FAF&,(TG TAF) +Fccp,(TG TR) +QL. (59)
The rate of carbon formation, which appears in the right hand side of equation (57) is given by:
cc> +&CT,, Fc
Phc) Fc
(60)
The first term on the right hand side of (60) represents catalytic carbon formed by cracking, the second term represents the rate of coke entrainment in the stripper, and the third term is the rate of laydown of additive coke. A formula for coke burning similar to that used by Iscol [24] and by Lee and Kugelman [26] has been used in this model.
106
S. S. E. H. ELNASHAIE, S. S. ELSHISHINI
Edwards and Kim [27] use the following pseudosteady state relation for the computation the catalyst circulation rate when the gas oil conversion is known,
FCc~s(TG
of
TR) +FGF%~(TGF
TR.)FGF
(AH, +ecAHcr)=
0.
(61)
The authors used this model to investigate the behaviour of a commercial FCC unit and concluded that the phenomenon of the multiplicity of the steady state does exist, and they explained some of the pathological behaviour of the unit due to the existence of multiple steady states. Evaluation of the Model
It is extremely useful to have a view from industry. The model and the paper give lots of extra insight into the behaviour of the complex fluid catalytic cracking units. The neglect of the carbon and the heat capacity of the reactor makes the model valid only for systems where the inventory of catalyst in the reactor is much smaller than in the regenerator. However, in such systems, the reaction is taking place in the riser where the catalyst and gases are moving in plug flow, and hence, the lumped parameter formulation in terms of CSTR may not be valid. The model does not recognize the twophase nature of the fluidized beds in both the reactor and the regenerator, and is similar in this respect to the models of Kurihara [25], Iscol [24], and Lee and Kugelman [26]. In the expression for the rate of coke formation R,f, (60), the important first term expressing the rate of catalytic coke formation is made dependent upon Fc, the rate of catalyst circulation. In fact, Fc is neither a state variable nor a capacitance term. It is an inputoutput parameter, and therefore the rate of a process taking place inside the system should not be expressed as a direct function of it. The relation (62) for cc seems to be highly empirical, where E, is a function of (TR,TG, CG, Fc, FGF). In fact, any consistent mass and heat balance formulation will show that cc is not a direct function of FC or TG or FGF. Actually, these parameters, through the overall mass and heat balance, will affect TR in different ways depending upon the configuration, the size, and other conditions of the system. TR will then affect ec through the Arrhenius dependence of the rate constants upon TR. Edwards and Kim 1271reach opposite conclusions to those of Lee and Kugelman [26]. They conclude the existence of multiple steady states; however, their conclusions regarding the bifurcation behaviour of the system need to be clarified in two important points. 1. The relation between multiplicity of the steady states and catalyst circulation rate Fc. Heat is communicated from the regenerator to the reactor by means of the catalyst circulation rate, which is also responsible for transporting the carbon formed in the reactor to the regenerator. Therefore, too low a catalyst circulation rate will deprive the endothermic reactions in the reactor from the necessary heat. The cracking reactions will stop, and consequently, carbon formation in the reactor will stop, which results in a sharp drop of the carbon supply to the regenerator, and the whole system will quench. On the other hand, too high a catalyst circulation rate may supply too much heat to the reactor, raising its temperature and causing overcracking with large carbon formation. This, in turn, will raise the amount of carbon recirculated to the regenerator, and ignition occurs, causing complete loss in gasoline yield. For intermediate values of the catalyst circulation rate, which is the range in which most industrial units are operating, multiple steady states may exist. Actually, there are three steady states: a quenched low temperature steady state with almost no reactions taking place, an
of Industrial
FCC Units
107
steady state with almost zero gasoline yield and very high rate of unstable steady state with a moderate temperature and
high gasoline yield. This last steady state is the one at which most industrial units are operating. For any fixed value of catalyst circulation rate, in this region, multiple steady states do exist. Therefore, the conclusion of Edwards and Kim [27] that, for an open loop system, there exists one unique steady state solution when the catalyst circulation rate is fixed, is not correct. A unique steady state can occur if the chosen fixed value for the catalyst circulation rate lies outside the multiplicity region, since no system will exhibit multiple steady states over the entire range of parameters. A unique steady state can be obtained in a closed loop system, say, with a feedback proportional controller. The occurence of multiplicity will depend upon the controller gain [48]. For certain values of the controller gain, the middle steady state may become unique and stable, and the multiplicity may disappear altogether. 2. Multiplicity and the degree of combustion completion in the regenerator. that there are two sources of multiplicity in chemically reacting systems: (a) isothermal (or concentration) multiplicity, resulting from the nonmonotonic dependence of the rate of reaction upon the concentration of one or more of the reactants. (b) thermal multiplicity, resulting from the exothermicity of the reaction (the reaction should be highly exothermic and the activation energy of the reaction should be high). In FCC units, obviously the cracking reactions cannot be the source of multiplicity because the kinetics of the reactions are monotonic and the main reactions are endothermic. Therefore, neither thermal nor isothermal multiplicity is possible in the reactor. The only possible source of multiplicity is the regenerator, where a highly exothermic reaction is taking place, that is carbon burning. Therefore, partial combustion is not the source of multiplicity as stated by Edwards and Kim [27]. Actually, complete combustion of the carbon in the regenerator gives larger regions of multiplicity. This has been proved to be true by Elshishini and Elnashaie [31] (Figure 2). It is wellknown
FGM
RTR PR .
The volumetric gas flowrate at outlet of the regenerator is: & RTG GG = (0.5 WH + 0.5 Wco) 100
G
FAFRTG
29PG
The partial cracking of gasoline and gas oil to lighter hydrocarbons. The heats of cracking reported earlier [29] were based on complete cracking of hydrocarbons to carbon and hydrogen, and thus, were overestimated. In this model, the heats of cracking were modified. The overall heat of cracking obtained after introducing these modifications was found to be very close to the industrial value obtained empirically [51,52]. 3. The lumping of light hydrocarbon gases with coke. Weekman [46,47] kinetic scheme lumps light gases with coke. This is not suitable for realistic modelling of commercial FCC units; therefore, the amount of light gases was obtained from the weight ratio of coke to (coke + gases) given in plant data. 4. The recycle stream. Weekman [46,47] kinetic scheme does not account for the formation of HCO (heavy cycle oil), LCO (light cycle oil), and CSO (clarified slurry oil), which are 2.
108
S. S. E. H. ELNASHAIE, S. S. ELSHISHINI
the fractions produced in addition to gasoline. In the refineries, the only fraction recycled is HCO, and to calculate it, the ratio of HCO/(HCO + LCO + CSO) was obtained from plant data. Evaluation of Elshishini and Elnashaie Model The model was successfully compared with two industrial FCC units, and it was shown that both the units are operated at the middle steady state (Figure 3) and that the multiplicity region covers a very wide range of parameters. The model was also used to investigate the effect of feed composition on the performance of FCC units [31,32]. Figure 3 shows the Van Heerden diagrams (Figure 3a) and the unrescted gas oil and gasoline yield profiles (Figure 3b) for both industrial units simulated. It is clear that the maximum gasoline yield for both industrial units occurs at the multiplicity region and, specifically, at the unstable saddle type state. It is also clear from the figure that both units are not operating at their optimum conditions, with the operating point slightly shifted from the maximum gasoline yield. Simple manipulation of the operating variables can shift the units to their maximum gasoline yield with a considerable improvement in the productivity of the unit [30,31]. The model needs to be further improved to avoid the empirical evaluation of the ratio of carbon to light hydrocarbons from industrial measurements, by using a Ilump kinetic network [50]. Also, the effect of recycle on the kinetics needs to be incorporated into the model in a more rational way than its present empirical form. A more rigorous kinetic model for coke and hydrogen burning in the regenerator needs to be incorporated, instead of the simple kinetic model used. The model also needs further development to include modern riser type FCC units. Since the units are usually operated at the middle unstable steady state, extensive effort needs to be carried out for the analysis of the dynamic behaviour of open loop and closed loop systems [33].
CONCLUSION
Empirical models could be useful to simulate a unit operating at the conditions for which the empirical model was derived, but these models cannot simulate the performance of the reactor at any other conditions. Such models cannot be used reliably for design purposes or for the investigation of bifurcation behaviour, as was demonstrated in the evaluation of these models. Furthermore, the introduction of the twophase model of fluidization is not an unnecessary sophistication, since the role of bubbles is not only to achieve better mixing, but also to supply reactants to the active dense phase and to remove intermediate products from the active dense phase to the inactive bubble phase. Thus, bubbles have an important and complex effect on conversion, yield, and selectivity of the system. They also affect the heat balance of the system, especially in the regenerator, which is the source of heat to the system. Much experimental and theoretical work is needed in cooperation between industry and academia, to develop rigorous models of highfidelity for this industrially important system. Both the steady state and the dynamic behaviour of the unit need to be investigated. From a fundamental point of view, such a research will have a strong impact on the understanding of bifurcation behaviour in reactorregenerator systems. A richness of steady state and dynamic phenomena, exceeding those found for the classical CSTR problem, is certainly lying there waiting to be discovered. Our preliminary unsteady state investigation (331 has shown very interesting bifurcation behaviour including complex hysteresis and pitchfork type multiplicities. The dynamic behaviour also reveals very high sensitivity to initial conditions in the neighbourhood of the desirable middle steady state as well as high sensitivity to the dimensionality of the dynamic model and the different assumptions involved in it.
109
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