STUDIES IN THE CONTROL OF TUBULAR REACTORS-I

GENERAL CONSIDERATIONS

C GEORGAKIS,t R ARIS and NEAL R AMUNDSON

Department of Chemrcal Engmeermg and Mate& Science, Umversity of Mmnesota. Mmneapohs, MN 55455,
USA

(Recerved 20 July 1976, recerved for pubbcatlon 9 March 1977)

Abstract-In this part the dynamlcal model of a Jacketed non-adiabatic tubular reactor IS developed and the effect
of the wall heat capacity IS bnefly exammed The dlstnbuted stabdlty and feed-back control problems are defined
and the method of orthogonal collocattons IS used to obtam a discretrzed model The design of the coohng sectlon
around the reactor IS examined and the number of collocation points and theu location IS determined for an
accurate approximation of the dlstnbuted model

1 INTRODUCTION the control of an unstable steady state Of special in-

Dunng the last decade several expenmental and terest here wfi be the case where the non-adiabatic
theoretical studies have appeared deahng with the dy- tubular reactor model studied by Varma and Amundson
namics of tubular chemical reactors[l-131 Quite re- has a single unstable steady state surrounded by a stable
cently attention has focussed on the non-adlabatlc type hmlt cycle The phase plane trajectones at the exit of the
of tubular reactor [9-133, because of Its greater generality reactor, when no control 1s applied, are gven m Fig 2 3 1
as compared with the isothermal or adiabatic models An of [ll] which 1s reproduced here as Fig 1 for ease of
excellent review of the SubJect has been given by reference Our prunary goal LS to examine the design
Schnutz[l4] Experimental studies are presently out- methods for controllers that will stablllze this unstable
numbered by analytical studies and the large vmety of steady state
the phenomena demonstrated by the latter demand ex- In the first part of the present senes of papers a
perimental confirmation Since all the models are for- Jacketed cooler around the reactor IS desrgned to provide
mulated by makmg certain assumptions the need of the control action A model for the behavior of the Jacket
experimental studies for model dlscnmmatlon 1s press- must be adjoined to the reactor model w&ch is then
ing dlscrehzed to reduce the dlsmbuted form to an ap-
Most of the analytical studies have been mamly con- proximate finite dunenslonal one
cerned with the problem of multlphcity of steady states, IO0 L
the existence of limit cycles and the stab&y question
The present study goes one step farther and examines
the control problem The non-adiabatic tubular reactor
has been shown [ 11) to have a greater variety of dynaml- C0.t)
cal behavior than the contmuous stirred tank reactor
While both types of reactors can have three steady states
when the simplest reaction takes place, the non-adiabatic 10-l -
tubular reactor has been shown to have as many as five
steady states for certain parameter values (Fig 8c[fO],
Fig 6[131)
In many instances of multiple steady states the state
with the highest conversion may be unstable and it IS
lmposslble to operate the reactor without control Even
when the high conversion steady state IS locally stable,
IO2 -
most of the results reported to date show that Its domain
of attraction 1s quite unsymmetrical and for practical
purposes the steady state 1s metastable
If controller design 1s successful m makmg the reactor
operate at an unstable steady state the problem of avol-
dmg a runaway from a metastable steady state IS easily
handled also The present study will therefore focus on IO3 1 1 I

IO I I I2 I3
tPresent address Department of Chemical Engmeenng, Mas- T(1.t)
sachusetts Institute of Technology, Cambndge, MA 02139, Fu 1 Exit trajectones of non-adiabatic reactor with constant
USA ambient temperature

1359
1360 C GE~ROAKIS et al

2 JACKETED TUBULAR REACTOR MODEL

In most of the previous studies of the non-adlabatlc

v&p, s =&Pa (I,’Tzc-b- Ts)
tubular reactor the ambient temperature has been as-
+ GP~~V)(T~ tn - Td (7)
sumed constant, but for control purposes the ambient
temperature will be allowed to vary This IS done by
The boundary condltlons of x = 0 are taken to be
deslgnmg a heat exchanger around the reactor so that by
varying the flow rate of the coolant, the amblent tem-
perature of the reactor can be changed and hence reactor -D/+ v(C,,.-C*) (8)
behavtor Influenced The coolant flows through the outer
she& whde the mner shell of the heat exchanger 1s the
-DBz= u(CB,n-Ca) (9)
reactor, Fig 2 The coolant 1s well stlrred and Its tem-
perature kept umform so that it exhibits the dynamical
characterlstlcs of a stirred tank cooler - ~2 = C,,p,v(T,,. - TJ (10)

flow control
and at x = 1

“&@k. cl(i) ac, ac, aT,

r \ ax ax ax O
(11)
COOLANT Taft)

IN REACTOR OUT
There are two shortcommgs of the above model The
first one 1s shared with almost all previous work and has
T&t1 C(V)
to do with the enthalpy balance, eqn (5), where the term
COOLANT b(l) mvolvmg the product of the temperature and concen-
tration denvatlves is dropped The slgmficance of the
term IS dlscussed in Ref [ISI The second hmltatIon of
1
Frg 2 The reactor-cooler system the present model has to do wtth the boundary con-
ditions, which, though vahd m the steady state, are only
The dynamical model of the Jacketed tubular reactor, apphcable to the transient model d the upstream and
m the form of a set of partial and ordmary differential downstream dlffuslvltles outslde the reactor are both
equations 1s obtamed by makmg the usual differential zero [ 161
enthalpy and mass balances and IS based on the follow- Since Equations (4), (9) and (lib) can be solved se-
mg assumptions (1) heat transfer coefficients, densltles, parately once the solution for C,, and TI IS known, we
heat capacltles and the enthalpy of reaction are constant need not consider them further
with respect to temperature and concentration vart- By using the inlet temperature, inlet concentration of
atlons, (11)the volume of coolant m the outer shell of the A, reactor length and residence time as charactenstlc
reactor system is constant, (m) temperature vartations values, eqns (3), U)-(8), (10) and (11) are changed to the
across the reactor wall are neghglble followmg dunenslonless form
For a first order, exothermlc and ureverslble reactlon

A+B (1)
$=$-$+,(c, T) (12)

with reaction rate aT_

La’T-aT+p#R(c, T)+m,(T,-T) (13)
-E
at -LPe ag a5
r(C, T) = k,C exp RT (2)
( )
v%= m,(T- T,)+m,(T, - Tw) (14)
and an enthalpy of reaction AH, (-AH > 0), the model 1s
dT. ’
as follows, the symbols bemg given in the notation and Ppdt=mz o Twde - T. + /-@(MT, m - T.1 (15)
(I >
Ag 2

ac, a2c, with boundary condltlons at 5 = 0

-=Dn7 - u%- r(CA, T,> (3)
aft ax

ac, a’c,
$ =Pe(c - 1)
-=&_T - .$$+ r(C,, T,) (4)
at’ ax
$= LPe(T - 1) (17)
C,lP, $$ = K~-C~~~,Z)~+(-AH)T(C*, T,)
andatt=l
ac aT
-_=__=o
+F(T2- TI) (9 a.5 ag (18)

where
(6) t = t’vll, .f = xl1 (19)
 Studies m the control of tubular reactors--I 1361
1
and the rest of the dlmenslonal variables are given m the
h LdS-T., +c~Qs(T.m-Ta,)=O (27)
Notation The mltml con&Qons are now >

45 0) = cd& with boundary condltlons at 5 = 0

w, 0) = To(S) (20)
T,(O) = Too
s= Pe(c, - 1) (28)

3. RRDIJCRD MODEL
s = LPe( T, - 1)
When the heat capacity of the reactor wall 1s small, the
model can be reduced to a simpler one by ehmmatmg
and at .$ = I
eqn (14) The validity of tis reduction depends on the
value of the dimensionless parameter v, which IS the dcs dTs
(30)
o

ratio of the heat capacity of the reactor wall to that of d5 d5

the reacting mixture This ratio IS small when the reac-
tion IS takmg place m a liquid phase When the reacting
phase 1s gaseous, v IS small only when the reactor wall
heat capacity and cross section are small If v IS not
small the thermal dynamics of the reactor wall cannot be
neglected and, m fact, can greatly influence the dynamic
behavior of the whole system[17]
For small v eqn (14) reduces to
Here the subscnpt s 1s used to denote the steady state
values The steady state solution consists of a concen-
tratlon and temperature profile along the reactor ~~(0,
T,(e), (0 I .f 5 1) and an ambient temperature
The multiplicity diagrams of Figs 7(a) and 7(b) of [lo]
correspond to the followmg parameter values of the
present model

Pe=50
0 = m,(T, - T,) + mz(T, - Tw)
L=lO
which gives (31)
p=o1
m,T + m,T,
T, = (21)
m+m2 y=250

The reduced dynamical model 1s now gven by The ambient temperature was fixed (T,, = 1) and
parameters $( = a, exp ( - y)/Pe) of [ 101 and h ( = S/Pe of
[lo]) were vaned By appropriately designing the heat
Jg=&$-$-$R(c,T) (22) exchanger the steady state solutions of [lo] can be
steady state solutions of the present model given by eqns
aT_ (25)-(30) Upon rearrangement of eqn (27) we find
at - La2T-ac+/3#R(c,
LPe a% a&
T)+h(T. - T) (23)

Qs = h = - T.s (32)
Tm - Tom
Td5- T. +/.G(t)(T.,.- T.) (24)
where T., = 1, and

with boundary condltlons given by eqns (16)-(18) and

a= ’ Ts(5) d5 SW
eqns (20) as uutml condition Here h 1s defined as I0

l/h = l/ml + l/m? If eqn (32) 1s satisfied one of the steady state solutions
of the present model will be ldentlcal to the one given m
and represents the overall dlmenslonless heat transfer [lo] An additional point worth mentioning here 1s that
coefficient eqn (32) does not involve parameter p which means that
When the ambient temperature, T., LS assumed con- no restnctlon IS imposed on the volume of the coolmg
stant, as was done m previous stules, eqn (24) 1s not section
necessary 5 STABlLITY PROBLEM

4 STJLADY STATE. EQUATIONS

Although one of the steady states of the present model
might be ldentlcal to one of those m Ref [lo], the
The steady state equations of the reactor model are
stability characterlstlcs are not necessarily the same,
obtained by setting the time derivatives m the transient
smce the amblent temperature 1s now allowed to vary
equations equal to zero
By subtracting the steady state eqns (25)-(30) from the
transient eqns (22X24), (16x18) and lmearlzmg the
nonhnear terms, the perturbation equations are as fol-
lows

rd2T.-dT,+S*R(c,,T,)+h(T.,-T.)=0 (26) (33)

LPe dt’ d[
1362 C GEORGAKIS et al

av Because of the nonhnearlty of the steady state prob-

l a2v av + /3$(&d + I?#) + h(z - v) (34)
at=LPe*--iQ lem, an analytical form for I?, and RT as functions of 5 IS
not possible except m tnvlal cases, and although the
stab&y problem descrrbed by eqns (39)-(42) IS a Imear
wj$=h(lvdC-z)-_pQsz (35)
problem, the elgenvalues A* and ergenvector functions
(r.(t), So@), A,) must be calculated numerically
with boundary condltlons at 8 = 0
6 CONTROL PROBLEM

The main objective of the present study IS to m-

g= Peu (36)
vestlgate the design of feedback controllers that will
change the dynamical characteristics of a steady state of
interest Of primary importance 1s the design of feedback
$ = LPev (37)
controllers that will stabilize an unstable steady state
But the design of controllers which generate a hmlt cycle
and at 6 = 1
around the unstable steady state 1s worth conslderatlon,
au au
-_=-_=o either because this may be the only way of operating
(38)
a6 86 stably m such a regon or smce the hmlt cycle itself may
have some merit The design IS based on the lmearlzed
where
form of the equations near the steady state of interest,
u(Z, 0 = CC&0 - C,(5) but its global properties are tested using the full non-
linear model
v(5,t) = W, 0 - T,(5)
If the time dependence of the coolant flow rate which
z(t) = T.(t) - T,,. serves as a control variable IS written as

Here R,, R, are known functions of 5 and are gtven by QW = Q. + f(t) (44

the design of proportional feedback controllers of the

R, = R&)=~(c,, T,)=exp(y-T/T&~))
form

(45)
The stabdlty of the steady state 1s determined by the
reduces to the choice of the feedback kernels K,(t),
elgenvalues of the followmg multidlmenslonal dlstnbuted
&(5), KS
elgenvalue problem
The linearized reactor model IS given m eqns (33)-(38)
However, the existence of a forcing function f(t) as a
AT(S) j& PM-1 - r’(& - WW6) + &SW) (39) result of the control action introduces an addltlonal term
m eqn (35), which now appears as

As@) = j-& s”(Z) - s’(5) + BWM5) + JWZ))

~=~(I,‘vd~-z)-~z+T.‘npT.sf(t) (46)

+ My -s(5)) (40)
Imphclt m the form of eqn (45) IS the assumption that
concentration as well as temperature devlatlons from the
Ay=$ (I,‘s(5)d5-y)+ (41)
steady state values can be measured equally well When
only temperature measurements are possible there are
with boundary conditions two altematlves to the design problem of a feedback
controller The first investigates the possibility of the
r’(0) = Per(O) design of a feedback controller of the form
s’(0) = LPes(0) (42)
r’(1) = s’(0) = 0 f(t) = I’ K.&)vG 0 &F f GY (47)
0

Each value, &, of A for which a nontivlal solution
@&), s&), &) exists IS called an elgenvalue and the
corresponding solution an elgenvector function A steady
state IS asymptotically stable whenever a defined as
(Y = sup {ReAkIAkeigenvalue}
is negative
where concentration deviations do not enter m the con-
trol law The second alternative adheres to the type of
controller gven m eqn (45) and where the concentration
devlatlons are substituted by estimated values, these
being obtamed from the known dynamical structure of
the system
Smce the control theory of finite dlmenslonal systems
IS more complete than that of infinite dlmenslonal ones,
 Studies m the control of tubular reactors-I 1363

described by partial dlfferentlal equations, there IS a
great incentive m descretlzmg the dlstlbuted reactor
model given by eqns (22h(24) Thus IS done m the follow-
mg section by the method of orthogonal collocations
7 ORTROGONAL COLLQCATIONS
By ehmmatmg the d,(t)% and after some algebraic rear-
rangements the tist and second axial derivatives of the
concentration profile at a collocation point are ap-
proxunated by linear combmatlons of the concentration
values at all collocation points

The analytlcal solution of eqns (22)-(24) IS lmposslble

and they must be dlscretlzed to obtain approxunate, but
still accurate, solutions The method of fimte differences and
has been used qmte extensively m the past, but it usually
requues a large number of dlscretrzafion points and (53)
results m a correspondmgly large set of ordinary dlff-
erentlal equations On the other hand, the method of The (N +2)x(N +2) drscretlzmg matnces, A, &
orthogonal collocations approximates the solution by a depend on the collocation points &, (k = 0, 1, ,N+l)
polynomial trial function, and the resultmg set of or- and thus mduectly on the values of N, a and /3 At the
dinary differential equations IS often considerably smal- same tune defimte integrals can be approximated by the
ler This method has been modtied and Improved m followrng quadrature formula
recent years and successfully used m the solution of
many chemical engineering problems [M-23] It 1s a (54)
special case of the method of weighted residuals [19], and
thus closely related to quadrature formulas Only the where only the function values of the mterior collocation
bare essentials of the method as apphed to the problem pomts are used Similar formulae can be used also when
of mterest here wdl be given since a detaded account of the function value at either or both of the end points
it has been mven elsewhere [l&19] (&,, &,+,) IS used Detads on the calculation of matrices 4
The spatial dependence of the concentration profile, and jj and the W, values have been gven m [l&19,23]
c(& t), for example, IS approximated by a polynomial The tnal function (48) and a simdar one for the tem-
tnal function of the followmg form perature profile are asked to satisfy the partial dfieren-
teal eqns (22)-(24) at the mtenor collocation pomts Then,
45 t) = b(t) + e(t)E+ f(l - 8) 2
,=i
a,(tP%Y5) (48) with the help of eqns (52) and (53) thus set of partial
dfierential equations IS transformed to the followmg set
where b(t), e(t), a,(t) (I = 1,2, , N) are functions of of ordmary ddferenttal equations
time, as yet undetermined, and P,‘“@)(f) (I = 0, 1, ,N -
1) are the N first members of the class of orthogonal
M
dck= 1 cB,c,-gAk,c,-+exp Y-+ ck (55)
dt Pe +, ,=o ( k>
Jacob1 polynomials with we&t function tB( 1 - 5)” and
such that for mf R, G= 1
- 2 &,c, -5 A,c, +B+exp y-g ck
dt LPe ,i0 1-1 ( Ir>

I’ 0
p(l - t)“P.‘““‘([) Pm’“8’(~) de = 0 (49) + MT. - Tk> (56)

Upon rearrangement, eqn (48) can be written as

dTa= h
dt PP (2 IT,-T.)+$(Q,+f(t))(T.,“-T.)
I-I
(57)

N+l where k = 1,2, ,N (M=N+l)

CC&I)= F0 d,(M’ (50) On the other hand the concentration boundary con-
dition at 6 = 0, eqn (la), leads to the followmg dlscretlzed
Let 4 W=1,2, , N) be the N zeroes of P,‘“@)(f), form
then

P,‘“8’(&)=0 (k=1,2, ,N) 2 A,c, = Pe(c,, - 1) or (A, - Pe)c, + AoMcM

(51) ,‘0
These N pomts, 6, are always mslde the open interval =-Pe-2 A,c, (58)
(0,l) and are called the mterlor collocation points The ,=I
set of collocation pomts comprises the mtenor coI- The concentration boundary condltlon at 5 = 1, eqn (18a)
locatlon pomts and the two end-pomts & = 0, &.,+, = 1 IS
From eqn (50) it follows that
2 A,,c, = 0
N-Cl I’0
c*(t) E c(& t) = z. d,&%’ or
_.
&oco + &r.sc~ = - 2
,=1
&,c, (59)

Equations (58) and (59) can now be solved for co and

and cN+] to gve

CES Vol 32 No 114

1364 C GEORGAKISet al

follows that
cdt) = S, 2 h.do, - AM,I,(Aao- PeNc,(t) + SIPeAMo
St = S?
I=,

(61)
where Pk = qr, (k = 1,2, PM)
S, = {AMM(Am - Pe) - AoMAmJ-’ (42) Ek,=Dk,(krJ=1,2, ,N

In a slmllar way the temperature boundary condlhons, Rk, = Sk, (k-1 = 132, ,N)
eqns (17) and (18b), yield the followmg relations
8. COOLING SECTION DESIGN

T,(t) = SZ 2 (&AM, - &MUM) - &LPe&w (43) If the time denvatlves m eqns (66 j(68) are set equal to
,=L
zero the steady state equations are obtained
and
2 Rklcs~-~~sk exp (Y-j?)+pk =o (6%
,=I
C-At) = S2 $$ (AM&, -&A& - LPe)T,(t) + SZLPeAMo
,=1
(44) 2 &,c, + B&k exp y-y + h(T,, - T,,) = 0 (70)
,=1 ( T,,)
where

St = {AMM(A, - LPe) - A,,A,,}-’ (65) h 2 w,T,-T..)+cca(T~,.-T.,)=O (71)

( ,=L
Substltutmg eqns (60), (61), (63) and (64) m eqns (55)
where csc(Tsa) represents the steady state concentration
and (56) the dIscretied model of the tubular reactor
(temperature) at the kth collocation point Equations
takes the followmg form
(69)-(71) comprise a set of (2N + 1) nonlinear algebrac
relations, the solution of which pves the steady state
2 = 2 &c, - +ck exp (7 -$) + pk WI
k concentration and temperature values at the interior col-
location points and the steady state ambient temperature,
dT PJ
S*,T,+B&exp 7-F +h(T,-%)+a T.,
Tiik=z ( k >
Once the steady state concentration and temperature
(67)
values are found at the mterlor collocation points the
dT,
-=- h values at the boundary points &, = 0, EM= 1, can be
2 w,T - E) - ; (Qs + fOMT’.m - T-1 058)
dt PP ( ,=I calculated by use of eqns (60), (61), (63) and (64) since
these relations apply to the steady state as well, and
where
correspondmg values at any other pomt along the length
of the reactor can be found by the use of Lagrange’s
Rk, = j$ @k, - PeAk, + &Dk,)
mterpolatlon formula
The value of a aven by eqn (32a) can be calculated by
Sk, = j-& (Bk, - LpeAkj + &Ek,) quadrature formulas of the type gven by eqn (54) and
for the steady state profile of Fig 2 3 1 of [ 111 this value
ok, = (BkO - f’eAko)(&&o, - AMMAo,) IS equal to I 10105 If it 1s assumed that T. ,” = 0 8 eqn
+ @kM - peAkM) Uo~Ao, - AdA, - Pe)) (32) reduces to
j&S = 1 26316 (72)
Ek, = @kO - LP~Ako)(&M&~ - &d&d

+ (&a - LPeA,) b&A,, - Ad& - LPeN The dynamical behavior of the coolmg sectlon
depends on the values of the dunenslonless groups Q/p
and
and h/pp Smce the parameters as yet unspecified are
pk = - &&d~ko - PeAko) + &hm(Bk, - PeAkM) three (Q,, p, p), it IS evident that there wdl always exist a
one parameter family of cooling section designs that will
qk = - S2AMdBko - LPeAkd + S2&dBkM - LpeAw)
correspond to the same set of values of the groups f&/p,
This discrehzed model should approximate the dls- h/pp and thus have the same dynamical charactenstlcs
tnbuted one more and more accurately as the number of The values of these two groups must satisfy eqn (72) so
interior collocation points, N, gets larger and larger The that the steady states of [ll] are steady states of the
above argument can be lustied by regulanty arguments present model
of the dlstnbuted parameter model solution, Welerstrass’ Let us first examme the case where
theorem and convergence arguments valued for welghted
residual methods (pp 7-12, [13]) hlpp = 6 (73a)
The initial condltlons take the form It then follows from eqn (72) that

ck(o) = CkO = c(&o) Q/p = 3 0315 (73b)

T,(o) = Tko = T(tk, 0) Equations (73a,b) define Problem I with a coohng section
time constant equal to 9 0315 Some examples of the one
Z(O) = r.,
parameter famdy of designs that wffl have the dynamical
It IS proper to remark at this pomt that d L= 1. It charactenstlcs of Problem I are aven m Table 1
 Studies m the control of tubular reactors--I 1365

Table 1 Coobng section designs w~tb the dynamo- described by the followmg equations
cal cbaractenstlcs of problem I

P P Q.
$-Pt+ U, two,1)
Q,fi=l263 02 2 083 6 316 Ku=Pad, (=O
04 1042 3 158 d5
06 0 694 2 105
hlpp = 6 0 08 0 521 1 579 du
10 0 417 I 263 @ = 0, 6=1
0 278 0 842
QJp = 3 032 : i 0208 0 632 An analytical solution to the problem 1s easy to find and
25 0 167 0 505 the elgenvalues ~1 are gven by
30 0 139 0 421
2
p=_y’_!$ (77)
Problem II 1s defined by settmg
where y 1s a solution of
hlpp = 150 (74a)
and thus (78)

QJp = 0 758 (74b) and there 1s a countable set of values for p This problem
can also be solved by an orthogonal collocation ap-
with the coolmg section time constant equal to 2 258
proxunatlon If N 1s the order of approxlmatlon an
Table 2 gives some examples of the family of designs
N x N matnx IS formed and Its N elgenvalues ap-
Problem II represents
proxunate the N first elgenvalues of the eqns (75)-(76)
If we focus our attention for the moment to the case
Merent families of orthogonal polynomials, charac-
where the heat capacity of the coolant IS equal to that of
terrzed by the values of a and /3, were used and the
the reactmg mixture, CL= 1 and compare the volume of
values of N were vmed from N = 1 to N = 10 It was
the coolmg sectlon to that of the reactor, for Problems I
found[24] that Legendre polynomials (a = 6 = 0) ap-
and II we observe that this ratio, p, 1s equal to 0 417 and
proximate the largest elgenvalue of eqn (75) to up to 7
1 667 respectively Thus for the same reactor volume the
dlats and with the fewest collocation points (N = 7) In
volume of the coolmg section of Problem II 1sfour tunes
Table 3 the 15 algebraically largest values of p of eqn
larger than the correspondmg volume of Problem I
(77) are given In Table 4 the approxlmatlon to the first
elgenvalue CL,IS given for various types of Jacobi poly-
Table 2 Coolmg section designs with the dynamo- nomials and dtierent values of N The approximate
cal charactenstics of problem II values of the first SIXelgenvalues are aven m Table 5 for
different values of N, when usmg the shifted Legendre
CL P Q.
polynomials By companng Tables 5 and 3 one observes
Q.p = 1263 02 8 333 6 316 that for a aven value of N the error m the estimation 1s
04 4 167 3 158 small for 1~~and as the order of egenvalues increases the
06 2 778 2 10.5 error increases and becomes largest for cc~
hlPF = 1 5 08 2083 1579
10 1667 1 263 To determine more precisely the number of collocation
1111 0842 points needed for an accurate approximation of the
Q./p=0758 :i 0 833 0 632 dlstibuted set of eqns (22)-(24), three charactenstlc tra-
25 0 667 0 505
30 0 556 0421
Table 3 The exact values of the 15 alge-
bmcally largest elgenvalues of problem (75),
(76). (Pe = 5)
9 TRANSiEXT CALCULATIONS
k Pk
Smce the set of eqns (66$-o-(8) IS nonlinear the ex-
ammatlon of the transient behavior of the reactor system 1 -9 71523
must be done by numerical slmulatlon Furthermore, the 2 - 23 99727
above set of equations approximates accurately the dls- 3 - 54 85592
4 - 104 6285
trlbuted model (22x24) when N 1s large enough The 5 - 173 8%6
accuracy increases with mcreasmg N, but so does the 6 - 262 8142
computational effort The family of orthogonal polynoml- 7 - 371 4316
als and the value of N should be properly chosen so that 8 - 499 7685
9 - 647 8337
the computational effort is muumized wlule the accuracy IO -815 6316
remains very good 11 - 1003 165
As an uutlal mslght mto the proper choice of the 12 - 1210 434
family of orthogonal polynommls a simple stability prob- 13 - 1437 441
14 - 1684 186
lem IS solved This problem can be easily related to the - 1950 669
15
stablIlty analysis of an isothermal tubular reactor and 1s
1366 C GEORGAKIS
et al

Table 4 The vanation of p, with N for dtierent fam&es of orthogonal polynommls (Pe = 5)

a =-l/2 a=00 a = l/2 n=l a=1 a=0 a=2

N
#9=- 112 /3=00 j9 = l/2 /3=1 @=O #9=1 /3=2

1 - 6 086957 - 6 086957 - 6 086957 - 6 086957 - 9 069767 - 4 137931 - 6 08695

3
2 - - 10 905558
7 331540 - 9 7;7047 - 9 3%142 -9&813 - 9 794116
849121 -8 3;06L6 -88;3514
4 -9665056 - 9 709905 -9 763142 - 9 814827 - 9 720025 - 9 930349 - 9 904759
5 - 9 716331 -9715316 -9 713297 - 9 710859 -9715298 -9 708044 - 9 705738
6 -9 715345 -9 715233 - 9 714937 -9714535 -9715132 -9 713551 - 9 713599
7 -9 715214 - 9 715232 - 9 7 15289 -9715375 - 9 715214 -9 715580 -9 715602
8 - 9 715234 -9715232 -9 715226 - 9 715215 - 9 715231 -9 715197 -9715183
9 - 9 715232 - 9 715232 -9 715233 - 9 715233 -9715232 -9 715234 - 9 715235
10 - 9 715232 -9715232 -9 715232 - 9 715232 -9715232 -9 715232 - 9 715232

Table 5 The varlatlon of the SIX first eigenvalues with N (u = 0, fl = 0), (Pe = 5)

N <N> <IV, u.0 UJ, <N, CF.0

PI P2 Pa IL4 PI F6

1 - 6 086957

f - - 12
9 777047
0000 - +2511407041
20841 - 35 31497
4 - 9 709905 - 24 00869 - 56 74734 -78 67168
5 - 9 715314 - 24 02104 - 53 16897 - 114 9531 - 150 7156
6 -9715233 - 23 99669 - 55 06576 -9706475 - 211 9213 - 262 8761
7 -9715232 - 23 99727 - 54 85016 - 105 5316 - 155 1851 -3623817
8 - 9 715232 - 23 99727 - 54 85698 - 104 5023 - 176 9939 - 229 0452
9 - 9 715232 - 23 99727 - 54 85590 -1046444 - 172 9309 - 2717307
10 -9715232 - 23 99727 - 54 85592 - 104 6279 - 174 0050 - 258 7057
co - 9 715232 - 23 99727 - 54 85592 - 104 6285 - 173 8966 -2628142

Jectones were computed through the approxunate set of
eqns (66)-(68) with dtierent values of N We a small
number of collocation points gave an accurate descnp-
tion of some of the transient profiles, others that were
more steep along the reactor length required seven col-
locations points
Integration m tune of the nonlinear set of ordinary
dtierential eqns @X9-(68) IS not an easy task As the
number of collocation pomts IS mcreased to give a more
accurate approxlmatlon of the profiles along the reactor,
the set of equations becomes stti and the success of the
mtegratlon becomes largely dependent on the method
used The fourth order Runge-Kutta algorithm, bemg an
exphclt one, fouled to gve meanmgful results, although
an error control subroutine was used Imphclt methods
have a better chance of success than explicit ones[25]
and the method of quastinearmtlon was finally used for
the present problem The nonlinear equations are first
quasdmeanzed, the Crank-Nicholson method 1s used to
get an estimate of the values of the dependent vanables
at the next value of time and iterations are performed to
take mto account the effect of the nonhneanties A
detied descnption of the method has been gwen by
Lee[26] and tts apphcatlon to the present problem with
some mmor moficatlons 1s given m [24] and [27]
Table 6 Defimtlon of some mitral profiles
Name 8, & &
A 0 10 100 1 10
B 001 1 20 090
C 100 100 0 85
Any translent calculation is characterized by the IN&II
values of the dependent vanables Since the system of
interest 1s a dlstnbuted one there IS an mfimte number of
possible 1Ntld profiles of particular interest here 1s a set
of uuti profiles that satisfy the boundary condltlons of
the problem gwen by eqns (10)-(18) The sunplest such
profiles have the general form
co(5) = & VW - s&W - 2) + 2s, + Pe1 (75)
To(e) = & {LPe(l - S&$(5 - 2) - 2& + LPe) (76)
and for the ambient temperature we let
T., = 8, (77)
where 8, and & are the exit concentration and tem-
perature values of the u&al profiles The values of &,
S,, 8, Hrllldetermme the mltml conchtions and thus the
tralectones themselves In Table 6 the symbohc names
of some tralectones of thustype are defined for ease of
reference m the following figures Another nnportant
class of trajectones 1s the one that starts close to the
steady state of interest and IS defined as follows
G(5) = (I+ e,)c,(5)
T&3 = (I+ +)Ts(E) (78)
T., = (I+ ~97’0.
where Ed,4, es are small posltwe or negative real num-
bers These trajectones wdl be called “D”
In Fgs 3 and 4 one observes that for the present
system, where the amblent temperature can vary with
tune, the dynanucs are Merent from the dynanucs of
 Studies m the control of tubular reactors--I 1367

081
09 IO I I 12 13 09 IO I I 12 13

T( I.?) T( 1.t)

Fig 3 Exit tralectones of problem I wIthout control

IO

c&t)

08
T,(t)
I2
I
-

06

00 081
09 IO II 12 I3 09 IO I I I2 I3
T(l.1) T(1.t)

Fig 4 Exrt trajectories of problem II wIthout control

Fig 2 3 1 of [ll] Whde the unstable state of mterest CONCLUSIONAND REMARKS

(SS2) remains unstable there are two additional steady
states that are locally stable and the stable lnrut cycle has
dlsappeared Addlbonal steady states, especrally unstable
ones, as well as unstable lmut cycles, cannot be ruled out
as posslbdlties m Frgs 3 and 4 but are very ddiicult to
calculate due to the Qmenslonahty of the system Smular
tralectones can be drawn for any other pomt along the
reactor Seven collocation pomts are needed for the
accurate calculation of trajectones “B” wNe tra-
Jectones “A” and “C” can be accurately calculated by
less than seven collocation pomts The same trajectorres
were calculated vvlth N = 15 and It was observed that no
additional accuracy was gamed
The three steady states are Identical for Problems I
and II due to the way the coohng section was designed
The second steady state (SS2) 1s Identical to one of Fig
2 3 1 of [ll] Problems I and II differ m theu dynanucal
charactenstlcs as can be seen by comparmg Fes 3 and
4 In FQ 5 the steady state concentration and tem-
perature profiles are mven We SS3 is the high con-
version state, it 1s characterrzed by a regon, m the lmtsal
part of the reactor, with very hrgh temperatures, and that
nught not be deslrable
In this part the dynarmcal model of a Jacketed tubular
chermcal reactor was presented Because of its dls-
tnbuted and nonlinear character it was approximated by
a set of ordinary &fferentlal equations by use of the
method of orthogonal collocations The approxunate set
of equations has as dependent vanables the concen-
tration and temperature functions at certam points along
the reactor It was determined that seventh order poly-
normal approxunatlons were enough to render a set of
ordmary dtierentlal equations approxlmatmg the dls-
tibuted system very accurately The approxnnatlon of a
Qstibuted chemical reactor wrth the use of a set of
approxlmatmg functions has been also examined by
FJeld and Ursm[28] Their reactor model was the plug
flow one and thus quahtatively and quantitatively dti-
erent from the one of interest here smce It can have only
one stable steady state These authors found that the
attempt to approximate the plug flow model by or-
thogonal polynommls was not very successful (Ref [28],
p 7) and they concluded that a timte dtierence method
was preferable From our expetrence with the dlstnbuted
model It seems very clear that the method of orthogonal
collocations can be used to gve an accurate ap-
 C GEORGAKIS et al

PI, P, area per umt length of reactor wall from the

mslde and outside, cm
vllD.,
&
q(t)
df’)/-4v
coolant’s flow rate, cm3 set-’
r(C, T) reaction rate, gr-moles crne3 set-’
WC, T) r(G, T,MG.w T,,3
T T,I Tat,
T, TJT,,
T, TJ T,,
Ta m Td T,,.
T,, T2, T, temperature of reactor, reactor wall, coolant,
“K
T Irn9 Txsn mcommg temperature of reactants, coolant,
“K
t dunenslonless time, t’v/f
t’ dunenslonless time, set
V3 volume of coohng Jacket, cm’
V velocity of reactmg rmxture, cm set-’
X &stance along the reactor, cm

Greek symbols
B (- AHP,TI,.IKC.,,.
IO
Y EIRT,,
K heat dlsperslon coefficient, cal cm-’ OK-’
set-’
09
fi CP~P,lCP,Pl
00 02 04 06 oec IO
V AL’PzPxIA,CP,P~
Fig 5 Steady state profiles for problems I and II 5 dnnenslonless length, x/l
P VJA,I, ratio of coolmg volume
to reactor
proxunation of the &stnbuted model Their dtierent volume
6ndmgs may be due to the type of trtal function and the PI densities of reactants 0 = l), reactor wall
plug flow model that they have used 0 = 2), coolant 0 = 3), gr cm-’
ti r(G,., TI.,NG~v = W exp (- Y)/O
Acknowledgements-We would hke to thank Profs A Foss and
Y A Lm for some helpful suggestions Rnancml support from
REkERENCE3
the National Science Foundation IS greatly acknowledged We
[l] Ans R , Introductron to Ihe AsaIysis of Chemrcal Reactors
are also mdebted to the Umversdy of Mrnnesota Computer
Prentice Hall, Englewood Cliffs, New Jersey, 1%5
Center for providmg computer tune
121 Raymond L R and Amundson N R , Can J Chem
Engng 1964 42 173
[3] Amundson N R, Can J Chem Engng 1%5 43 48
NOTATION [4] Luss D and Amundson N R , Chem Engng Scr 1%7 22
cross-sectional area of reactor 0 = l), reactor
wall (J = 2), cm* [5] zts D and Amundson N R. Can J Chem Engng 1%7 45
341
heat capacity of reactmg nuxture 0 = l),
[6] Amundson N R and Luss D , Can J Chem Engng 1%8 46
reactor wall (J = 2), coolmg fled 0 = 3), 424
cal gr-’ cm-’ [71 Markus L and Amundson N R, J Diff EQMS 1968 4 102
GIG, C81Varma A and Amundson N R , Chem-Engig Scr 1972 27
concentration of A, B, gr-moles cm-’ 907
PI Varma A and Amundson N R , Can J Chem Engng 1972 50
mcommg concentrattons for A, B, gr-moles 470
crne3 WI Varma A and Amundson N R , Can J Ckem Engng 1973
dlsperslon coefficient of A, B. cm* see-* 51 206
activation energy, cal gr-mole-’ 1111 Varma A and Amundson N R , Can J Chem Engng 1973
51 459
reaction rate constant, set-*
WI Varma A and Amundson N R , Can J Chem Engng 1974
heat transfer coefficient between wall and 52 580
reactmg mixture, coohng fluid, Cal cm-’ II31 McGovln C R and Perlmutter D D , A 2 Ch E J 1971 17(4)
set-’ K-’ 831
CP,PIWK
El41 Schrmtz R A, Adu Chem 148 Am Chem Sot Washmg-
tin 1975
reactor length, cm WI Amundson N R ,Ber Bunsen-Ges Phys Chem 1970 74 90
hnP,UA,Cp,P,v Cl61 Wehner J F and Wdhelm R H , Chem Engng Sci 1956 6
h,P,llA,Cp2p, v 89
 Studtes m the control of tubular reactors-I
[17] Etgenberger G , Adu Chem 133 Am Chem Sot Washtng-
ton 1974
[18] Vtlladsen J , Selected Approxrmation Methods for Chemrcal
Engmeenng Problems Denmarks Tekmske Holskole, Dan-
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[19] Fmalyson B A, The Method of Werghted Resrduals and
Varwtronal Pnncrples Academic Press, New York 1972
[20] Vdladsen T and Stewart W E , Chem Engng Scl 1967 22
1483
[21] Michelson M L , Algonthms for Collocatron Solution of
Ordinary and Partial hflerentlal Equatrons Danmarks
Techrnske HoJskole, Inshtutet for Kemrtekmc Report, Den-
mark 1973
1369
r221 Ferguson N B and Fmlayson B A, Chem Engng J 1970 1
327
[23] Mrchelson M L and Vffladsen J , Chem Engng J 1972 4 64
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(1975)
WI Fmlayson B A, Pnvate commumcatron (1975)
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Academic Press, New York 1968
I271 Varma A, Georgakts C , Amundson N R and Arts R ,
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[281 Fteld M and Ursm B , presented at the 2nd IFAC Symp on
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