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Howard P. Isermann Department of Chemical Engineering Rensselaer Polytechnic Institute Troy, NY 12180-3590 bequeb@rpi.edu Fax: (518)276-4030 Tel: (518)276-6683 Submitted to Chemical Engineering Science July 1996
Keywords.
ABSTRACT
Steady-state multiplicity analysis is used to study the operability of a jacketed exothermic styrene polymerization CSTR. The global multiplicity behavior is characterized in terms of an initiator decomposition Damkohler number and the dimensionless heat of reaction. Low and high temperature infeasibility regions are shown to occur under certain design conditions. The approach developed is based on using a combination of analytical and numerical techniques to guide the analysis, rather than using a purely numerical approach. A reactor design used by previous researchers to show poor closed-loop performance from a single input-single output control strategy is studied in this paper. It is shown how this poor performance could have been predicted, and eliminated, at the process design stage using our bifurcation-based approach.
1 Introduction
The integration of process design and control (or operability) has been recognized as an important objective for many years. A number of relevant techniques have been proposed, including exibility analysis (based on nonlinear programming and steady-state models), resiliency (based on linear, multivariable models), and steady-state and dynamic \back-o " analysis (where the actual operating point is chosen by \backing o " from the optimum point which lies at the intersection of constraints). In this paper we present an approach, based on bifurcation (singularity) theory, to understand how design parameters in uence the characteristic input/output behavior of process systems. We study the steady-state multiplicity behavior of a jacketed exothermic styrene polymerization CSTR. Since the structure and properties of polymers are determined primarily by the operation of the chemical reactor in which they are made, there is signi cant motivation to optimize the process design and operation to improve controllability. Previous researchers showed poor single input-single output control performance for a given set of polymerization CSTR design parameters. In this work we show how this poor performance could have been predicted, and eliminated, at the process design stage using our bifurcation-based approach. The bifurcation results presented in Russo and Bequette (1995, 1996a, 1996b) are particularly important from a practical \controllability" point of view. This analysis demonstrates that in some regions of the parameter space there does not exist any manipulated variable value which will allow operation at a steady-state setpoint (using the cooling jacket owrate as the single manipulated variable). Russo and Bequette (1995) showed that under certain conditions a two-state CSTR model (neglecting cooling jacket temperature dynamics) could have a monotonic steady-state relationship between the reactor temperature and cooling jacket temperature, while a three-state CSTR model operated under the same conditions exhibited multiple steady-state behavior between the reactor temperature and the cooling jacket owrate. Thus, we see that an analysis of the two-state CSTR model could lead one to believe that the system is inherently \safer" and easier to operate than is the case as predicted by a more realistic three-state CSTR model incorporating a cooling jacket energy balance. We are motivated in our studies to consider these attributes of \process controllability" and \process operability" in order to understand how modeling decisions (and ultimately, design and operation decisions) e ect the operating characteristics of the chemical reactor.
MMA. They studied the homopolymerizations of MMA and vinyl acetate, and their copolymerization. The steady-state and dynamic behavior was classi ed in the parameter space by varying system parameters and using the Routh-Hurwitz criteria to give conditions on the characteristic equation coe cients for a speci ed eigenvalue structure. Schmidt et al. (1984) demonstrated the experimental existence of multiple steady-states under nonisothermal reactor conditions, and presented experimental veri cation of steady-state isolas for the homopolymerizations of MMA and vinyl acetate. Previous modeling studies were used to guide experiments in nding multiplicity behavior. Choi (1986) compared the bifurcation results for two models of the homopolymerization of MMA. The rst model utilized the \standard" kinetic description (common to free radical initiation), whereas the second model assumed that the initiator concentration was constant. A slightly di erent dimensionless group parameterization was used which provided a more detailed steady-state structure, as compared to previous work. Teymour and Ray (1989) performed a bifurcation analysis of a model of an experimental polymerization reactor. The model parameters used were obtained from the literature (no adjustment was made to these parameters for the present experimental system). They presented the rst experimental evidence of limit cycle behavior in the solution polymerization of vinyl acetate, and classi ed the steady-state and dynamic behavior in the parameter space. This analysis was used to guide experiments to nd regions of process parameters where limit cycles were predicted to occur. Adebekun et al. (1989) analyzed the steady-state multiplicity behavior possible in the polymerization of MMA in a CSTR. The primary focus of this work was to include polymer properties such as the molecular weight distribution (MWD), number average chain length, and polydispersity of the MWD in the bifurcation analysis. They rea rmed work by Schmidt and Ray (1981) which indicated that the multiplicity behavior in an isothermal polymerization reactor was the result of the \gel e ect". The presence of two steady-state isolas over a very small region of solvent volume fractions was demonstrated. Kim et al. (1991) studied the homopolymerization of styrene in a series of two CSTR's. One important point made in this work was that an understanding of the reactor behavior is important for the design of control systems for producing polymers with the desired physical properties. The use of more than one reactor was justi ed by noting that often the rst reactor serves to prepolymerize the monomer. Kim et al. (1991) found limit point bifurcations, Hopf bifurcations, in nite periodic orbits, period doubling bifurcations, isola behavior, and multiple Hopf bifurcation 6
points. Teymour and Ray (1992a) presented an extensive study of limit cycle behavior in an experimental laboratory reactor. They found that a major problem with studying the dynamics of small (lab-scale) reactors is the damping e ect of reactor externals such as the reactor wall, impellor blades and shaft, etc. Teymour and Ray (1992a) found that either increasing the residence time or decreasing the coolant temperature lead to limit cycle behavior in the experimental polymerization reactor. The model was able to predict the oscillation amplitudes and limit cycle periods well, with only small adjustments in a heat transfer coe cient. Teymour and Ray (1992b) focused their analysis on a full-scale polymerization reactor. They modi ed the model used in previous studies to more accurately describe conditions in an industrial polymerization reactor. The bifurcation analysis package AUTO (Doedel, 1986) was used to obtain an understanding of the di erent types of behavior possible in this reactor system. The full-scale model demonstrated even more complex dynamics than the lab-scale model. Pinto and Ray (1995a) constructed a mathematical model of the copolymerization of MMA and vinyl acetate in a lab-scale reactor. The bifurcation behavior of the system was examined using AUTO (Doedel, 1986) and the e ect of perturbations in the heat transfer coe cient and the coolant temperature were studied. Experimental support for limit cycle behavior demonstrated that decreasing the percentage of MMA monomer in the feed removed the stable limit cycle. Pinto and Ray (1995b) studied the copolymerization of MMA and vinyl acetate in a lab-scale reactor. They demonstrated that the system dynamics were very sensitive to small changes in the feed conditions, particularly, the initiator feed concentration. In an extremely small area of parameter space, two isolas were predicted. However, they determined that the appearance of the second isola was related to the \gel e ect" correlation and may not be an actual feature of the physical system. They showed that a boiling constraint that arises due to operation at atmospheric conditions was responsible for regions of up to ve steady-states. Multiple stable periodic orbits and isolas of periodic solutions were also found.
primary manipulated variable used to control the reactor temperature (which in turn speci es the conversion and thus the polymer properties). It is worthwhile to note that none of the studies reviewed considered the e ect of a cooling jacket on the steady-state and dynamic behavior of polymerization CSTR's. Congalidis et al. (1989) assumed that a \properly tuned" PI controller could be used to manipulate the coolant ow rate in order to obtain any value of the reactor jacket temperature. However, it was demonstrated in Russo and Bequette (1995) that for even simple 1st order kinetics (A ! B ) that including a thermal energy balance around the cooling jacket lead to interesting bifurcation results which are not present in a lower order (two-state) model of the reactor. Perhaps the most important result obtained was that even for the simple kinetic model used, the presence of infeasible reactor operating regions is predicted. Therefore, it is a poor assumption to neglect the cooling jacket energy balance in the control system design. It is well known that constraints on input variables can result in severe di culties in obtaining robust control. However, these constraints are not due to any process equipment limits (such as a maximum owrate for a pump) but are chosen as physical limits on the cooling jacket owrate. Pinto and Ray (1995b) stressed that the role of physical constraints on the model has been largely overlooked in the past. These constraints, taken with the mathematical model, create a new model which may or may not present completely di erent bifurcation structures that can improve the design and operation of real processes (Pinto and Ray, 1995b). Since the cooling jacket owrate is the primary manipulated variable for control of reactor temperature, it is crucial to use it as the bifurcation parameter in order to understand how it in uences the behavior of the system.
In this case, the cooling jacket owrate was the primary manipulated variable while the monomer owrate (the secondary manipulated variable) was only \changed" if the cooling jacket owrate \hit" a constraint. A number of di erent control case studies were conducted by Hidalgo and Brosilow (1990). The response of a conventional SISO controller (manipulating cooling jacket owrate alone) was compared to a MISO controller (coordinated control manipulating cooling jacket owrate and monomer owrate). The performance of the MISO control strategy was substantially better than the SISO control strategy. In fact, for a large enough setpoint change, the SISO control strategy is unstable. However, Hidalgo and Brosilow never explain why the SISO controller performs so poorly, especially in light of the fact that a nonlinear model of the process is used which incorporates a great deal of process information in the control strategy. Hidalgo and Brosilow (1990) note that \safe control of an unstable process requires the availability of a su cient control action to keep the process in a small region about the desired operating point in spite of disturbances and control e ort constraints." They claim that the styrene polymerization CSTR \can not be safely controlled by manipulating only the cooling jacket owrate", yet no physical explanation is presented. It has been surmised from the review section that few if any bifurcation studies have been conducted on a jacketed polymerization CSTR. This fact coupled with the intriguing results of Hidalgo and Brosilow (1990) make this polymerization system an ideal choice for further study.
10
kd ?!
2R
ki M + R ?! kp Pn + M ?!
P1 Pn+1
ktd T n + Tm Pn + Pm ?! ktc Pn + Pm ?!
Tn+m
where I is the initiator, R is the radical produced by initiator decomposition, M is the monomer species, P is the growing polymer chain, and T is the terminated polymer chain (cf. Billmeyer (1984) for a discussion on free radical polymerization kinetics). A number of assumptions were used by Hidalgo and Brosilow (1990) in obtaining the styrene polymerization CSTR model. In particular, the quasi-steady-state approximation and the long chain hypothesis were employed in the kinetic modeling. The quasi-steady-state approximation can be made by realizing that the lifetimes of the radical species R, P are short compared to the system time constants (Jaisinghani and Ray, 1977). Hence, the net reaction rate of the radicals is near zero (rR 0, rP 0). The long chain hypothesis states that most of the monomer is added to existing polymer chains as opposed to starting new polymer chains. In addition, the \gel e ect" (a decrease in termination rate associated with increased viscosity as the reaction proceeds) was neglected, since the reactor was operated at a relatively high solvent volume fraction. Choi (1986) notes that this is generally a good assumption for high solvent volume fractions. Termination for the styrene polymerization is generally due to combination (i.e. kt = ktc ). Physical properties of the reaction mixture such as density, heat capacity, heat transfer coe cient, etc. were assumed constant. The reader is referred to Appendix 1 and Hidalgo and Brosilow (1990) for additional details concerning the modeling assumptions and derivation of the modeling equations. The model for polystyrene polymerization as given by Hidalgo and Brosilow (1990) is: dCi = (QiCif ? (Qi + Qm + Qs )Ci) ? k C
d i V dCm = (QmCmf ? (Qi + Qm + Qs)Cm) ? k C C p m gp dt V
dt
(1) (2)
11
reactor temperature, cooling jacket temperature, concentration of growing polymer, and cooling jacket owrate, respectively. The initiator is azobisisobutyronitrile (AIBN) dissolved in benzene, while the monomer is styrene and the solvent is benzene. The process ow diagram for the styrene polymerization CSTR with a cooling jacket is shown in Figure 1. Five di erent sets of numerical values of the process parameters are given in Hidalgo and Brosilow (1990). The variables of the styrene polymerization model are de ned in Table 1, while a representative selection of the process parameters is shown in Table 2. No analysis of the multiplicity or open-loop dynamic behavior of this model has been performed. The four-state polymerization CSTR model can be extended in order to calculate the numberaverage molecular weight (NAMW) Mn . Following Schmidt and Ray (1981), two polymer chain moment equations are appended to the current model:
dT = (Qi + Qm + Qs)(Tf ? T ) + (? Hr ) k C C ? UA (T ? T ) (3) c dt V Cp p m gp CpV dTc = Qc(Tcf ? Tc) + UA (T ? T ) (4) c dt Vc c Cpc Vc s d Ci Cgp = 2fk (5) kt where Ci , Cm, T , Tc , Cgp , and Qc represent the concentration of initiator, concentration of monomer,
where 0 is the total molar concentration of dead polymer and 1 is the total molar concentration of monomer units present as polymer (Schmidt and Ray, 1981). It can be shown (Appendix 2) that equation 7 becomes: d 1 = k C C ? Qt (8) p m gp V 1 dt The number-average molecular weight (NAMW) Mn is de ned as:
P1 i=1 Mi Ni P 1
d 0 = 1 k C 2 ? Qt dt 2 tc gp V 0 d 1 = 1 k C 2 ? Qt dt 1 ? tc gp V
(6)
1
(7)
Mn =
i=1 Ni
(9)
where Mi is the molecular weight of the ith polymer and Ni is the number of molecules of type i (Billmeyer, 1984). For most polymers the number-average molecular weight (NAMW) lies close to the peak of the molecular weight distribution curve (Billmeyer, 1984). The number-average 12
molecular weight (NAMW) can be obtained from the moment equations by noting that Mn is simply: Total mass of polymer = 1 MWmono V Mn = Total (10) moles of polymer V where MWmono is the molecular weight of the repeating monomer unit, which in our case is styrene (?CH2CH (C6H5 )?) with MWstyrene = 104:15g/mol. Equations 1 { 5 can be written in the following dimensionless form:
0
dx1 = q x ? (q + q + q )x ? i 1f i m s 1 d dx2 = q x ? (q + q + q )x ? m 2f i m s 2 d
d d (x3)x1 p p (x3)x2 x5
where x1 , x2 , x3 , x4 , x5 , and qc are the dimensionless initiator concentration, monomer concentration, reactor temperature, cooling jacket temperature, growing polymer concentration, and cooling jacket owrate, respectively. We demonstrated in Russo and Bequette (1996b) that this type of cooling jacket energy balance holds for recirculating cooling jackets and that the use of multiple cooling jacket compartments does not change the qualitative steady-state input-output behavior. As noted by Aris (1993), if one is interested in examining the e ect of varying reaction kinetics, then it should not be used to scale the time variable. We are interested in varying the residence time (by varying the reactor owrate) and the reaction kinetic parameters, hence time is scaled using a V . The dimensionless variables and parameters are de ned in the nominal reactor residence time, Q t0 Table 3, with values of the corresponding dimensionless parameters shown in Table 4 (for Table 2 conditions). The dimensionless moment equations are: dx6 = 1 (x )x2 ? x (16) d 2 t t 3 5 6 The number-average molecular weight (NAMW) Mn is:
d d (x3 ) x 1 t t (x3)
dx7 = d
p p (x3)x2x5 ? x7
(17) (18)
7 Mn = MWmono x x
13
of x3 . Finally, equation 14 can be solved for x4 as a function of x3. Now, substituting this into equation 13 (at steady-state) gives: c + p p (x3 ) (x3) + (x4f ? x3 ) q h(x3; qc; p) = qm x2f q + q + q + ( x ) ( x ) + i m s p p 3 3 2 qc (qi + qm + qs )(x3f ? x3 ) = 0 (19) where (x3 ) is 2f d d (x3)qi x1f = x5 (20) t t (x3)(qi + qm + qs + d d (x3)) where x3 (dimensionless reactor temperature) is the controlled output, qc (dimensionless cooling jacket owrate) is the manipulated input, and p is a vector of parameters. (x3) = It is interesting to note that this equation is very similar in nature to the equivalent equation for the three-state CSTR model. ) + q (x ? x ) + (x ? x ) qc = 0 h(x2; qc; p) = qx1f q + (x(2x (21) 2f 2 3f 2 2) 2 + qc The essential di erences in these two equations are in the numerator and denominator of the term. In the three-state CSTR case there is a single nonlinearity ( (x2)) while in the fourstate polymerization CSTR case the nonlinearities ( p (x3) (x3)) multiply each other. This makes a complete analytical treatment for the bifurcation analysis much more di cult. Therefore, a combination analytical/numerical bifurcation analysis is performed.
s
Now, we want to determine if it is possible for the polymerization CSTR model to have input @h . The result is: multiplicity or isolas. Consider the value of @q c @h 2 (x4f ? x3) (25) @qc = 2 ( 2 + qc)2 6= 0 15
@h = 0 h = @q c @h = @h = 0 h = @x 3 @qc
@h = 0 h = @x
3
Therefore, when qc is the manipulated variable then input multiplicities, isolas, transcritical bifurcations, and pitchfork bifurcations cannot occur between x3 and qc . Upon examination of the derivatives of h(x3; qc ; p) with respect to the parameters, it can be determined that qi , qm , and qs are the only parameters that when varied can lead to input multiplicities or isola behavior; these are therefore important disturbance variables. The derivatives of h(x3; qc ; p) with respect to the other parameters remain the same sign. Elementary catastrophe theory allows one to characterize the number of multiple steady-state solutions to equations 11 { 15. The appearance or disappearance of output multiplicities occurs when higher order derivatives of h with respect to x3 are zero.
The highest order singularity (value of k) satisfying equation 26 determines the number of steadystate solutions. A multiplicity of k + 1 solutions exists around the codimension k singular point satisfying equation 26 (Stewart, 1981). As noted previously, the more complicated structure of the polymerization CSTR modeling equations make an analytical treatment di cult. The highest order singularity found numerically corresponds to k = 2, hence up to three di erent steady-state dimensionless reactor temperatures may exist for a given dimensionless coolant owrate. The determination of regions of feasible and infeasible reactor operation are important for feedback control purposes, since one can see directly if the current operating conditions are \feasible" in a steady-state sense. Therefore, the global parameter space is divided into regions with di erent types of multiplicity behavior. However, there are a large number of parameters associated with the polymerization system so it is not clear how to best present the bifurcation results. This current study portrays the singularity loci on the d - 2-D cross section of the parameter space. This follows the development in Russo and Bequette (1995, 1996a, 1996b) in that kinetic and thermodynamic properties of the system are used to classify the behavior. d is the Damkohler number associated with the dissociation of the initiator into the radical species. If one examines equation 19 we see that as d ! 0 no reaction occurs, since there are no radicals present to initiate the the reaction. (dimensionless heat of reaction) is a direct measure of the exothermicity of the reaction. 16
(26)
The singularity described by equation 26 is strictly not a \point" but a locus of points in the global parameter space. It is possible to construct singularity loci for a number of low dimensional cross sections of the parameter space. However, since we are interested in how changes in process parameters in uence the location and existence of these singularities on the steady-state inputoutput (x3 - qc ) curves, the singularity locus is constructed over the bounds on the dimensionless coolant owrate (qc ).
@h = @ 2h = 0 h = @x 3 @x2 3 qc 2 0; 1)
(27)
We denote d , , and x3 that satisfy the hysteresis condition (equation 27) as d?hyst , hyst , and x3?hyst . The singularity locus described by equation 27 bounds the region of output multiplicity behavior in the parameter space. A codimension 1 fold bifurcates from the bounds on the cooling jacket owrate. This lower order singularity separates the global multiplicity behavior in the d parameter space.
@h = 0 h = @x 3 qc = 0 @h = 0 h = @x 3 qc ! 1
(28)
(29)
Equations 28 and 29 satisfy the \0-disjoint" and \1-disjoint" loci, respectively. In general, equations 28 and 29 can be satis ed for \low" and \high" temperature limit points, as qc approaches zero or in nity, respectively. Hence, there are a total of four curves in the d - space that bifurcate from the singularity locus given in equation 27.
also seen if one neglects the cooling jacket energy balance in the modeling equations, which results in a three-state model. Figure 3 corresponds to the same conditions as the d = 0:006 line on Figure 2. Notice that over a range of dimensionless cooling jacket temperatures the reactor temperature is predicted to be less than the cooling jacket temperature, which results in the cooling jacket owrate being negative (cf. Figure 2). A negative cooling jacket owrate is physically impossible. The reactor temperature can not be less than the cooling jacket temperature, since the reactor and cooling jacket have equal feed temperatures and the reaction is exothermic. Figure 4 shows the e ect of increasing d for a \larger" value of ; as d is increased the steady-state input-output curve behavior changes from multiple steady-states to a region of high temperature infeasibility. The high temperature limit point (LP) moves toward in nite cooling jacket owrate. Once again, this infeasibility can be seen in a lower dimensional model that neglects the cooling jacket energy balance. Figure 5 corresponds to the same conditions as the d = 0:008 line on Figure 4. Notice that over a range of dimensionless cooling jacket temperatures the cooling jacket temperature is predicted to be less than the cooling jacket feed temperature. This is impossible, since the reaction is exothermic and the feed temperatures of the reactor and cooling jacket are equal. The codimension 2 (cusp) singularity locus (which speci es the set of hysteresis points) and codimension 1 (fold) \0-disjoint" and \1-disjoint" loci (which specify the set of limit points) divide the d - parameter space into ve di erent regions as shown in Figure 6. These regions correspond to ve di erent steady-state input-output curves, shown in Figure 7. The d and values in regions I - V of Figure 7 are given in Table 5. Region I in the d parameter space corresponds to a monotonic relationship between x3 and qc , while in region II output multiplicity exists between x3 and qc (inverse S shaped input-output curve). Regions III and IV exhibit low temperature and high temperature infeasibilities, respectively, corresponding to \0-disjoint" and \1-disjoint" bifurcations. The presence of \0-disjoint" behavior is associated with overcooling of the reactor by the cooling jacket, whereas \1-disjoint behavior occurs when there is not su cient cooling by the cooling jacket (the heat transfer characteristics of the reactor are poor, as seen in large scale industrial reactors). Region V is an overlap of regions III and IV, where low and high temperature infeasibilities exist when the \0-disjoint" and \1-disjoint" loci intersect. The \dimensional" steady-state input-output curve indicated by the + mark in Figure 6 is shown in Figure 8; notice the reactor operation falls in a \high" temperature operating region of region I. Figure 9 is a plot 18
of the steady-state number-average molecular weight (NAMW) Mn as a function of the coolant owrate. Notice that the \high" temperature operating region has resulted in the production of polymer with \low" number-average molecular weight (NAMW). The d - diagram for the nominal dimensionless operating parameters (given in Table 4) is shown in Figure 10; notice the reactor operation falls in region IV. The steady-state input-output (x3 - qc ) curve is shown in Figure 11; this reactor design exhibits a \high" temperature infeasibility region. This input-output curve is shown in \dimensional" form in Figure 12, where the reactor temperature is shown as a function of the cooling jacket owrate. Figure 13 is a plot of the steady-state numberaverage molecular weight (NAMW) Mn as a function of the coolant owrate for the low and high temperature branches. Notice that the \high" temperature infeasibility region shown in Figure 12 has resulted in a corresponding infeasibility region of number-average molecular weights. Values of the NAMW from 8400 to 12000 do not exist under these operating conditions. The numberaverage molecular weight for the upper branch of Figure 13 is shown as a function of the steady-state temperature in Figure 14. The NAMW changes by almost an order of magnitude over a 40 degree Celsius range. The number-average molecular weight for the lower branch of Figure 13 is shown as a function of the steady-state temperature in Figure 15. The NAMW changes by approximately 15% over a 100 degree Celsius range, with a minimum around 115 oC . The number-average molecular weight is plotted versus the corresponding steady-state coolant owrate in Figure 16. Figure 16 shows that there could be potential problems controlling the number-average molecular weight by manipulating coolant owrate solely, due to the input multiplicity behavior in the \low" molecular weight region. Hidalgo and Brosilow (1990) claimed that this reactor could not be operated safely using only the coolant owrate as the manipulated variable for feedback control, but did not present an explanation. It is clear that the problem is that near the operating range of interest (corresponding to x3 0:75 or T 80 oC ) the gain between the dimensionless reactor temperature and the cooling jacket owrate is approaching zero as one moves further into the infeasibility region (cf. Figure 12. Hidalgo and Brosilow (1990) also placed a maximum constraint on the cooling jacket owrate of Qc = 60 liters min ; this corresponds to a maximum dimensionless cooling jacket owrate of qc = 3:8095. Notice from Figures 11 and 12 that this constraint virtually eliminates any ability to operate in the reactor range of interest with only the cooling jacket owrate. 19
q+ q
hyst (qc = 0)
(30)
Hence, in this case we can clearly see how the multiplicity behavior changes as a function of the dimensionless heat transfer coe cient ( ). If the residence time is held constant upon reactor 1 scaleup, then Dr , where Dr is the diameter of the reactor. Therefore, a \larger" reactor will have a lower value of , resulting in a shorter hysteresis locus. This larger reactor has less e cient cooling characteristics, which can shift the reactor operation into an undesirable region. 20
We compare the d - diagrams for two di erent reactor systems in order to demonstrate that the polymerization CSTR system exhibits the same type of dependence on dimensionless heat transfer coe cient (when the cooling jacket feed temperature is equal to the reactor feed temperature). Figure 6 corresponds to a 3000 liter reactor volume ( = 0:74074) whereas Figure 17 has a reactor volume of 1500 liters ( = 0:93328). As one can see, the larger reactor has a shorter hysteresis locus. It is clear that if we scale down the reactor size \enough" the reactor operation will move from region I through region IV into region II, resulting in multiple steady-state behavior. The multiplicity behavior in this case is a result of the \low" temperature operating region becoming feasible as the heat transfer characteristics improve when we \scaledown" the reactor size. An important point is that the hysteresis locus length is once again related to the value of the dimensionless heat transfer coe cient ( ) and the process owrates. Table 6 shows the values of hyst (qc = 0) and hyst (qc ! 1) for a number of process owrates and dimensionless heat transfer coe cients (the unspeci ed parameters are the default values given in Table 4). If we examine hyst(qc !1) we see that hyst(qc=0) hyst (qc ! 1) = qi + qm + qs + (31) qi + qm + qs hyst (qc = 0) which is the same relationship that was seen in the simpler three-state CSTR model presented in Russo and Bequette (1995).
hence it does not make physical sense to allow these dimensionless activation terms to become large. Consider instead a situation where the individual activation energies become large with respect to the reactor temperature. In this case, we see that d ! 1, t ! 1, and p ! 1. The resulting d - diagram is shown in Figure 18. The multiplicity behavior is grossly overestimated and shifted in the parameter space, as compared to Figure 6. The reactor operation is predicted to lie in region III whereas the operation exists in region I. We see that this form of the positive exponential approximation obscures the true nature of the multiplicity behavior.
Ep p = RTf 0 ,
reactor feed temperature. We want to understand how the various process owrates (initiator, monomer, and solvent) in uence the multiplicity behavior. The Damkohler number along the hysteresis locus ( d?hyst ) is not simply a linear function of the owrate as it was in the threestate CSTR model. For example, notice the behavior of d?hyst in Figure 19. We see that as one varies the initiator owrate (qi ) that d?hyst initially decreases and then it levels out and starts increasing (for a xed value of the solvent owrate qs ). This behavior is unique to the four-state polymerization CSTR model, in that there are multiple values of the initiator owrate for the same hysteresis Damkohler number. There exist certain operating regimes in which multiple steady-states can be avoided by either increasing the initiator owrate \enough" (thus decreasing the residence time of the reactor for a lower conversion), or by decreasing the initiator owrate \enough" (thus e ectively \quenching" the reaction due to an absence of radicals). In addition, notice on Figure 19 that decreasing the monomer owrate (qm ) tends to decrease d?hyst . Therefore, one can remove multiple steady-state behavior by decreasing the monomer owrate. This gure allows one to nd process operating conditions to guarantee a monotonic steady-state input-output curve over a range of operating conditions. For example, consider a Damkohler number of d = 0:015. For monomer owrates of qm = 0:3 and below (with a xed solvent owrate of qs = 0:48571) we see that there exists a wide range of initiator owrates which guarantee operation with a monotonic steady-state input-output curve. It is well-known that the amount of initiator present in the system generally controls the polymer properties (Hidalgo and Brosilow, 1990), hence the initiator owrate may only be varied over a narrow range to obtain the desired polymer properties. We see in Figure 20 that d?hyst initially decreases then starts increasing as one increases the initiator owrate (qi ) for a xed value of qm . We can set the desired initiator owrate and nd from Figure 20 the solvent owrate which guarantees monotonic steady-state input-output behavior. For example, for a value of d = 0:0175 and qi = 0:1, values of the solvent owrate qs = 0:4 and lower satisfy the monotonicity conditions. Figures 21 and 22 represent cases where the initiator owrate is xed and the monomer (qm ) and solvent (qs ) owrates were varied. We see in these cases that the hysteresis Damkohler number is a monotonic increasing function of both the solvent and the monomer owrates. Consider a polymerization CSTR with d = 0:0175 and a monomer owrate of qm = 0:4. We see in Figure 21 that we are guaranteed monotonic steady-state input-output behavior only if the solvent owrate is 23
lower than qs 0:5. However, if the monomer owrate is decreased from qm = 0:4 to qm = 0:2 then monotonic steady-state input-output behavior is possible with larger values of the solvent owrate (qs 0:7 and lower).
24
8 Conclusions
We have shown in this work that the bifurcation analysis shown in Russo and Bequette (1995, 1996a, 1996b) could be applied to a jacketed styrene polymerization CSTR. The role of physical constraints on the steady-state input-output behavior of a styrene polymerization model was studied. In particular, an analysis of the steady-state multiplicity behavior was conducted, and the e ect of dimensionless values of the heat of reaction, overall heat transfer coe cient, cooling jacket feed temperature, and physical limits on the cooling jacket owrate were considered. It was shown in Russo and Bequette (1996b) that this type of cooling jacket energy balance holds true for recirculating cooling jackets and that the use of multiple cooling jacket compartments does not change the qualitative steady-state input-output behavior. The global multiplicity behavior was characterized in terms of a Damkohler number for initiator decomposition and the dimensionless heat of reaction. The presence of low and high temperature infeasibility regions associated with disjoint bifurcation behavior was demonstrated. Polymer chain moment equations were appended to the four-state polymerization model. These equations were used to calculate the number-average molecular weight (NAMW). The addition of these equations does not change the underlying steady-state multiplicity or dynamic behavior of the polymerization CSTR. However, these polymer chain moment equations may exhibit interesting behavior of their own. For example, when the polymerization CSTR has a high temperature infeasibility region, there exists a range of infeasible number-average molecular weights. A polymerization CSTR with solely a high temperature operating region (e.g. the cooling jacket feed temperature may be too high) results in the production of polymer with a low number-average molecular weight (NAMW). Polymers with a low NAMW may exhibit input multiplicity with respect to cooling jacket owrate and thus may be di cult to control. The e ect of process design and operation parameters on the bifurcation behavior was considered. In particular, when the cooling jacket feed temperature is equal to the reactor feed temperature, the hysteresis locus length (which speci es the di erent types of input-output behavior) was a function of the process owrates and the dimensionless heat transfer coe cient. The positive exponential approximation was shown to obscure the true nature of the multiplicity behavior. The hysteresis Damkohler number ( d?hyst ) was not a linear function of the process owrates, unlike 25
the A ! B reaction network case. However, the in uence of the various process owrates on the Damkohler number hysteresis locus was determined in order to guarantee monotonic steady-state input-output behavior. We saw that under certain conditions a 3000 liter CSTR exhibited a region of high temperature infeasibility which was not present when the reactor was scaled down to 1500 liters. Decreasing the cooling jacket feed temperature was also found to move the steady-state input-output behavior into a globally feasible operating region.
Acknowledgment
This work was partially supported by a grant from the Petroleum Research Foundation, administered by the American Chemical Society. A portion of this work was performed while Wayne Bequette was on sabbatical at Northwestern University.
26
References
Adebekun, A.K., K.M. Kwalik, and F.J. Schork (1989). Steady-state Multiplicity During Solution Polymerization of Methyl Methacrylate in a CSTR. Chem. Eng. Sci., 44, 2269-2281. Aris, R. (1993). Ends and Beginnings in the Mathematical Modelling of Chemical Engineering Systems. Chem. Eng. Sci., 48, 2507-2517. Balakotaiah, V., D. Luss, and B.L. Key tz (1985). Steady-state Multiplicity Analysis of Lumpedparameter Systems Described by a Set of Algebraic Equations. Chem. Eng. Comm., 36, 121-147. Billmeyer, F.W. (1984). Textbook of Polymer Science., Wiley and Sons. Brooks, B.W. (1981). Dynamic Behaviour of a Continuous- ow Polymerisation Reactor. Chem. Eng. Sci., 36, 589-593. Choi, K.Y. (1986). Analysis of Steady State of Free Radical Solution Polymerization in a Continuous Stirred Tank Reactor. Polym. Eng. Sci., 26, 975-981. Congalidis, J.P., J.R. Richards, and W.H. Ray (1989). Feedforward and Feedback Control of a Solution Copolymerization Reactor. AIChE J., 35, 891-907. Doedel, E.J. (1986). AUTO: Software for Continuation and Bifurcation Problems in Ordinary Di erential Equations., California Institute of Technology, Pasadena, CA. Farr, W.W. and R. Aris (1986). \Yet who would have thought the old man to have had so much blood in him?" - Re ections on the Multiplicity of Steady States of the Stirred Tank Reactor. Chem. Eng. Sci., 41, 1385-1402. Hamer, J.W., T.A. Akramov, and W.H. Ray (1981). The Dynamic Behavior of Continuous Polymerization Reactors - II. Nonisothermal Solution Homopolymerization and Copolymerization in a CSTR. Chem. Eng. Sci, 36, 1897-1914. Hidalgo, P.M. and C.B. Brosilow (1990). Nonlinear Model Predictive Control of Styrene Polymerization at Unstable Operating Points. Comp. Chem. Eng., 14, 481-494.
27
Jaisinghani, R. and W.H. Ray (1977). On the Dynamic Behavior of a Class of Homogeneous Continuous Stirred Tank Polymerization Reactors. Chem. Eng. Sci., 32, 811-825. Kim, K.J., K.Y. Choi, and J.C. Alexander (1991). Dynamics of a Cascade of Two Continuous Stirred Tank Polymerization Reactors with a Binary Initiator Mixture. Polym. Eng. Sci., 31, 333-352. Pinto, J.C. and W.H. Ray (1995a). The Dynamic Behavior of Continuous Solution Polymerization Reactors - VII. Experimental Study of a Copolymerization Reactor. Chem. Eng. Sci., 50, 715-736. Pinto, J.C. and W.H. Ray (1995b). The Dynamic Behavior of Continuous Solution Polymerization Reactors - VIII. A Full Bifurcation Analysis of a Lab-scale Copolymerization Reactor. Chem. Eng. Sci., 50, 1041-1056. Ray, W.H. (1993). Modeling and Control of Polymerization Reactors. In Dynamics and Control of Chemical Reactors, Distillation Columns, and Batch Processes (DYCORD+ 1992), J.G. Balchen (Ed.), Pergamon Press, 161-170. Razon, L.F. and R.A. Schmitz (1987). Multiplicities and Instabilities in Chemically Reacting Systems - a Review. Chem. Eng. Sci., 42, 1005-1047. Russo, L.P. and B.W. Bequette (1995). Impact of Process Design on the Multiplicity Behavior of a Jacketed Exothermic CSTR, AIChe J., 41, 135-147. Russo, L.P. and B.W. Bequette (1996a). E ect of Process Design on the Open-Loop Behavior of a Jacketed Exothermic CSTR, Comp. Chem. Eng., 20, 417-426. Russo, L.P. and B.W. Bequette (1996b). Operability of Chemical Reactors: Multiplicity Behavior of Extended CSTR Models, AIChE J., Submitted July 1996. Schmidt, A.D., A.B. Clinch, and W.H. Ray (1984). The Dynamic Behavior of Continuous Polymerization Reactors - III. An Experimental Study of Multiple Steady-states in Solution Polymerization. Chem. Eng. Sci., 39, 419-432. Schmidt, A.D. and W.H. Ray (1981). The Dynamic Behavior of Continuous Polymerization Reactors - I. Isothermal Solution Polymerization in a CSTR. Chem. Eng. Sci., 36, 1401-1410. 28
Stewart, I. (1981). Applications of Catastrophe Theory to the Physical Sciences. Physica, 2D, 245-305. Teymour, F. and W.H. Ray (1989). The Dynamic Behavior of Continuous Polymerization Reactors - IV. Dynamic Stability and Bifurcation Analysis of an Experimental Reactor. Chem. Eng. Sci., 44, 1967-1982. Teymour, F. and W.H. Ray (1992). The Dynamic Behavior of Continuous Polymerization Reactors - V. Experimental investigation of Limit-cycle Behavior for Vinyl Acetate Polymerization. Chem. Eng. Sci., 47, 4121-4132. Teymour, F. and W.H. Ray (1992). The Dynamic Behavior of Continuous Polymerization Reactors - VI. Complex Dynamics in Full-scale Reactors. Chem. Eng. Sci., 47, 4133-4140.
29
Table 1: Variables in the styrene polymerization model. f - Initiator e ciency Ci - Initiator concentration Cm - Monomer concentration Cgp - Growing polymer concentration T - Reactor temperature Tc - Cooling jacket temperature 0 - Concentration of dead polymer 1 - Concentration of monomer units present as polymer Hr - Heat of reaction - Density of the reaction mixture - Density of the cooling jacket mixture c Cp - Heat capacity of the reaction mixture Cpc - Heat capacity of the cooling jacket mixture U - Overall heat transfer coe cient A - Heat transfer area kd - Rate constant for initiator decomposition kp - Rate constant for propagation kt - Rate constant for termination t - time Qi - Initiator owrate Qm - Monomer owrate Qs - Solvent owrate Qt - Total owrate through reactor Qc - Cooling jacket owrate V - Reactor volume Vc - Cooling jacket volume Cif - Initiator feed concentration Cmf - Monomer feed concentration Tf - Reactor feed temperature Tcf - Cooling jacket feed temperature 30
Table 2: Representative values of the styrene polymerization parameters (taken from Hidalgo and Brosilow, 1990).
= 0.6 = 5.95 * 1013 s?1 = 123,855.658 J mol?1 = 1.25 * 109 s?1 = 7008.702 J mol?1 = 1.06 * 107 l mol?1 s?1 = 29572.898 J mol?1
Qi Qs
? Hr = 69,919.56 J mol?1
UA Cp
c Cpc
Tcf = 295 K
31
Table 3: Dimensionless variables and parameters for the four-state polymerization CSTR model (Qt0 = Qio + Qm0 + Qs0 ).
x1 x3 x6 qi qs x1f x3f
d p
1
i = CC mf 0
x2 x4 x7 qm qc x2f x4f
t
m = CC mf 0
Tf 0 = T? Tf 0 p
0 = Cmf 0
?Tf 0 = TcT f0 p
1 = Cmf 0
Qi = Q t0 Qs = Q t0
if = CC mf 0
Qm = Q t0 Qc = Q t0 Cmf = C mf 0 Tf 0 = TcfT? p f0 Et = E p
?Tf 0 = TfT f0 p
d = E Ep
Ep = RT f0 V = V c
2
= =
(? Hr )Cmf 0 p Cp Tf 0
Cp c Cpc
=
t
UA Cp Qt0
d p d (x3 ) p (x3)
V kd0 exp(? d p ) = Q t0
mf 0 = VC Qt0 kp0exp(? p ) dx = exp( 1+ x3 3 ) p
mf 0 = VC Qt0 kt0exp(? t p) t0 = Q V t
t (x3)
tx = exp( 1+ x3 3 ) p gp = CC mf 0
x3 = exp( 1+ x3 )
p
x5
32
qi
= 0.11429
= 0.23699 = 13.17936
d p
= 9.6583e12
Table 5: d and values used in Figure 7 (x4f = 0:0). region d I 0.018 8 II 0.01 8 III 0.003 8 IV 0.004 14 V 0.001 14 33
Table 6: Representative values of hyst (qc = 0) and hyst (qc ! 1) for a number of di erent process parameters. hyst(qc!1) Parameter hyst (qc = 0) hyst (qc ! 1) hyst(qc =0) = 0.74074 4.86712 8.47244 1.74074 = 0.93328 4.86712 9.40955 1.93328 qi = 0.15 4.88992 8.38717 1.71520 qm = 0.3 5.65829 10.31529 1.82304 qs = 0.4 4.33069 7.83932 1.81018
34
Appendix 1
Derivation of the Polymerization Kinetic Expressions
Reaction rates of the free-radical polymerization kinetics (Hidalgo and Brosilow, 1990):
rI rR rP rM
= ?kd Ci = 2fkd Ci ? ki Cm Cr
2 = ki Cm Cr ? ktCgp
The long chain hypothesis is made to the monomer reaction rate, i.e. ki Cm Cr kpCm Cgp, because most of the polymer consumed is added to existing polymer chains and not in forming new polymer chains. In this case, rM becomes: rM = ?kpCmCgp (36) The quasi-steady-state approximation is made to the radical species R, P , since the radical species lifetimes are short compared to the system time constants (Jaisinghani and Ray, 1977). It is also assumed that no radicals exit the reactor. In this case, the radical reaction rates are set to zero (quasi-steady-state approximation), i.e. rR 0, rP 0. Solving these equations allows us to obtain the expression for the growing polymer chain concentration Cgp . 2fkd Ci = ki Cm Cr
2 kiCmCr = ktCgp
(37) (38)
(39)
Cgp =
2fkd Ci
kt
(40)
35
Appendix 2
Derivation of the Polymer Chain Moment Equations
From Schmidt and Ray (1981), the two polymer moment equations are written as:
Here, 0 is the total molar concentration of dead polymer and 1 is the total molar concentration of monomer units present as polymer (Schmidt and Ray, 1981) and is:
d 0 = 1 k C 2 ? Qt dt 2 tc gp V 0 d 1 = 1 k C 2 ? Qt dt 1 ? tc gp V
(41)
1
(42)
(43)
d 1 = k C 2 + k C C ? Qt (44) tc gp p m gp V 1 dt 2 . From the long chain However, from the quasi-steady-state approximation: ki Cm Cr = ktc Cgp hypothesis we note that: ki Cm Cr kpCm Cgp. Therefore, under these assumptions
2 ktcCgp
kpCmCgp
(45)
d 1 = k C C ? Qt p m gp V dt
(46)
36
Qm Cmf Tf
feed temp
solvent Tf Q s flowrate
coolant temp
Tc
x3
0.3
qc
Figure 2: Steady-state dimensionless reactor temperature versus cooling jacket owrate, x4f = 0:0. 37
= 6,
x3
0.8 0.6 0.4 0.2 0.0 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6
x3 > x4 x3 < x4
x4
Figure 3: Steady-state dimensionless reactor temperature versus cooling jacket temperature, d = 0:006, = 6, x4f = 0:0.
3.5 3.0 2.5 2.0 d = 0.008 d = 0.0065 d = 0.00625 d = 0.006
x3
1.5 1.0 0.5 0.0 0 5 10 15 20
qc
Figure 4: Steady-state dimensionless reactor temperature versus cooling jacket owrate, = 10, x4f = 0:0. 38
2.0
1.5
x3
1.0
0.5
x4
Figure 5: Steady-state dimensionless reactor temperature versus cooling jacket temperature, d = 0:008, = 10, x4f = 0:0.
20.0x10-3
I
16.0 12.0 Hysteresis locus "0-disjoint" loci "-disjoint" loci
II
8.0 4.0
III
0.0 4 6 8 10
IV
12 14 16 18 20
Figure 6: Global multiplicity behavior for the styrene polymerization CSTR model, x4f = 0:0, = 0:74074. 39
2.6 2.2 1.8 1.4 1.0 0.6 0.2 0 1 2 3 4 2.8 2.4 2.0 1.6
x3
2.6
2.2 1.8
x3
II
x3
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
qc
qc
III
1.2 0.8 0.4 0.0 0.0 0.1 0.2 0.3 0.4 5 0.5 0.6
qc
4
IV
4
3
3
x3 x3
1 0
0 0 5 10 15 20 25 30
qc
10
15
20
25
qc
40
210
190
T (oC)
170
150
130 0 20
Qc (liters/min)
40
60
80
Figure 8: Steady-state reactor temperature versus cooling jacket owrate, d = 0:01688, 13:17936, x4f = 0:0.
8400 8200
NAMW (g/mol)
Qc (liters/min)
40
60
80
Figure 9: Number-average molecular weight (NAMW) versus cooling jacket owrate, d = 0:01688, = 13:17936, x4f = 0:0. 41
I
0.15
d
0.10
II
0.05 0.00 4 6 8 10 12
IV
14 16 18 20
Figure 10: Global multiplicity behavior for the styrene polymerization CSTR model, x4f = ?1:14320.
3.0 2.5 2.0 1.5
x3
1.0 0.5 0.0 -0.5 0 2 4 6 8 10 12 14
qc
Figure 11: Steady-state dimensionless reactor temperature versus cooling jacket owrate, d = 0:01688, = 13:17936, x4f = ?1:14320. 42
T (oC)
Qc (liters/min)
Figure 12: Steady-state reactor temperature versus cooling jacket owrate, d = 0:01688, 13:17936, x4f = ?1:14320.
3
80x10
70
NAMW (g/mol)
Qc (liters/min)
Figure 13: Number-average molecular weight (NAMW) versus cooling jacket owrate, d = 0:01688, = 13:17936, x4f = ?1:14320. 43
80x10
70
NAMW (g/mol)
60 50 40 30 20 10 40 50 60 o 70 80
T ( C)
Figure 14: Number-average molecular weight (NAMW) versus steady-state reactor temperature: low temperature operating region, d = 0:01688, = 13:17936, x4f = ?1:14320.
8400 8200
NAMW (g/mol)
T ( C)
Figure 15: Number-average molecular weight (NAMW) versus steady-state reactor temperature: high temperature operating region, d = 0:01688, = 13:17936, x4f = ?1:14320. 44
160
180
200
8400 8200
NAMW (g/mol)
Qc (liters/min)
Figure 16: Number-average molecular weight (NAMW) versus cooling jacket owrate: high temperature operating region, d = 0:01688, = 13:17936, x4f = ?1:14320.
20.0x10
-3
I
16.0 12.0
II
8.0 4.0
III
0.0 4 6 8 10 12
IV
14 16 18 20
Figure 17: Global multiplicity behavior for the styrene polymerization CSTR model, x4f = 0:0, = 0:93328. 45
II IV III
20
25
30
Figure 18: Global multiplicity behavior for the styrene polymerization CSTR model using the positive exponential approximation, t ! 1, d ! 1, p ! 1, x4f = 0:0.
50x10-3
40
d-hyst
30
20
qi
Figure 19: Damkohler number hysteresis locus as a function of the initiator owrate for various values of the monomer owrate, x4f = 0:0, qs = 0:48571. 46
70x10-3 60 50
d-hyst
qi
Figure 20: Damkohler number hysteresis locus as a function of the initiator owrate for various values of the solvent owrate, x4f = 0:0, qm = 0:4.
70x10-3 60 50
d-hyst
40 30 20 10
0.0
0.2
0.4
0.6
0.8
qm
Figure 21: Damkohler number hysteresis locus as a function of the monomer owrate for various values of the solvent owrate, x4f = 0:0, qi = 0:11429. 47
d-hyst
30 20 10 0
0.2
0.4
0.6
0.8
1.0
qs
Figure 22: Damkohler number hysteresis locus as a function of the solvent owrate for various values of the monomer owrate, x4f = 0:0, qi = 0:11429.
II
IV
14
16
18
20
Figure 23: Global multiplicity behavior for the styrene polymerization CSTR model, V = 1500 liters, = 0:93328, x4f = ?1:14320. 48
x3
qc
Figure 24: Steady-state dimensionless reactor temperature versus cooling jacket owrate, V = 1500 liters, d = 0:01688, = 13:17936, = 0:93328, x4f = ?1:14320.
I
d
0.3 0.2 0.1 0.0 4 6 8 10 12
II IV
14
16
18
20
Figure 25: Global multiplicity behavior for the styrene polymerization CSTR model, x4f = ?1:5. 49
x3
1.0 0.2 -0.6 0 1 2 3 4 5
qc
Figure 26: Steady-state dimensionless reactor temperature versus cooling jacket owrate, d = 0:01688, = 13:17936, x4f = ?1:5.
50