coo9 2509/91 53 00 + 0.

00 Q 1991 Pergaamon Press plc

THE EFFECT OF NONIDEAL MIXING ON INPUT MULTIPLICITY IN A CSTR

CHING-TIEN
Department of Chemical Engineering,

LIOU

and YU-SHU
Instilute

CHIEN
of Technology, Taipei, Taiwan 10772,

National

Taiwan R.O.C.

(First received 20 December

1989; accepted in revised form 1 October 1990)

Abstract-Input multiplicity is a strange situation in which different input concentrations can give the same output concentration. In this paper the nonideal concept of Choke s model is employed to investigate the problem of multiplicity of steady states in a CSTR where the chemical reaction rate is y. = - kCa/ (I + KCa) . The analytical results show that the parameter n (the fraction of the feed entering the zone of perfect mixing) dominates the occurrence of phenomena of input multiplicity. It is found that the necessary and sufficient conditions and the exact region of input multiplicity are determined by the parameters m (the fraction of the feed entering the zone of perfect mixed) and n.

INTRODUCTION

The occurrence of different steady states under the same operating condition is an interesting phenomenon often encountered in chemical reacting systems. It therefore has an impact on the design of the controller and start-up of chemical reactors. Recently, a number of comprehensive reviews of steady-state multiplicity in various reacting systems have been preet al. (1986) and Razbn and sented by Morbidelli Schmitt (1987). These reviews consider situations where different output concentrations occur, i.e. output multiplicity, although the input concentrations and other operating conditions are the same. An illustration of this was the classical work of Aris and Amundsen (1958), which showed that a given flow rate of coolant to a stirred exothermic reactor can lead to three steady-state temperatures. However, output multiplicity is very different from input multiplicity. The phenomenon of input multiplicity is often encountered in chemical process control when more than one set of manipulated parameters can produce the desired steady state, as was discovered by Koppel(l982, 1983 and 1985). He shows that process behavior such as divergence phenomena (the design of steady-state jumps to one of the other two steady states) and unconstrained limit cycles are caused by input multiplicity. He suggests that if input multiplicity does occur in industrial systems, it should be detected and eliminated since the input multiplicity causes the operation problems. In addition, Chang and Chen (1984) have recently shown that in certain nonlinear systems, the same control output can be obtained from different control inputs. Thus, the complication of the input multiplicity can be overlooked in the design of a process controller and lead to unexpected pitfalls. Again, Balakotaiah and Luss (1985) have used singularity theory to examine what might lead to input multiplicity. They predicted a number of the possible solutions and presented different types of diagrams de-

scribing the relationship between the input (manipulated) variables and the output (controlled) state. The purpose of this paper is to discuss the phenomenon of input multiplicity under the condition of nonideal mixing of Cholette s model for an isothermal CSTR where the reaction rate is y. = - kCa/(l + KCa) . The results show that a fraction of the feed does not enter the zone of perfect mixing. This suggests the occurrence of input multiplicity. It was found that the necessary and sufficient conditions and the exact region of input multiplicity were determined by the parameters m (the fraction of the total volume which is perfectly mixed) and n (the fraction of the feed the zone of perfect mixing), respectively. entering These results are distinct from those of the output multiplicity deduced by Liou and Chien (1990).

MODEL The reactor of Fig. 1 is a representation of a reactor

as described by Cholette s model. The value of n is the fraction of the reactant feed that enters the zone of perfect mixing. The value of m is fraction of the total volume of the reactor. When these values of m and n are equal to 1, the system is ideally mixed. The m and n can be determined by residence parameters time distribution. In this paper, we consider the reacting system to be isothermal, and the reaction rate expression is y. = ~ kCa/(l + KCa) in a CSTR. From Fig. 1, mass balance gives: nq(Ca, and n&a + (1 - n)qCa,
= qca. (2)

- Ca ) = mVkCa /(l

+ KCa )2

(1)

Equations (1) and (2) can be rewritten sionless form as:

in dimen-

2113

c-x 1
n

Da

J-

(Xa,

- Xa ) = Xn /(l

+ Xa )Z

(3)

2114

CHING-TIEN

Lrou and

YLJ-SHUCHIEN

Fig. 1. Schematic representation of the Cholette s model of a CSTR. and nXa + (1 - n)Xa, where
Da = k,, T = V/q, Xa = KCa , Xa = KCa

Equation (6) can be analyzed by referring to Fig. 2. The RHS of eq. (h) is the dimensionless consumption rate of reactant A in the chemical reaction, and the LHS of eq. (6) is the dimensionless net input of reactant A into the reactor through the fluid flow. For the latter, the intercept is Xa/[m(l - n)Da] and the slope is - l/[mn(l - n)Da]. From Fig. 2, we see that the solutions of D on a graph intersect either once or thrice. Since we know Xa and n, this suggests that we have one or three values for Xa,. This is called input multiplicity; there could be three input concentrations of Xa, whereas there is only one output concentration of Xa.

= Xa

(41
Necessary condition for input multiplicity

Equation (6), on taking to D, yields:

1

the derivative
n-D

with respect

and

Xa,

= KCa,.

The RHS ofeq. (3) is the dimensionless reaction rate and the LHS of eq. (3) is the dimensionless net input of reactant A in a nonideal mixing CSTR. When the curve (the dimensionless reaction rate) and the line (the dimensionless net input of reactant A) have more than one intersection point, it follows that the system has output steady-state multiplicity. However, our task is to concentrate on the phenomenon of input steady-state multiplicity as determined by parameter n. Equation (4) is rewritten as:
Xa = Xa-((1 -nn)Xa, n (3

mn(1 - n)Da + (n + D)3 =

(8)

Following bifurcation theory, we can determine one of the necessary conditions of input multiplicity by solving eqs (6) and (8) simultaneously: 2DZ - DnXa
+ dXa = 0.

(9)

The roots D+, D- are easily obtained D +r D_ = nCXa * J-1 4

as (10)

D, and D_ exist when Xa 3 8. Hence, one of the necessary conditions of input multiplicity is Xa>8. (11)

If we substitute
Xa, mnDa

eq. (5) into eq. (3), we get Xa - (1 - n)Xa,

= [n + Xa - (1 - n)Xa,]

- Xa

Another necessary condition can be derived by measuring the minimum slope of the mass consumption curve, i.e. taking the second derivative of eq. (6) with respect to D, whence
D = 2n. (12)

which may be rearranged

nXa-D

as
D

mn(1 - n)Da = (n where

D = Xa - (1 - @XL-J,.

(6)

Substituting

eq. (12) into eq. (X), we get 1

mn(1 - n)Da =m

1
for input multipli-

(7)

Thus, another city is

necessary condition 27n m(1 - n)

The

dimensionless

net

input

of

reactant

Da>-----.

(13)

The

dimensionless

D-

o+

DO 0

SufJicient condition for input multiplicity In a given reaction system, if Da, n, m, and Xa do not correspond to the necessary conditions of multiplicity in eqs (11) and (13), we have a unique solution. When Da, n, m and Xa do correspond to the aforesaid necessary conditions, three steady-state solutions exist if the slope of
AD, < ~ l/[mn(l

- n)Da] (14)

Fig. 2. Schematic representation

of eq. (6).

d the slope of m

The effect of nonideal

mixing

in a CSTR

211s

where A and B are high- and low-bifurcation points for D, respectively. The abscissa of A and B are obtained from eq. (10). The ordinates of A and B are obtained from the RHS of eq. (6). These conditions are clearly demonstrated in Fig. 2, which shows that three steady states must have occurred in the range comprising a and BD,, From the previous discussion, the necessary and sufficient conditions for a nonideal mixing CSTR having input multiplicity are determined by combining the conditions in eqs (1 l), (13), and (14). The exact region of input multiplicity Following Fogler s method (1986), we let y = D/ nXa, and eqs (9) and (6) are written as
XA =

(1) When n is fixed, we may consider the parameter

of m in eq. (16). If m increases, the exact region of input multiplicity will be lower in Fig. 3, i.e. the value of the Damkijhler number will be lower. Likewise if m decreases, the exact region of input multiplicity will be higher. We know the range of m to be 61. When m is fixed, we may consider the parameter of n in eq. (16). If n increases in the range of O-1, the exact region of input multiplicity will be higher in Fig. 3, i.e. the value of the Damkohler number will be higher. When n equals 0.5, the

(2)

1 Y(l W

Da=m(L

4n(l - yj -n)y(l -2~) is established

The exact region of input multiplicity through the following steps:

the value of y (y must be smaller than OS). (2) Finding the value of Xa, by substituting y into eq. (15). the value of Da, by substituting the (3) Obtaining values of m, n, and y into eq. (16). The values of DA and Xa define the exact region of input multiplicity. The parameters m and n occur in eq. (16), and since eq. (16) is an important formula for determining (ordinate) Da, the exact region of input multiplicity wil1 be lower or higher, depending on parameters m and n.
Table I. A comparison between

(1) Ascertaining

81

10 I Outlet

12 1

14 I

16 I

Ia I

20 1
Xa

22 I

dimensionless

concentration

Fig. 3. The exact region

of input multiplicity cases.

of the different

input multiplicity and output multiplicity considering condition and the exact region of multiplicity Input
Xa 38 Da > ~ 27n

necessary

conditions,

suflicient

Output multiplicity Necessary conditions

Xa, > 8

multiplicity

27n Da>m

m(1 - n)
<

Sufficient
condition

the slope of AXa, _ n/bnDa) s

the slope of m
1

the slope of AD, < - l/(mn(l - n)Da) < the slope of BD,j 1
Xa = ~

Exact

region of

Xa,

multiplicity
Da =

= ~ PU - 2P)

Y(l - W
Da =

4n(l - P)J V(l - 2PY

4n(l - y)3 m(1 - n)y(l - 2y)J [Xa - (1 - n)Xa,]

where P = Xa/Xa,

where y = @Xfl)

A and B are high- and low-bifurcation t A and E are high- and low-bifurcation

points for Xa,, respectively. points for D,, respectively.

2116

CHING-TIEN LIOU and Yu-SHU CHIEN

factor of n in the numerator and the factor of 1 - n in the denominator can be cancelled. It is important to note that when n equals 1, input multiplicity does not occur. m and n are free. In eq. (16), 112 and n (3) Parameters simultaneously. The factor must be considered n/[m(l - n)] is the determination of the variation of (ordinate) Da between ideal and nonideal mixing. For different values of m and n, four cases are simulated and the results are shown in Fig. 3. It is important to note that when the same value of n/[m(l - n)] is chosen for different combinations of 111 and n in different systems, the ordinate Da in the exact region
of input multiplicity will not change.

Ca

@%I
D

DO D+
DDa K k m n P 4 V Xa
Xa

concentration of reactant in active space of the CSTR, mol/l feed concentration of reactant, mol/l defined in eq. (7) the position of the dimensionless net input of reactant A into the reactor through the fluid flow when D = nXa the abscissa of low-bifurcation point the abscissa of high-bifurcation point DamkBhler number = kz constant, l/m01 reaction rate constant, s- the fraction of the total volume which is perfectly the mixed, fraction dimensionless of the feed entering the zone

of

DISCUSSION

We have seen how the exact region of input multiplicity can indeed exist in nonideal mixing, and how it exists in the nonideal model by parameters of m and n. A comparison between input multiplicity and output multiplicity derived by Liou and Chien (1990) is shown in Table 1, including the necessary conditions for multiplicity, the sufficient condition for multiplicity, and the exact region of multiplicity. We also found that when the parameters m and n are smaller than 1, the Da value in the exact region of output multiplicity is always smaller than the Da value in input multiplicity. These two regions of input multiplicity and output multiplicity will always intersect. The region of overlap could be an important consideration in the design of chemical reactors. It was also suggested that the phenomenon of input multiplicity exists under two conditions: one is that nonideal mixing is due to the fact that a fraction of the feed does not enter the zone of perfect mixing, and the second is that the phenomenon of output multiplicity occurs at the nonlinear reaction rate. Thus nonideal mixing affects not only output multiplicity but also input multiplicity. This input multiplicity, affected by nonideal mixing, is different from the input multiplicity that occurs in process control. In reality, an ideal mixing situation cannot be achieved in a CSTR, so that care must be taken to account for input multiplicity in a real CSTR.

Xa,
Y

perfect mixing, dimensionless Xa/Xa,, dimensionless flow rate, l/s reactor volume, 1 KCa, dimensionless KU, dimensionless KG,,, dimensionless [Xa - (1 - n)Xa,]/[nXa], dimensionless

Greek letters Ya
5 reaction rate

reactor

holdup

time

REFERENCES

Aris, R. and Amundscn, N. R., 1958, An analysis of chemical reactor stability and control. Chem. Engng Sci. 7, 121-131. Balakotaiah, V. -and Luss, D., 1985, Input-multiplicity in lumped- parameter systems. Chem. Engng Commun. 39, 309-322. Chang, H. C. and Chen, L. H., 1984, Bifurcation characteristic PID control. Chrm. Engng Sci. 39, 1127-l 142. Fogler, H. S., 1986, Element ofchemical reactor engineering, in International Science in the Physical and Chemical Engineering Science, p. 419. Prentice-Hall, Englewood Cliffs, NJ.

Koppel, L. B., 1982, Input multiplicity in nonlinear multivariable control systems. A.I.Ch.E. J. 28, 935-945. Koppel, L. B., 1983: Input multiplicity in.process control. Chsm. Engng Edu. 17, 58-92. Koppel, L. B., 1985, Conditions imposed by process statics on multivariable process dynamics. A.1.Ch.E. J. 31, 70-75. Liou, C.-T. and Chien, Y.-S., 1990, The effect of macromixing and micromixing on multiplicity in a CSTR. J. Chin. Inst. them. Engng 13. 533-542. Morbidelli, M., Vartna, A. and Aris. R., 1986. Reactor steady

NOTATION

A B Ca

high-bifurcation low-bifurcation

point for D, point for D,

state multiplicity and stability, in Chemical Reaction and Reactor Engineering (Edited by Carberry, J. J. and Varma, A.), Chap. 14. ChemicaI Industries Vol. 26, Marcel in a CSTR,
Dekker, New York. Raz6n, L. F. and Schmitz, R. A., 1987, Multiplicity and instability in chemical reacting systems-a review. Chem. Engng Sci. 43, 1005-1047.

outlet mol/l

concentration

of reactant