DESIGN AND CONTROL OF INTEGRATED STYRENE - ANILINE PRODUCTION PLANT

Octavian Parteniea, Vincent van der Lastb, Costin Sorin Bildeaa, Pietro Altimaric

a
University “Politehnica” Bucharest, Polizu 1-7, RO-011061, Bucharest, Romania
b
Delft University of Technology, Julianalaan 136, 2628BL, Delft, The Netherlands
c
Università “Federico II” Piazzale Tecchio 80, 80125 Napoli, Italy

Abstract: The paper illustrates the operational difficulties arising from simultaneously
performing exothermic and endothermic reactions, and demonstrates that the plant can be
built and safely operated by integrating the design and plantwide control issues. The
behaviour of reactor – separation – recycle systems carrying the coupled reactions A →P + Q
(endo) and B + Q → R (exo) is investigated. Irrespective of the control structure, state
multiplicity cannot be removed if the intermediate component Q is recycled. Therefore, the
chemical reactor should be designed such the recycle of Q can be avoided without economic
penalty. The theoretical findings are applied to the design and control of a plant coupling
ethylbenzene dehydrogenation and nitrobenzene hydrogenation for simultaneous production
of styrene and aniline. After plant design, a rigorous dynamic model is developed using
AspenDynamics. A plantwide control structure is implemented and shown to be able to
achieve large production rate changes and to effectively reject various disturbances.
.

Keywords: Reaction coupling; Design and control; Nonlinear dynamics; Styrene; Aniline

1. INTRODUCTION

Direct coupling of endothermic and exothermic reactions leads to improved thermal efficiency and, for reversible
reactions, to increased equilibrium conversion and reaction rate due to equilibrium displacement (Towler and Lynn,
1994). As a result, energy savings and reduced reactor size can be achieved. However, while enhancing reactor
performance, coupling endothermic and exothermic reactions in a single unit may require additional separation units
and recycles. In practice, energy savings and reduced reactor investments must outweigh the cost of required
additional units. Furthermore, it is important to remark that recycle of unconverted reactants can lead to undesired
nonlinear phenomena in plantwide systems, with important implications for design and control (Bildea and Dimian,
2003).

The research on reaction systems coupling endothermic and exothermic reactions has been mainly focused on the
efficient design and analysis of stand-alone reactor units, with the simultaneous ethylbenzene dehydrogenation and
nitrobenzene hydrogenation as a frequent example demonstrating the effectiveness of the idea (Qin et al, 2003, Abo-
Ghander et al, 2008). To assess the feasibility of coupling endothermic and exothermic reactions, operational and
control difficulties arising from the more complex behaviour should be taken into account. Recent studies (Altimari
and Bildea, 2008) addressed the problem of integrated design and control of plantwide systems coupling
endothermic and exothermic reactions. Hypothetical processes were considered. For several flowsheets and different
plantwide control strategies, multiple steady states were invariably detected. Singularity theory was exploited to
divide the space of reactor-design parameters into regions characterized by qualitatively-different solution diagrams,
implications of the observed behaviour on plant controllability being thoroughly discussed.

In the first part of this contribution, we investigate the behaviour of reactor – separation – recycle systems carrying
the coupled reactions A →P + Q (endo) and B + Q → R (exo) with the goal of identifying the conditions which
guarantee a unique, stable steady state. To achieve this, we attempt to avoid the feedback arising due to material
recycles by fixing the reactor-inlet flow rates (Bildea and Dimian, 2003). We show that, irrespective of the control
structure, state multiplicity cannot be removed if the intermediate component Q is recycled. Therefore, we conclude
that the operational difficulties can be solved not by control, but by considering the chemical reactor. This should be
designed such that the reactor-outlet flow rate of the intermediate component Q is minimized, and its recycle can be
avoided without a significant economic penalty. The second part of the paper applies the theoretical findings to the
design and control of a plant coupling ethylbenzene dehydrogenation and nitrobenzene hydrogenation for
simultaneous production of styrene and aniline. Compared to the classical processes, the main advantages are
reduced sensitivity of the chemical reactor which can be operated adiabatically or at low heat-transfer capacities, and
the reduced energy consumption due to low steam requirements. After plant design, a rigorous dynamic model is
developed using AspenDynamics. A plantwide control structure is implemented and shown to be able to achieve
large production rate changes and to effectively reject various disturbances.

In conclusion, this paper illustrates the operational difficulties arising from simultaneously performing exothermic
and endothermic reactions, and demonstrates that the integrated plant can be built and safely operated by integrating
the design and plantwide control issues.

2. NONLINEAR BEHAVIOUR OF REACTOR – SEPARATION -RECYCLE SYSTEM

2.1 Mathematical model

The system investigated in this section considers the following system, where the product Q of the first reaction is
consumed in the second one. In turn, the exothermic second reaction provides the energy necessary for the first
reaction to take place.
A k P Q
1
H 0
k2
B Q R H 0

Fig. 1 shows the general structure of the Reactor – Separation – Recycle system. Ideally, the reactants A, B and Q
are recycled, while the products P and R are removed from the plant.
A, B A, B, Q
0
3
1

P, R

2 4
Reactor Separation
A, B, Q, P, R

Fig. 1. General structure of the Reactor – Separation – Recycle system

The steady state behaviour of the Reactor – Separation – Recycle system contains the reactor equations (1) - (6),
which assume a plug-flow model and Arrhenius dependence of the reaction constants versus temperature. The
reactor-inlet temperature (0) is fixed by feedback control of a heat exchanger placed upstream of the reactor at the
value (0) = 1. Equation (7), assuming that the reactants A, B and the intermediate product C are recycled, while
the products P and R are withdrawn from the plant, describes the separation, recycle and the mixing point.
df A fA (1)
Da exp
d 1 f
df B G21 fB fQ (2)
K 21Da exp
d 1 f f
d Da fA G21 fB fQ (3)
B exp K 2,1H12 B exp c
d f 1 f 1 f f
 fQ fQ ,1 f A,1 fA f B ,1 fB ; fR f A,1 f A ; fP f B ,1 fB (4)
f fA fB fQ fP fR (5)
fA 0 f A1; fB 0 f B1; 0 1
(6)
f A1 f A0 f A 1 ; f B1 f B0 f B 1 ; fQ1 fQ 0 fQ 1 ; (7)

The variables appearing in the mathematical model are the dimensionless axial coordinate , the dimensionless flow
rates f, the temperature along the reactor, and the dimensionless recycle flow rates fK(1) = fK3. The model
parameters are the Damkohler number Da, the ratio between the kinetic constants K21, the dimensionless adiabatic
temperature rise B, the ratio between the reactions enthalpies H21, the dimensionless heat transfer capacity , the
dimensionless cooling temperature c.

The model contains three algebraic equations (7) containing six unknowns: fA0, fB0, fQ0, fA1, fB1, fQ1. In addition, the
differential equations require the reactor-inlet temperature to be specified as initial condition. Therefore, a total of
four specifications are needed.

2.2 Classification of the steady state behaviour

In practice, a set of specifications needed to solve the model (1) - (7) corresponds to a feasible plantwide control
structure. In the following, we will consider that reactants A and Q are recycled together. A feasible set of
specifications is given by equations (8), where t and u are given values.

f A1 fQ1 t ; f B1 u ; fQ0 = 0; 1 =0 (8)

Fig. 3 presents the classification of the steady state behaviour of the reactor – separation – recycle system, with the
parameter t as bifurcation parameter, and the conversion XA as variable representative for the state of the system.
The space of the reactor design-parameters c – is divided into several regions, each region being characterized by
a specific t – XA bifurcation diagram. Fig. 2 demonstrates the complex behaviour, including state multiplicity,
isolated solution branches, and regions of feasibility.
1 1 1

0.8 I 0.8 II 0.8 III

12 0.6
XA / [-]

0.6 0.6
XA / [-]

XA / [-]
isola 0.4 0.4 0.4

cusp 10 7
isola
cusp
0.2

0
0.2

0
0.2

0
IX 0 1 2 3 4 5 6 7 8 9 10 11 0 1 2 3 4 5 6 7 8 9 10 11 0 1 2 3 4 5 6 7 8 9 10 11
6.6 t / [-] t / [-] t / [-]
IX I

8
β

6.2 VIII
VII

I
1
5.8
III IV IV 1
V 1
VI
0.8 0.8 0.8
V
6
β

5.4
0.6
XA / [-]

XA / [-]

0.6
XA / [-]

0.6
0.011 0.012 0.013 0.014 0.015
θc
0.4 0.4 0.4

4
0.2 0.2 0.2

0 0 0
0 1 2 3 4 5 6 7 8 9 10 11 0 1 2 3 4 5 6 7 8 9 10 11 0 1 2 3 4 5 6 7 8 9 10 11
t / [-] t / [-] t / [-]
II 2 V VI 1 1 1

III 0.8 VII 0.8 VIII 0.8 IX

0
XA / [-]

0.6
XA / [-]

0.6
XA / [-]

0.6

-0.1 -0.05 0 0.05 0.1 0.4 0.4 0.4

θc
0.2 0.2 0.2

0 0 0
0 1 2 3 4 5 6 7 8 9 10 11 0 1 2 3 4 5 6 7 8 9 10 11 0 1 2 3 4 5 6 7 8 9 10 11
t / [-] t / [-] t / [-]

Fig. 2. Classification of the steady state behaviour.

2.3 Discussion: design and plantwide control implications

From an operational point of view, the complex behaviour depicted in Fig. 2 is undesired. For this reason, we
attempt to simplify it by decoupling the reaction and separation sections. This can be achieved by fixing all reactor-
inlet reactor flow rates (Bildea & Dimian, 2003). This can be done only freeing one specification, te corresponding
variable being used as a manipulated variable in a control loop. In the following, we investigate two alternatives: 1,
or c, corresponding to specifications (9) and (10), respectively.
f A1 t ; f B1 u ; fQ0 0 ; fQ1 v ; (9)
f A1 t ; f B1 u ; fQ 0 0 ; fQ1 v; (10)
Fig. 3 shows representative t – XA bifurcation diagrams. Although the behaviour seems simpler that the one
displayed in Fig. 2, state multiplicity and regions of unfeasibility still exists. We conclude that the desired pattern of
behaviour cannot be achieved by control, but more profound changes are needed. Indeed, if the flowsheet is such
that no intermediate reactant Q is recycled, then the reactor-inlet flow rates of A and B can be easily controlled.
When the reactor-inlet temperature q1 is also fixed, the feedback effect of the separation section on the chemical
reactor is effectively broken. From an economic point of view, this option is attractive when a limited amount of
reactant Q leaves the plant, which requires a proper design of the chemical reactor.
1 1 (b)
(a)
0.8 0.8
f Q,1 = 0.2
f Q,1 = 0.2
0.6 0.6
1

XA
XA

1
0.4 0.4
5 5
10 0.2
10
0.2

0 0
0 1 2 3 4 5 0 1 2 3 4 5
t t

Fig. 3. Fixing all reactor-inlet flow rates by using 1 (a) and c (b) as additional manipulated variables: t – XA
bifurcation diagrams showing multiple steady states.

3. INTEGRATED STYRENE – ANILINE PLANT

3.1 Design
Styrene (ST) is currently produced by dehydrogenation of ethyl-benzene (EB). The reaction is reversible,
endothermic, and severely limited by the thermodynamic equilibrium. Reaction can proceed to high conversions
only when a significant amount of steam is used, which acts as a heat-carrier and simultaneously lowers the EB
partial pressure. After the reaction and before separation of the reaction mixture, steam must be condensed before
being recycled. Therefore, the energy consumption of the process is high. Aniline (AN), the second product
considered, is obtained by hydrogenation of nitrobenzene (NB). The reaction very exothermic and can easily lead to
reaction runaway. In this section, we investigate the design and control of an integrated process for simultaneous
production of styrene and aniline, according to the following reactions:

C6 H 5 C2 H 5 C6 H 5 C2 H 3 H2
C6 H 5 NO2 3H 2 C6 H 5 NH 2 2 H 2O

In absolute values, the enthalpy of EB dehydrogenation is 4 times lower than the enthalpy of NB hydrogenation. On
the other hand, one mole of hydrogen is produced in the first reaction, while three moles are consumed in the second
reaction. According to the previous section, the behaviour of the plant is simpler when the intermediate reactant
(hydrogen) is not recycled, but removed from the plant. To avoid the economic penalty, there should be a small
amount of hydrogen at the outlet of the reactor. This can be achieved by a suitable choice of reactor-inlet mixture
and of ratio between amounts of catalysts. In our example, the reactor is fed with 38 kmol/h EB and 11.6 kmol/h of
NB, at 640 ºC and 1 bar. The reactor has 150 tubes of 0.1 m diameter and 5 m lengths. Conservative values of 50
kcal/h/m2/K for the heat-transfer coefficient (meaning almost adiabatic operation) and a coolant temperature of 620
ºC were assumed. The kinetics of the reactions were taken from Lee (2005) and Amon et al (1999). The densities of
catalysts were assumed to be equal. Fig. 4 shows temperature and mole fraction profiles along the catalytic bed.
Although the heat-transfer capacity is low, the processes take place almost isothermally. In addition, the
concentration of hydrogen is low.
 650 0.8

645
0.6
EB
T / [ºC]

640
0.4 ST

y
635
NB
0.2
630 AN
H2
625 0
0 1 2 3 4 5 0 1 2 3 4 5
z / [m] z / [m]

Fig. 4. Temperature and mole fraction profiles along the chemical reactor.

Fig. 5 presents the entire flowsheet. After reaction, the mixture is cooled and water and gaseous products are
separated (S-101). Column T-101 (30 stages) removes the light by-products, such as benzene and toluene. Column
T-102 (20 stages) achieves the split between ST and EB (in the distillate) and AN and NB (in the bottoms). The
products are obtained in columns T-103 (55 stages) and T-104 (stages), respectively. The whole process was
simulated in AspenPlus. After all units were sized, a dynamic model was obtained using AspenDynamics.
Lights

Lights

P-5

Gases
EB Recycle

PC

PC

LC
FC P-7

M-101 PC
EB
TC
S-40
LC FC T-103
R-101 FC
S-39
LC
P-2 P-2

LC
TC
FC
S-45
TC TC CC
PC
P-5 S-46 P-3
T-101 T-102
TC S-101 TC
NB PC P-5

TC CC
CC
LC
S-41

P-1
Styrene
I-70 LC
I-69
S-42
P-6
P-4

Water
PC
M-102

LC

Aniline
S-38

LC

T-104

FC S-37

LC

NB Recycle

Fig. 5. Flowsheet of the integrated styrene-aniline plant

3.2 Plantwide control and dynamics

Fig. 5 presents the plantwide control system. The reactor-inlet temperature and flow rates of EB and NB are fixed,
fresh reactants being fed on inventory control. Control of heat exchangers, vapour-liquid-liquid separator and
distillation columns is standard. It should be remarked that dual-composition control of the column T-102 is
required, because the AN which escapes in the distillate will end in the ST product, while the EB from the bottoms
will be found in the AN product. Fig. 6 presents results of dynamic simulation. Starting from the steady state,
different variables are changed at time t=5 hr, in order to investigate the effect on the plant throughput. In simulation
(A), the EB reactor-inlet flow is increased by 10%. The effect on production rates is 4% (ST) and 4.8% (AN). The
dynamics of the ST is quite fast, while more than 55 hours are needed until the AN rate stabilizes. In simulation (B)
the reactor-inlet flow rate of NB is increased by 10%. The plant does not reach a new steady state, and sustained
oscillations seem to emerge. In simulation (C), both reactor-inlet flowrates of EB and NB are increased by 10%,
while in simulation (D) the reactor-inlet temperature is increased by 20 ºC. In both cases, new steady states are
reached, the dynamics of the AN rate being significantly slower.
31 10

30
F Styrene / [kmol/h]

F Aniline / [kmol/h]
(C) 9.5 (A) (C)
29 (D)
(A)
28 9 (D)
(B)
27 (B)
8.5
26

25 8
0 5 10 15 20 25 30 35 40 0 10 20 30 40 50 60
t / [h] t / [h]

Fig. 6. Dynamic simulation results

4. CONCLUSIONS

In reactor – separation – recycle systems carrying the coupled reactions A →P + Q (endo) and B + Q → R (exo),
irrespective of the control structure, state multiplicity cannot be removed if the intermediate component H is
recycled. The operational difficulties can be solved not by control, but by considering the chemical reactor, which
must minimize the reactor-outlet flow rate of the intermediate component Q and avoid its recycle without a
significant economic penalty.

The design and control of a plant coupling ethylbenzene dehydrogenation and nitrobenzene hydrogenation for
simultaneous production of styrene and aniline is presented. Compared to the classical processes, the main
advantages are reduced sensitivity of the chemical reactor which can be operated adiabatically or at low heat-
transfer capacities, and the reduced energy consumption due to low steam requirements. A plantwide control
structure is implemented and shown to be able to achieve large production rate changes

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