Copyright @ IF AC Advanced Control of Chemical Processes,

Pisa, Italy, 2000

BIFURCATION CONTROL OF SAMPLE CHEMICAL

REACTION SYSTEMS

Bodil Recke >,1 Britta R0nde Andersen »,2

Sten Bay J0rgensen »>,3

>FLS-Automation, H0ffdingsvej 34, DK2500 Valby, Denmark

» Haldor Tops0e A/S, Nym0llevej 55, DK2800 Lyngby, Denmark
»> Dept. Chem. Eng. , DTU Build. 229, DK2800 Lyngby,
Denmark

Abstract: Bifurcation control of Hopf bifurcations is applied to two systems exhibiting

a subcritical Hopf bifurcation . A subcritical Hopf bifurcation is characterized by
the emergence of an unstable periodic solution, quite often coexisting with a stable
periodic solution in a hysteresis scenario. This type of scenario can lead to large
amplitude oscillations if the Hopf bifurcation point is crossed. Therefore it is desirable
to change this bifurcation scenario, which can be achieved with the bifurcation control
described in this paper. The purpose of this type of control is to convert a subcritical
Hopf bifurcation to a supercritical one. An additional benefit is that the resulting
stable periodic solution will have a relatively small amplitude at least close to the
Hopf bifurcation point . The method is first successfully applied to a small example
system, to illustrate the calculations and subsequently to an industrial size heat
integrated ammonia reactor . For the ammonia reactor the existence region of the
sustained oscillation is reduced dramatically and the maximum amplitude is reduced
from approximately 200°C to about 60°C. Furthermore the nominal operating point
no longer coexist with stable periodic solution. Copyright © 2000 IFAC

Keywords: Partial Differential Equations , Oscillation, Nonlinear analysis , Nonlinear

control, Reactor Control

1. INTRODUCTION (Recke, 1998; Andersen, 1999). In this paper spe-

Complex dynamic behaviour is often experienced
in chemical processes. This behaviour is associ-
ated with the nonlinearities in the process. These
nonlinearities have the most pronounced effect
around bifurcation points i.e. points where the
system solutions change stability and/or number
of possible solutions. This type of behaviour have
been seen in a host of chemical systems as di-
verse as azeotropic distillation systems (Esbjerg
et al. , 1998) and fixed bed reactors with recycle
I bre@fisautomation .com
bra@topsoe.dk
Corresponding author, sbj@kt .dtu .dk
cific attention is paid to Hopf bifurcations . These
bifurcations often occur in recycle systems where
either energy or mass is recycled. An industrial
case resulting in oscillation with amplitudes in
the order of 200°C was reported by (Naess et
al. , 1993) . This quite damaging event was in-
vestigated by (Morud and Skogestad, 1998) and
further elaborated on by (Andersen , 1999) . The
purpose of this paper is to show how knowledge of
the nonlinear dynamic behaviour can be utilized
in designing a control for the process converting
the dynamic behaviour of the closed loop system
to a more desirable one.
The chemical system investigated initially in the
present paper is the simple Salnikov model. That

569
has the possibility of exhibiting periodic solutions.
These oscillating solutions arise as a consequence
of a supercritical Hopf-bifurcation resulting in a
• • ••
stable periodic solution and an unstable steady •
state. The periodic solution undergoes a cyclic 50 •
o
fold bifurcation and finally terminates in a sub-
critical Hopf-bifurcation, where the steady state o

regains stability. The purpose of the bifurcation o

control used in this article is to convert the sub- o
critical Hopf-bifurcation into a supercritical one.
Additionally the bifurcation control should sta-
bilize the bifurcation point it self. Furthermore •••
I
10
the control applied is capable of diminishing the
amplitude of the stable periodic solution obtained o ~--
in the controlled system. The advantage of this is o 0005 0 .01 0.01S 0.02 0.025 003
Initial Precur80f Concentration M
0 .035 0.04 0 .045 0 .05

that the rather 'nasty' behaviour of an unstable

periodic solution can be converted to a stable
small amplitude periodic solution without chang-
ing the static behaviour of the system.
The same bifurcation control is then applied to
an industrial scale ammonia reactor with similar
bifurcation behaviour. The results demonstrate
that the dynamics of the industrial reactor can be
changed significantly resulting in more desirable
properties around optimal productivity operating
conditions.
2. SIMPLE MODEL
The model investigated in this section is the
so called Salnikov model proposed by (Salnikov,
1948 j Scott, 1991). This set of equations de-
scribes a system which exhibits oscillations for an
exothermic reaction in a closed chemical system.
It is included to illustrate the technic which will
be applied to an industrial scale ammonia reactor
in section 3. The simple reaction scheme involved
is
P-+A rate = kopj Eo = 0
A-+B+Q rate = kIa, kI = Al exp( -Ed RT)
where it is assumed that P is a 'pool chemical' i.e.
the concentration does not change as a function of
time or has infinite capacity. A model in dim en-
sionless variables is given by.
-do. = J1. - Ko.exp ( -8- ) (1)
dT 1 + 108
-d8 = o.exp (8)
-- - (8 - 8a ) (2)
dT +
1 108
Fig. 1. Bifurcation behaviour showing the maxi-
mum temperature 8 with J1. as bifurcation pa-
rameter. (--) stable steady state, (- --)
unstable steady state, (.) stable periodic so-
lution, (0) unstable periodic solution .
system. The one occurring at the lowest value of J1.
is a supercritical Hopf leaving the formerly stable
steady state unstable, and marking the initiation
of a stable periodic solution. The Hopf bifurcation
occurring at the higher value of J1. is a subcritical
one, where an unstable periodic solution and an
unstable steady state merges resulting in a stable
steady state. In the bifurcation diagram the cyclic
fold marking the exchange of stability of the
periodic solution can also be seen.
2.2 Bifurcation Control
The purpose of bifurcation control is to transform
the subcritical Hopf bifurcation occurring in the
open loop system, to a supercritical one, and
at the same time stabilize the bifurcation point
itself. This effect can be accomplished with a
non linear controller consisting of quadratic and
cubic terms according to (Abed and Fu, 1986).
The notation used in theorem 1 can be explained
from a standard dynamical system given by:
;i; = Jp. (x, u(x)) (3)
For the system described by equation (3) , at some
parameter value of J.I. a bifurcation occurs. At this
value the left and right eigenvectors ([' and r'
respectively) can be calculated from.

ojp. = Lo (4)
2.1 Open Loop Bifurcation Behaviour ox
Lor' = >..r' (5)
A brief review of the bifurcation behaviour of the
I'Lo = I' >.. (6)
Salnikov model can be found in (Scott, 1991).
The bifurcation parameter shown in figure 1 is Where>.. is the critical eigenvalue at the bifurca-
the initial (and constant) concentration of the tion point. The eigenvectors are then normalized
precursor in the reaction (J1.) . The figure shows by setting the first component of r' to 1 and then
that two Hopf bifurcations exist in the present choosing /' such that Ir = 1. The vector notation
with no I refers to the normalized version of the
eigenvectors. "Y is defined as. "Y = !!j;;
Theorem 1. Let the hypothesis (H) hold,
(H) The matrix Ao = (8 f / 8x )(0,0) has a pair
of simple, complex conjugate eigenvalues >'1 =
iw c, >'2 = iwc on the imaginary axis, where
Wc i- O. Moreover, all other eigenvalues of Ao
have negative real part.
Additionally assume that h i- O. That is, the
critical eigenvalues are controllable for the lin-
earized system. Then there is a feedback u(x)
with u(O) = 0 which solves the local smooth
feedback stabilization problem for x = f(x , u)
and the local Hopf bifurcation control problem for
equation (3) . Moreover, this can be accomplished
with only third order terms in u(x) , leaving the
critical eigenvalues unaffected.
The condition is that h i- 0 is checked, and the
results is that at the subcritical Hopf bifurcation
point the value of h : : : 0 + 3.6737e- 3 i i- 0
(numerical values can be found in (Recke, 1998)) .
Consequently it is possible to convert the subcriti-
cal Hopf bifurcation to a supercritical one by using
a nonlinear feedback with only cubic terms. The
intended manipulated variable in the system is Ba,
and the following feedback control will be applied
Ba = -GB3 .
2.3 Results and discussion
Adding a washout filter to the system, as sug-
gested by (Abed et al. , 1995) restricts the non-
linear control to changing the dynamic behaviour
(i.e. the stability of the periodic solutions) , with-
out changing the location and stability properties
of the open loop steady states of the system. A
washout filter is in essence just a stable high-pass
filter. The reSUlting extended control system can
be written as.
dz
dT = B - wzBa = -G (B - WZ)3 (7)
Two parameters needs to be set now, are the gain
in the controller (G) and w in the washout filter.
The value of w determines the cutoff frequency.
The obvious constraint on w, is that it must be
positive. Furthermore it should be chosen below
the characteristic frequency of the periodic solu-
tion . The required gain for stabilization of the bi-
furcation point and transformation of the bifurca-
tion depends on the value of w. As a rule of thumb
it can be said that the higher w the higher gain is
necessary. In this application w = 0.5 is used. The
result of two different gains are shown in figure 2,
corresponding to one just before transformation of
571
Table 1 Minimum gains necessary to stabilize the
bifurcation point for different w-values
w-value minimum stabilizing gain
0.5 2e 3
2 0.059
the Hopf bifurcation, and one well after the trans-
formation. By increasing the gain in the controller
it is possible to not only transform the subcritical
Hopf bifurcation into a supercritical one, but also
to diminish the amplitude of the resulting periodic
solution. The latter result implies that it is pos-
sible to reduce the effect of the periodic solution
since small amplitude oscillations possibly will be
acceptable in most chemical systems.
3. AMMONIA REACTOR
3.1 Open Loop Bifurcation Behaviour
Ammonia reactors are industrially important re-
actors. (Naess et al. , 1993) reports an incident
with large amplitude temperature oscillations in
an industrial ammonia reactor with three cata-
lyst beds, quench cooling between the beds and
a feed-effluent heat exchanger. (Morud and Sko-
gestad, 1998) studied this incident and explained
the temperature oscillations with a Hopf bifurca-
tion. (Andersen, 1999) studied a simpler ammonia
reactor with only one catalyst bed and a feed-
effluent heat exchanger. The occurrence of peri-
odic solutions was investigated using bifurcation
analysis. Also for the simpler reactor sustained
temperature oscillations can occur due to a Hopf
bifurcation. However, the periodic solution arising
in the Hopf bifurcation point Hw is unstable due
to a subcritical Hopf bifurcation. Continuation of
the unstable periodic solution revealed a cyclic
fold bifurcation elL turning the periodic solution
stable, figure 3. The subcritical Hopf bifurcation
followed by a cyclic fold bifurcation explains the
sudden large amplitude oscillations experienced
in the industrial reactor. Thrning the sub critical
Hopf bifurcation supercritical must be of interest
to industry, not only because smaller amplitude
oscillations are expected but also because hys-
teresis phenomena are avoided. Figure 4 shows
a sketch of the reactor system consisting of a
single catalyst bed with a feed-effluent heat ex-
changer. The model of this reactor is described in
(Andersen, 1999) . The mass and energy balances
are
 50
•
45
•
40 •
• •
••
.;30.. / ... • 14

! • 0

i25
• 0

>- • 0

)20
15
• --~ •
•
10
• ·• "

5 j'------- 2~,"
~~-0~,~~-0~,0~,~0,~0175~0~
,02~~0,=~~0,0~3~0~=~~0~
, ~--~0,~~~o~· °01o::.--:0""
,OO-:::5-:0""
,01---::-0,0""15::---::-0,'-:02--0~,0'::25--0~,03:---::-0,-::0375~O,~~--O:-:,~':=--O...J,~
Initial Preanot ConcenIration (Ja) Initial Precursor Concentration ijL)

Fig. 2. Closed loop bifurcation behaviour, depicting the maximum temperature of the periodic solution
(B) with J.t as bifurcation parameter and w = 0.5 and gains left: 0.01 Oust before the Hopf bifurcation
is transformed), right: 5 (well after transformation). (--) stable steady state, (---) unstable
steady state, (e) stable periodic solution, (0) unstable periodic solution.

with the boundary conditions

400 III IV :V VI

380 ....············8 in
Xi = Xi
/ n 8Xil
z=o - xPeM 8z z=o
0= 8Xi I
c,J00J'i '
1U
OO~.lL
0 0
00 0
.
8z z=l
§:a60 o (12)
~ 0: 00: ).F
000 0 '.. 0.", ' U
2340
f!! o
00 ",," :0
0
: .
Bin = B/ _ _ 1_8BI 0- 8BI
~320 c,j z=o xPeH 8z z=o - 8z z=l
E
~300 . ' 0
0_ -
.. J.(,I,.0
:..:.
•
:
:

•: ...
(13)

~280
,

," : 0 The ammonia reaction is reversible. The work

~ by (Andersen, 1999) indicates that the reversible
F"~
'0
~260 OOOoooo !!; ·····.
o 0 .0 : ••• C:'L nature of the reaction causes the Hopf bifurcation
: . ~ 0 0 0 ooooo~
240 to be subcritical. Earlier work with bifurcation
220L-~60:--~---8~0~----~10~0~----1~2~0~ analysis of irreversible reactions has found super-
Feed Flow Rate [%] critical Hopf bifurcations (Recke, 1998; Kienle et
al., 1995). The feed effluent heat exchanger is of
Fig. 3. I-Parameter bifurcation diagram for open the shell and tube type. Each side is approximated
loop system, continuation of feed flow rate. with one well-mixed tank.
(--) stable steady state, (- - -) unstable dBin ,
steady state, Hopf bifurcations (Hw,Hld, Ctube dT = Bleed - Bm + NTUtubeflBtube
fold bifurcation points (Fu,FL), (e) sta- (14)
ble periodic solution, (0) unstable periodic
solution and cyclic fold bifurcation points dB~h!ll _ out out
C.hell~ - Bbed - B. hell + NTUshellflBshell
(C w , C1L).
(15)

Reactor outlet Heat exchanger Bad outlet

Catalyst bed 3.2 Results and Discussion

Fig. 4. Sketch of the ammonia reactor system. In this work it was chosen to use the feed tem-
perature (Bleed) as actuator. As measurement the
TM ,,8Xi = - x8Xi 8 ( -n- -
- + -- 8X-i) + Dar
-H-
TH 8T 8z 8z PeM 8z inlet temperature to the catalytic bed is used
(Bin)such that the delay from the control action
(8) to the measurement is relatively small.
8B It can be seen from figure 3 that the bifurcation
8B = _x + i. (_1_8B) + /3Dar (9)
8T 8z 8z PeH 8z point Hw is a subcritical Hopf bifurcation and

r' = kl (PN2 ( ~~2

PNH3
) ~ 2.K (P~H3)
_

PH,
i) (10)
thus an eligible point for bifurcation control. The
purpose of the control is to convert the sub critical
Hopf bifurcation into a supercritical one. This
conversion will eliminate region IV where the
In K = blln T + ~ + b3 + b4 T + b5 T2 + b6 T3 upper stable steady state coexists with a stable
(11)

572
 ~51
:J

~500
Ql
Cl.
~490
J-
]i480
:;
o
"0 "0470
~350
,,,
Ql
co
,
V III III
v VI , III

50 100 150 200 250 300 350 50 100 150 200 250 300 350
Dimensionless Time Dimensionless Time

Bifurcation x Region Static Periodic Bifurcation x Region Static Periodic

(%) S U S U (%) S U S U
I 1 I 1
Fold (FLl 57.38 Fold (FLl 57.38
II 2 1 II 2 1
Hopf (HIL) 69.15 Hopf (HILl 69.15
III 2 1 1 III 2 1 1
Cyclic Fold (Cw) 98 .04 Hopf (Hw) 102.1
IV 2 1 1 2 V 1 2 1 1
Hopf (Hw) 102.1 Cyclic Fold (CILl 103.0
V 1 2 1 1 VII 1 2
Fold (Fu) 104.7 Fold (Fu) 104.7
VI 1 1 1 I 1
Cyclic Fold (CILl 128.0
I 1

Fig. 6. Feed flow rate step change simulations for open and closed loop ammonia converter. left: Open
(with hysteresis) , right: Closed (without hysteresis) . The number and stability of the solutions in
the different regions can be seen from the tables.

and an unstable periodic solution (and of cause a

stable and an unstable steady state) . This region 400
is potentially dangerous since a disturbance could 380
result in the system settling to the stable peri-
§:s60
odic solution even if no flow rate changes occur. ~
With some numerical manipulations it can be seen .2340
~
that this Hopf point (Hw) satisfy the conditions 8.320
E
of theorem 1. The remaining work is to choose ~300 H,,§_-- 0 0 0
;'~
the gain and the cutoff frequency in the washout 0 0

filter. It was chosen to use the same frequency ~280

"0
as with the simple system investigated initially ~260
i.e. w = 0.5 . The gain has to be sufficiently 240
large to ensure that the Hopf bifurcation of the
220L-~60--~---8~0------1~0~0~----12~0--­
closed loop is supercritical. The result of the one
Feed Flow Rate [%]
parameter bifurcation analysis for the closed loop ,
with x used as bifurcation parameter is depicted
Fig. 5. I-Parameter bifurcation diagram for closed
in figure 5. Comparing the two I-parameter bi-
loop system, continuation of feed flow rate.
furcation diagrams in figure 3 and 5 it is obvi-
(--) stable steady state, (- - -) unstable
ous that the region labeled IV is non-existing in
steady state, Hopf bifurcations (Hw , H 1L ) ,
the closed loop system. This result demonstrates
fold bifurcation points (Fu ,Fd, (.) sta-
the desired feature, that the nominal operating
ble periodic solution, (0) unstable periodic
point formerly located in region IV is no longer
solution and cyclic fold bifurcation points
coexisting with a stable periodic solution. Thus
the possible hysteresis scenario is eliminated in (CW , C1L) .
the closed loop. In figure 6 a dynamic simulation
sequence of subsequent step changes in feed flow rate is performed for both the open and the closed
loop. Initially the system is at the upper stable

573
 steady state with )( = 1.0 (in open loop this
is region IV, in closed loop it is region Ill) . At
time T = 0 the flow rate is increased beyond
=
the Hopf bifurcation point to )( 1.025 resulting
in sustained oscillations for both systems, but as
can be seen the amplitude of the closed loop is
significantly smaller. The flow rate is then reduced
back to )( = 1.0 here the hysteresis of the open
loop system is seen since the system stays on the
stable periodic solution. For the closed loop the
system settles back on the upper stable steady
state i.e. the hysteresis is eliminated. Next the flow
rate is reduced further to )( = 0.95 i.e. below the
upper cyclic fold of the open loop system (into
region Ill) and now both systems settles to the
upper stable steady state. The locations and types
of solutions for open and closed loop are shown in
figure 6, where the existence range of the stable
periodic solutions is dramatically decreased in the
closed loop. Figure 7 shows the control action
necessary to stabilize the periodic solution after
a step change in the feed flow rate from )( = 1.0
to )( = 1.025. From this figure it can be seen that
the control requires changes of approximately 10
QC which is not unrealistic. Note that the feed
temperature has to oscillate with a period time
close to the thermal residence time of the bed.
4. CONCLUSIONS
In summary, bifurcation control is a very easy
method to apply. Only a few conditions needs to
be checked in order to assure that the method
is applicable. The inclusion of washout filters
further makes it possible to preserve the open
loop stability scenario of the steady states and
only affect the dynamics and thereby the stability
240.-----~----~------~----~--~
v III
()
~235
:::l
~ ing dynamic process simulation from concep-
~ tion to normal operation of process plants.
E
Q)
f-
~ ~;jIJ~---...
Q)
u.
50 100 150
Dimensionless Time
Fig. 7. Control action (Bleed) necessary to trans-
form the Hopf bifurcation from sub- to super-
critical. Effect of feed flow rate change )( =
1.0 to )( = 1.025.
574
of the periodic solutions. The main advantage of
the bifurcation control is that unstable periodic
solutions can be transformed into stable small
amplitude ones, which often can be considered as
acceptable behaviour.
On the specific example of an industrial ammonia
converter it has been shown that the hysteresis
scenario of the open loop can be eliminated with
the bifurcation control investigated in this paper.
This bifurcation control converts the subcritical
Hopf bifurcation into a supercritical one. This
control action additionally reduces the maximum
amplitude or the stable oscillation drastically.
All in all the dynamic behaviour is improved
significantly.
5. REFERENCES
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(1995). Control of bifurcation and chaos. In:
The Control Handbook (W. S. Levine, Ed.).
eRC Press. Boca Raton, FL.
Andersen , Britta R0nde (1999) . Nonlinear Dy-
namics of Catalytic Ammonia Reactors. PhD
thesis. Technical University of Denmark. De-
partment of Chemical Engineering.
Esbjerg, Klavs , Torben Ravn An-
dersen , Dirk Mller, Wolfgang Marquardt and
Sten Bay J0rgensen (1998). Multiple steady
states in heterogeneous azeotropic distillation
sequences. Ind. Eng. Chem. Res. 37, 4434-
4452.
Kienle, A., G. Lauschke, V. Gehrke and E.D.
Gilles (1995). On the dynamics of the cir-
culation loop reactor- numerical methods
and analysis. Chemical Engineering Science
50, 2361-2375.
Morud, John C. and Sigurd Skogestad (1998).
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Naess , L., A. Mjaavatten and J-O. Li (1993). Us-
Computers chem. Engng. 17(5/6) , 585-600.
Recke, Bodil (1998) . Nonlinear Dynamics and
Control of Chemical Processes. PhD thesis.
Technical University of Denmark. Depart-
ment of Chemical Engineering. in Press.
Salnikov, 1. Ye. (1948) . Themokinetic model of a
homogeneous periodic reaction. Dokl. Akad.
Nauk SSSR 60, 405-8.
Scott, S. K. (1991). Chemical Chaos. number 24
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on Chemistry . Oxford University Press.