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DOI: 10.2478/s11696-007-0078-4
ORIGINAL PAPER
Institute of Chemical and Environmental Engineering, Faculty of Chemical and Food Technology,
Slovak University of Technology, Radlinského 9, 812 37 Bratislava, Slovak Republic
A methodology for hazard investigation based on the integration of a mathematical model ap-
proach into hazard and operability analysis is presented. This approach is based on mathematical
modelling of a process unit where both steady-state analysis, including analysis of the steady states
multiplicity and stability, and dynamic simulation are used. The dynamic simulation serves for the
investigation of consequences of failures of the main controlled parameters, i.e. inlet temperature,
feed temperature and feed composition. This simulation is also very useful for the determination
of the influence of failure duration on the reactor behaviour. On the other hand, the steady state
simulation can predict the reactor behaviour in a wide range of failure magnitude and determine
the parametric zones, where shifting from one steady state to another one may occur. A fixed bed
reactor for methyl tertiary-butyl ether synthesis was chosen to identify potential hazard and oper-
ational problems of a real process.
c 2008 Institute of Chemistry, Slovak Academy of Sciences
Keywords: fixed-bed reactor, safety analysis, HAZOP, mathematical modelling, nonlinear dynam-
ics
Weatherill and Cameron (1989), and Mushtaq and The dynamic analysis serves for analysing the time
Chung (2000). and trajectory of shifting from one steady state to an-
In contrast to the knowledge-based approach, the other one due to a failure deviation. It is also very
model-based approach has gained more importance in useful for the investigation of dynamic behaviour of
recent years. It is based on the description of a chem- the reactor with respect to the time duration of the
ical plant using a mathematical model. This proce- failure. Finally, the results of safety analysis were re-
dure holds the promise of reducing the time and effort produced and utilised in HAZOP studies. The contri-
required in HAZOP significantly, making the study bution of this work is to demonstrate that combination
more smooth and detailed and minimising the influ- of a standard identification method, like HAZOP, with
ence of human factors. Parmar and Lees (1987) at- mathematical modelling has the potential to become
tempted, as the first, to automate the HAZOP study a very practical and robust tool for the reactor safety
using qualitative propagation equations for the initi- analysis.
ation and termination events. A hybrid model pre- However, it is important to point out that the in-
sented in (Dimitriadis et al., 1996) uses a continu- vestigation of multiple steady states for the chosen sys-
ous description of differential equations supplemented tem is affected by the selection of an adequate math-
with discrete controller actions. Graf and Schmidt- ematical model and is strongly dependent on the pa-
Traub (2001) used a combination of expert and model- rameters which describe physical properties, kinetics,
based approaches with the aim to take advantage of mass and heat transfers, etc.
qualitative modelling of chemical plants and methods
for logical controller verification. Other model-based
approaches were published by Eizenberg et al., (2006) Case study
and Srinivasan et al., (1997).
The model-based approach with a set of mathe- The presented safety analysis methodology is
matical equations derived from the quantitative de- demonstrated on the case study of a fixed bed reactor
scription of a chemical plant seems to be the most for the methyl tertiary-butyl ether (MTBE) synthesis
straightforward procedure. Usually, the HAZOP anal- according to the following reaction scheme
ysis does not consider the duration and amplitude of
the deviations generated during the operation. How- CH3 OH + (CH3 )2 C = CH2 ⇔ (CH3 )3 COCH3 (1)
ever, what exactly does the deviation ‘less flow’ mean:
90 % or 20% of the usual operation value? Does the where isobutene (IB) reacts with methanol (MeOH) to
deviation occur as an immediate (step) decrease of the form MTBE in a reversible exothermic reaction. The
flow lasting 10 min or more, or is it only an impulse? reaction is catalysed by a strong acid ion-exchange
Is this decrease continuous at some rate? Answers to resin. The reaction rate equation and its parameters
these questions can be obtained using an appropriate are given by Rehfinger and Hoffmann (1990). Possi-
mathematical model. In such a model, the extent of ble side-reactions were ignored. Reaction rates were
the deviations can be easily incorporated and possi- calculated assuming a pseudo-homogenous model.
ble consequences investigated (Labovský et al., 2006, The reaction is usually carried out in the presence
Švandová et al., 2005a, 2005b). of inert components. These components result from
In the presented paper, the model-based approach upstream processing where isobutene is produced. In
including the HAZOP methodology was applied for our case study, 1-butene (1-B) was used as the inert.
a fixed bed reactor for MTBE synthesis. In the first Physical-chemical properties of all pure components
step, a mathematical model of the fixed bed reactor were taken from the HYSYS 2.1 database.
was formulated. In the next step, a safety analysis The adiabatic fixed bed reactor (Fig. 1) was filled
using the steady state and dynamic approaches was with a catalyst (ion-exchange resin) and the design
performed (Molnár et al., 2005). operation parameters were set in the following way:
The steady state approach was used for the anal- – temperature of the fresh feed (stream 3) to 302 K,
ysis of the system stability and the locus of operating – molar flow rate of fresh methanol into the fixed
conditions. It was focused on identification of the phe- bed reactor (stream 1) to the value of 96 kmol h−1 ,
nomenon of multiple steady states and regions where – molar flow rate of the mixture of IB (18.7 %) and
oscillation may occur. The selected reaction system 1-B (81.3 %) into the fixed bed reactor (stream 2) to
(MTBE production) is known for its ability to switch the value of 460 kmol h−1 ,
between different steady states. A detailed descrip- – the mixture of stream 1 and stream 2 was pre-
tion of the multiple steady states in MTBE produc- heated in the heat exchanger to the temperature of
tion units can be found in several articles (Chen et 302 K,
al., 2002, Güttinger & Morari, 1997, Mohl et al., 1999, – the fixed bed reactor reflux (stream 4) to the
Švandová, et al., 2006). Sustained oscillations in a re- value of 0.5,
active distillation column for the production of MTBE – the fixed bed reactor pressure to the value of 1940
can be found in the paper (Schrans et al., 1996). kPa.
J. Labovský et al./Chemical Papers 62 (1) 51–57 (2008) 53
NI
NI
dT
wF CiF Cpi T F = w Ci Cpi T − λEZ (5)
i=1 i=1
dz
and for z = L,
dCi dT
=0 =0 (6)
dz dz
where wF is the superficial fluid velocity on the reactor
inlet, CiF concentration of component i in the feed, T F
feed temperature, and L reactor length.
The initial conditions are as follows
T /K
0.6
302
F
0.910
XIB
0.5
XIB
300
0.4
298
0.3 0.905
0.2 296
0.1 294
0.900
0.0 0 2 4 6 8 10 12 14
280 285 290 295 300 305 310 315 320
F
time / h
T /K
T /K
0.75 302
XIB
F
0.70 300
flow rate of all feed streams into the system and also 0.65 298
of the recirculated stream, as well as all deviations of 0.60
296
their combinations and their consequences. This com- 0.55
294
plex task was, however, out of the range of this paper. 0.50
0 2 4 6 8 10 12 14
Therefore, only the temperature of fresh feed into the time / h
fixed bed reactor (stream 3) is analysed and discussed
here in detail. The rest of the deviations is briefly sum-
marised at the end of this chapter in the form of con- 1.0 310
tinuation diagrams. 308
The main monitored output parameter is the 0.8
306
isobutene conversion (XIB ) in the fixed bed reactor c 304
outlet. The fixed bed reactor conversion of isobutene
T /K
0.6
302
F
is defined in our case-study as the difference of the
XIB
0.4 300
molar feed flow rate of isobutene into the fixed bed re-
298
actor (stream 5) and the reactor outlet molar flow rate
0.2
of isobutene (stream 6) divided by the molar feed flow 296
rate of isobutene into the fixed bed reactor (stream 5). 0.0
294
0 2 4 6 8 10 12 14
time / h
Steady state analysis
Fig. 3. The effect of the step change of the reactor feed inlet
A steady state solution diagram of the isobutene temperature to the values 299 K (a), 297.5 K (b), and
conversion in the reactor as a function of the feed in- 295 K (c) (solid lines – IB conversion at the reactor out-
let temperature (stream 1) is depicted in Fig. 2. This let XIB , dashed lines – reactor feed inlet temperature
(T F )).
solution diagram (Fig. 2) has a typical ‘S’ profile and
the maximum number of steady states for some values
of the feed temperature is equal to three. The desired
operating point (Fig. 2, upper steady state with the regime characterised by sustained oscillations. When
temperature of 302 K) is located inside the region of a further decrease of the feed inlet temperature to the
multiplicity. Thus, branch switching may occur dur- value of 297 K occurred, a new steady state, on the
ing the failure in the reactor inlet temperature. Due lower stable steady state branch characterised by a
to a close location of the reactor operation point to the very low conversion, was reached. From these results
region of multiple steady states and regions of oscilla- follows, that the feed inlet temperature has a signifi-
tion regimes, the reactor is parametrically sensitive in cant influence on the isobutene conversion in the fixed
the context of safe operation. bed reactor.
The decrease in the feed inlet temperature caused
a slight growth of the isobutene conversion which fol- Dynamic Analysis
lows the upper stable steady state branch up to the
value depicted by the Hopf bifurcation point. After When a step change of the inlet temperature of the
crossing this point, the reactor entered the dynamic feed into the fixed bed reactor from the designed op-
J. Labovský et al./Chemical Papers 62 (1) 51–57 (2008) 55
0.93 325
0.92 320
0.91
a
315
0.90
T /K
310
XIB
0.89
F
305
0.88
300
0.87
0.86 295
0.85 290
0 2 4 6 8
time / h
T /K
XIB
0.6
F
stable steady state was achieved (Fig. 3a). This steady 305
0.5
state corresponds with the steady state depicted in 300
0.4
the solution diagram (Fig. 2). The solution diagram of
295
isobutene conversion in a fixed bed reactor (Fig. 3a) 0.3
T /K
310
XIB
0.6
F
the reactor in this case. The originally stable branch 0.5 305
entered a dynamic regime characterised by sustained 0.4
300
oscillations. The maximum difference between the 0.3
higher and the lower isobutene conversion was 0.25. 0.2
295
1.0
1.0
0.9
0.9 b
0.8
0.8 a 0.7
0.7
XIB
0.6
0.6
XIB
0.5
0.5
0.4 0.4
0.3 0.3
0.2 0.2
0.1 0.1
0.0 0.0
60 80 100 120 140 160 180 200 100 200 300 400 500 600 700 800
-1 -1
FMEOH /(kmol h ) Fbutenes /(kmol h )
1.0 1.0
0.9 0.9
0.8 c 0.8 d
0.7
XIB 0.7
0.6
XIB
0.6
0.5 0.5
0.4 0.4
0.3 0.3
0.2 0.2
0.1 0.1
0.0 0.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 0.06 0.09 0.12 0.15 0.18 0.21 0.24 0.27 0.30
Rx xIB
Fig. 6. Solution diagram for the continuation parameter - fresh methanol feed flow (FMEOH ) (a), butenes feed flow (Fbutenes ) (b),
reactor reflux Rx (c), mole fraction of IB in butanes feed (xIB ) (d). ◦
limit points; •
Hopf bifurcation point; desired
operating point, solid lines – stable steady states, dashed line – unstable steady state.
tion value, the reactor became stabilised in the original Hopf bifurcation point at 122 kmol h−1 (feed flow
steady state, without any significant MTBE produc- by 35 % higher than the designed value) or the limit
tion loss. Fig. 5b shows the effect of a 45 min duration point at 144 kmol h−1 (by 50 % higher than the de-
of the failure. In this case, the return to the original signed value). A different situation occurs in the case
steady state took more than 5 h and the losses of the of butenes. The designed molar flow rate of butenes is
MTBE production were considerable. Finally, Fig. 5c 460 kmol h−1 (marked with an empty square, Fig. 6b)
clearly shows that in the case of a failure longer than and is located in the area of multiple steady states.
1 h, the reactor became stabilised in the lower steady If the feed flow rate of butenes increases, the reactor
state characteristic by a very low isobutene conversion. will follow an upper stable steady state branch and the
Moreover, the reactor stayed in the lower steady state conversion of isobutenes will slowly decrease. However,
in spite of the feed inlet temperature being returned the possibility of shifting to the lower steady state is
to the original operating value. To return the produc- quite impossible due to the transport limitations. This
tion of MTBE to the designed value, a new start up situation could theoretically occur if the butenes feed
of the reactor was required. flow rate increased to the value of 900 kmol h−1 , which
is practically impossible.
Analysis of remaining parameters Another investigated parameter was the reactor re-
flux. In the described reactor, the reflux served for
Methanol and butenes feed flow rates are the ba- adjusting optimal temperature and concentration con-
sic regulation parameters which affect the reactor be- ditions in the reacting zone. The designed value was
haviour significantly. Fig. 6a shows the continuation 0.5. Fig. 6c shows that a decrease of the reactor reflux
diagram for the feed flow rate of methanol. This fig- causes a slight reduction of the reactor conversion. On
ure reveals that a failure in the methanol feed flow the other hand, if the reflux crosses the value of 0.725,
rate may result in switching to lower steady state or the reactor shifts to the lower steady state and the
to formation of oscillations if its value exceeds the conversion decreases significantly. The last analysed
J. Labovský et al./Chemical Papers 62 (1) 51–57 (2008) 57
parameter was the composition of the butenes feed. Mohl, K.-D., Kienle, A., Gilles, E.-D., Rapmund, P., Sund-
The considered content of isobutene was 18.7 %. The macher, K., & Hoffmann, U. (1999). Steady-state multiplic-
operating point lies very close to the bifurcation point. ities in reactive distillation columns for the production of
fuel ethers MTBE and TAME: theoretical analysis and ex-
Therefore, even a small disturbance in the butenes perimental verification. Chemical Engineering Science, 54,
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