See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/225397593

HAZOP study of a fixed bed reactor for MTBE synthesis using a dynamic
approach

Article  in  Chemical Papers- Slovak Academy of Sciences · February 2008

DOI: 10.2478/s11696-007-0078-4

CITATIONS READS

3 2,149

4 authors:

Juraj Labovský Zuzana Labovská

Slovak University of Technology in Bratislava Slovak University of Technology in Bratislava
20 PUBLICATIONS   176 CITATIONS    19 PUBLICATIONS   115 CITATIONS   

SEE PROFILE SEE PROFILE

Jozef Markoš L’udovít Jelemenský

Slovak University of Technology in Bratislava Slovak University of Technology in Bratislava
105 PUBLICATIONS   1,154 CITATIONS    77 PUBLICATIONS   766 CITATIONS   

SEE PROFILE SEE PROFILE

All content following this page was uploaded by Juraj Labovský on 21 May 2014.

The user has requested enhancement of the downloaded file.

 Chemical Papers 62 (1) 51–57 (2008)
DOI: 10.2478/s11696-007-0078-4

ORIGINAL PAPER

HAZOP study of a fixed bed reactor for MTBE synthesis using

a dynamic approach‡

Juraj Labovský, Zuzana Švandová, Jozef Markoš, Ľudovít Jelemenský*

Institute of Chemical and Environmental Engineering, Faculty of Chemical and Food Technology,
Slovak University of Technology, Radlinského 9, 812 37 Bratislava, Slovak Republic

Received 13 April 2007; Revised 6 August 2007; Accepted 7 August 2007

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

Introduction The second drawback is that HAZOP requires many

Hazard and operability (HAZOP) analysis is one of
the best and most rigorous techniques for identifica-
tion of hazard and operability problems in a chemical
plant. The HAZOP procedure formally examines all
equipment step by step as well as deviations from its
normal operation conditions, and considers what fail-
ures can appear. A HAZOP report includes all the
deviations, their causes, consequences on the equip-
ment performance, analysis of these consequences, im-
plemented protection (active and/or passive), and the
resulting suggestions. It can be successfully applied
not only to existing plants, but also to new designed
technologies and equipment. On the other hand, two
essential drawbacks of the HAZOP study exist. The
primary drawback is related to the possibility that
hazards and operability problems may be overlooked.
hours of work of a team of experienced engineers and
it is not easy to record the engineering reasoning,
basic input information, or the results. Therefore is
the application of the HAZOP technique to a detailed
chemical plant design a complex and time consuming
task. Both these drawbacks can be reduced by inte-
gration of a model approach into the HAZOP. In the
past 20 years, a lot of research effort has been ded-
icated to the development of computer-based analy-
sis methods which can be roughly divided into two
main groups: expert approach and model-based ap-
proach.
A typical expert approach to a HAZOP study,
which usually comprises three or four knowledge bases
and an inference engine, was proposed by Shimada et
al. (1996). Other expert approaches with additional fa-
cilities were developed by Göring and Schecker (1993),

*Corresponding author, e-mail: ludovit.jelemensky@stuba.sk.

‡ Presented at the 34th International Conference of the Slovak Society of Chemical Engineering, Tatranské Matliare,
21–25 May 2007.
52 J. Labovský et al./Chemical Papers 62 (1) 51–57 (2008)
Weatherill and Cameron (1989), and Mushtaq and
Chung (2000).
In contrast to the knowledge-based approach, the
model-based approach has gained more importance in
recent years. It is based on the description of a chem-
ical plant using a mathematical model. This proce-
dure holds the promise of reducing the time and effort
required in HAZOP significantly, making the study
more smooth and detailed and minimising the influ-
ence of human factors. Parmar and Lees (1987) at-
tempted, as the first, to automate the HAZOP study
using qualitative propagation equations for the initi-
ation and termination events. A hybrid model pre-
sented in (Dimitriadis et al., 1996) uses a continu-
ous description of differential equations supplemented
with discrete controller actions. Graf and Schmidt-
Traub (2001) used a combination of expert and model-
based approaches with the aim to take advantage of
qualitative modelling of chemical plants and methods
for logical controller verification. Other model-based
approaches were published by Eizenberg et al., (2006)
and Srinivasan et al., (1997).
The model-based approach with a set of mathe-
matical equations derived from the quantitative de-
scription of a chemical plant seems to be the most
straightforward procedure. Usually, the HAZOP anal-
ysis does not consider the duration and amplitude of
the deviations generated during the operation. How-
ever, what exactly does the deviation ‘less flow’ mean:
90 % or 20% of the usual operation value? Does the
deviation occur as an immediate (step) decrease of the
flow lasting 10 min or more, or is it only an impulse?
Is this decrease continuous at some rate? Answers to
these questions can be obtained using an appropriate
mathematical model. In such a model, the extent of
the deviations can be easily incorporated and possi-
ble consequences investigated (Labovský et al., 2006,
Švandová et al., 2005a, 2005b).
In the presented paper, the model-based approach
including the HAZOP methodology was applied for
a fixed bed reactor for MTBE synthesis. In the first
step, a mathematical model of the fixed bed reactor
was formulated. In the next step, a safety analysis
using the steady state and dynamic approaches was
performed (Molnár et al., 2005).
The steady state approach was used for the anal-
ysis of the system stability and the locus of operating
conditions. It was focused on identification of the phe-
nomenon of multiple steady states and regions where
oscillation may occur. The selected reaction system
(MTBE production) is known for its ability to switch
between different steady states. A detailed descrip-
tion of the multiple steady states in MTBE produc-
tion units can be found in several articles (Chen et
al., 2002, Güttinger & Morari, 1997, Mohl et al., 1999,
Švandová, et al., 2006). Sustained oscillations in a re-
active distillation column for the production of MTBE
can be found in the paper (Schrans et al., 1996).
The dynamic analysis serves for analysing the time
and trajectory of shifting from one steady state to an-
other one due to a failure deviation. It is also very
useful for the investigation of dynamic behaviour of
the reactor with respect to the time duration of the
failure. Finally, the results of safety analysis were re-
produced and utilised in HAZOP studies. The contri-
bution of this work is to demonstrate that combination
of a standard identification method, like HAZOP, with
mathematical modelling has the potential to become
a very practical and robust tool for the reactor safety
analysis.
However, it is important to point out that the in-
vestigation of multiple steady states for the chosen sys-
tem is affected by the selection of an adequate math-
ematical model and is strongly dependent on the pa-
rameters which describe physical properties, kinetics,
mass and heat transfers, etc.
Case study
The presented safety analysis methodology is
demonstrated on the case study of a fixed bed reactor
for the methyl tertiary-butyl ether (MTBE) synthesis
according to the following reaction scheme
CH3 OH + (CH3 )2 C = CH2 ⇔ (CH3 )3 COCH3 (1)
where isobutene (IB) reacts with methanol (MeOH) to
form MTBE in a reversible exothermic reaction. The
reaction is catalysed by a strong acid ion-exchange
resin. The reaction rate equation and its parameters
are given by Rehfinger and Hoffmann (1990). Possi-
ble side-reactions were ignored. Reaction rates were
calculated assuming a pseudo-homogenous model.
The reaction is usually carried out in the presence
of inert components. These components result from
upstream processing where isobutene is produced. In
our case study, 1-butene (1-B) was used as the inert.
Physical-chemical properties of all pure components
were taken from the HYSYS 2.1 database.
The adiabatic fixed bed reactor (Fig. 1) was filled
with a catalyst (ion-exchange resin) and the design
operation parameters were set in the following way:
– temperature of the fresh feed (stream 3) to 302 K,
– molar flow rate of fresh methanol into the fixed
bed reactor (stream 1) to the value of 96 kmol h−1 ,
– molar flow rate of the mixture of IB (18.7 %) and
1-B (81.3 %) into the fixed bed reactor (stream 2) to
the value of 460 kmol h−1 ,
– the mixture of stream 1 and stream 2 was pre-
heated in the heat exchanger to the temperature of
302 K,
– the fixed bed reactor reflux (stream 4) to the
value of 0.5,
– the fixed bed reactor pressure to the value of 1940
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=0 Ci = Ci0 T = T0 (7)

The mathematical model for the description of the

fixed bed reactor behaviour consisted of a set of six
partial differential equations (PDE) (five mass bal-
Fig. 1. Schematic flow diagram of the MTBE synthesis reactor. ances of the individual species plus an enthalpy bal-
ance). These were solved by the in-house software
DYNHAZ based on the C++ code, which uses:
– the length of the reactor was 10 m and the di- – the method of finite differences – for discretiza-
ameter 0.9 m. tion of the set of PDE in axial coordinate. In all pre-
sented results 100 discretization points were used. The
Mathematical models and computational meth- influence of the number of discretization points was
ods first tested by changing from 20 to 5000 points,
– backward difference formulas up to the 5th or-
Due to mild temperature profiles and negligi- der with a step controller for the time integration of
ble differences (of both, temperature and concentra- (PDE) implicit schemes (Boyce & DiPrima, 2000),
tion) between fluid bulk and solid catalyst, a pseudo- – LAPACK library for solving sparse linear equa-
homogeneous model was chosen for the description of tions.
the reactor behaviour. This model, which describes We used our implementation of the DERRPAR al-
only the axial profile of the radially averaged temper- gorithm (Kubíček, 1976) for finding the dependence
atures and concentrations, reads of the model equations in steady state solution on
a parameter. For the stability and bifurcation points
NR


∂Ci ∂Ci ∂ 2 Ci identification, methods described by Holodniok et al.
ε +w − DEZ = − νji ξ˙Vj (Ci , T ) (2) (1986) were used.
∂t ∂z ∂z 2 j=1

Results and discussion

NI
∂T ∂T ∂2T During a HAZOP study, possible deviations are
Cp ρ +w Ci Cpi − λEZ 2 =
∂t i=1
∂z ∂z generated by rigorous questioning, prompted by a se-
NR
ries of standard “guidewords” applied to the intended

4UW design (Kletz, 1999). After the guideword is matched
= −∆R Hj ξ˙Vj (Ci , T ) − (T − TC ) (3)
j=1
dR with a parameter, a deviation is generated. The next
step in the HAZOP study is to look for potential con-
where Ci is the concentration of component i in the sequences. At this moment, the application of mathe-
fluid phase, T is the fluid temperature, ε porosity, Cp matical modelling (steady state analysis and dynamic
medium heat capacity of the bed, ρ medium density analysis) is useful in order to find adequate conse-
of the bed, w superficial fluid velocity, Cpi mole heat quences. Steady state solutions over a large interval
capacity of the component i, DEZ axial dispersion co- of operating parameters are obtained by a continua-
efficient, λEZ axial heat conductivity, UW overall heat tion algorithm. This algorithm is able to identify the
transfer coefficient, dR reactor diameter, TC cooling quality of a steady state solution (stability analysis)
medium temperature, z axial position in the reactor, t and multiple steady states (Kubíček, 1976). The infor-
time, νji are stoichiometric coefficients of the i-th com- mation about trajectories and conditions able to shift
the system from one steady state to another can be
ponent in j-th reaction, ξ˙Vj rate of chemical reaction,
obtained by dynamic analysis.
∆R Hj reaction enthalpy. The boundary conditions are
For the proposed safety analysis methodology it
for z = 0
dCi is necessary to investigate all deviations of all oper-
wF CiF = wCi − DEZ (4) ating parameters; i.e. temperature, composition, and
dz
54 J. Labovský et al./Chemical Papers 62 (1) 51–57 (2008)

1.0 0.920 310

0.9 308
0.8 306
0.915
0.7 a 304

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

Fig. 2. Solution diagram for the reactor feed inlet temperature

as the continuation parameter. ◦
limit points, Hopf • 0.95
310
bifurcation point, desired operating point, solid lines 308
0.90
– stable steady states, dashed line – unstable steady 306
0.85
state. b
0.80 304

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).
Steady state analysis
A steady state solution diagram of the isobutene
conversion in the reactor as a function of the feed in-
let temperature (stream 1) is depicted in Fig. 2. This
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
temperature of 302 K) is located inside the region of
multiplicity. Thus, branch switching may occur dur-
ing the failure in the reactor inlet temperature. Due
to a close location of the reactor operation point to the
region of multiple steady states and regions of oscilla-
tion regimes, the reactor is parametrically sensitive in
the context of safe operation.
The decrease in the feed inlet temperature caused
a slight growth of the isobutene conversion which fol-
lows the upper stable steady state branch up to the
value depicted by the Hopf bifurcation point. After
crossing this point, the reactor entered the dynamic
0.0
294
0 2 4 6 8 10 12 14
time / h
Fig. 3. The effect of the step change of the reactor feed inlet
temperature to the values 299 K (a), 297.5 K (b), and
295 K (c) (solid lines – IB conversion at the reactor out-
let XIB , dashed lines – reactor feed inlet temperature
(T F )).
regime characterised by sustained oscillations. When
a further decrease of the feed inlet temperature to the
value of 297 K occurred, a new steady state, on the
lower stable steady state branch characterised by a
very low conversion, was reached. From these results
follows, that the feed inlet temperature has a signifi-
cant influence on the isobutene conversion in the fixed
bed reactor.
Dynamic Analysis
When a step change of the inlet temperature of the
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

Fig. 4. The temperature profile of the fluid phase in the reactor

during oscillations as a function of the reactor length
1.0 325
and time.
0.9 320
0.8 b 315
0.7
eration value of 302 K to 299 K was considered, a new 310

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

indicates that at this moment the reactor works in 0.2

0 2 4 6 8
290

the steady state, which is localised on the upper sta- time / h

ble steady state branch. After returning the feed tem-
perature to the designed operation value at the time
of 10 h (Fig. 3a), the system returned to the original
steady state without any additional loss of the MTBE 1.0 325
production. 0.9
320
When the feed inlet temperature was changed from 0.8
302 K to 297.5 K, the reactor crossed the Hopf bifur- c 315
0.7
cation point. Fig. 3b shows the dynamic behaviour of

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

The temperature profile during several periods of sus- 0.1 290

tained oscillations is shown in Fig. 4. Figs. 3b and 4
show that the period of the oscillations was approxi-
mately 17 min. After returning the feed temperature
to the designed operation value (Fig. 3b), the reactor
became stabilised in the original steady state. The op-
eration of the reactor in a region of sustained oscilla-
tions would have an unwanted effect on the equipment
connected to the reactor outlet.
Finally, when the feed inlet temperature dropped
below the value of 295 K, the reactor switched to the
lower steady state. The lower steady state is char-
acterised by a very low value of the isobutene con-
version. When the feed inlet temperature reached the
designed operation value again (Fig. 3c), the reactor
continued operating in the lower steady state and a
significant loss of the MTBE production occurred. To
switch the reactor to the upper steady state, the feed
inlet temperature had to be increased up to 303.5 K
when the limit point on the lower steady state was
crossed (Fig. 3).
0 2 4 6 8
time / h
Fig. 5. Evolution diagram of a failure of the reactor inlet tem-
perature (step change of the reactor feed inlet tempera-
ture to the value 295 K) for 15 min (a), 45 min (b) and
60 min (c) (solid lines – IB conversion at the reactor
outlet XIB , dashed lines – reactor feed inlet tempera-
ture (T F )).
In many cases, the duration of the failure may dra-
matically affect the response although this aspect is
not usually investigated during a “typical” HAZOP
procedure. Thus, for the next simulation, the same
deviation – higher reactor feed inlet temperature was
taken into account. The failure was simulated as a
step change from the operating temperature of 302 K
to the value of 295 K with varying failure durations
(Figs. 5a–5c). In the first case, the failure duration
was set to the value of 15 min (Fig. 5a). After return-
ing the feed inlet temperature to the designed opera-
56 J. Labovský et al./Chemical Papers 62 (1) 51–57 (2008)

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
steady state, without any significant MTBE produc-
tion loss. Fig. 5b shows the effect of a 45 min duration
of the failure. In this case, the return to the original
steady state took more than 5 h and the losses of the
MTBE production were considerable. Finally, Fig. 5c
clearly shows that in the case of a failure longer than
1 h, the reactor became stabilised in the lower steady
state characteristic by a very low isobutene conversion.
Moreover, the reactor stayed in the lower steady state
in spite of the feed inlet temperature being returned
to the original operating value. To return the produc-
tion of MTBE to the designed value, a new start up
of the reactor was required.
Analysis of remaining parameters
Methanol and butenes feed flow rates are the ba-
sic regulation parameters which affect the reactor be-
haviour significantly. Fig. 6a shows the continuation
diagram for the feed flow rate of methanol. This fig-
ure reveals that a failure in the methanol feed flow
rate may result in switching to lower steady state or
to formation of oscillations if its value exceeds the
Hopf bifurcation point at 122 kmol h−1 (feed flow
by 35 % higher than the designed value) or the limit
point at 144 kmol h−1 (by 50 % higher than the de-
signed value). A different situation occurs in the case
of butenes. The designed molar flow rate of butenes is
460 kmol h−1 (marked with an empty square, Fig. 6b)
and is located in the area of multiple steady states.
If the feed flow rate of butenes increases, the reactor
will follow an upper stable steady state branch and the
conversion of isobutenes will slowly decrease. However,
the possibility of shifting to the lower steady state is
quite impossible due to the transport limitations. This
situation could theoretically occur if the butenes feed
flow rate increased to the value of 900 kmol h−1 , which
is practically impossible.
Another investigated parameter was the reactor re-
flux. In the described reactor, the reflux served for
adjusting optimal temperature and concentration con-
ditions in the reacting zone. The designed value was
0.5. Fig. 6c shows that a decrease of the reactor reflux
causes a slight reduction of the reactor conversion. On
the other hand, if the reflux crosses the value of 0.725,
the reactor shifts to the lower steady state and the
conversion decreases significantly. The last analysed
 J. Labovský et al./Chemical Papers 62 (1) 51–57 (2008)
parameter was the composition of the butenes feed.
The considered content of isobutene was 18.7 %. The
operating point lies very close to the bifurcation point.
Therefore, even a small disturbance in the butenes
feed composition can cause unwanted oscillations or
shift the reactor to the lower steady state.
All derived HAZOP deviations along with their
consequences can be analysed in a similar way us-
ing the DYNHAZ code. The results of this procedure
present a wide multidimensional view of the reactor
safety. This information could directly serve for the
examination of the reactor safety, or as a robust basis
for the subsequent ordinary HAZOP study.
Acknowledgements. This project was supported by the Slo-
vak Scientific Grant Agency VEGA, Grant No. 01/4447/07.
References
Chen, F., Huss, R., Doherty, M. F., & Malone, M. F. (2002).
Multiple steady states in reactive distillation: kinetic ef-
fects. Computers & Chemical Engineering, 26, 81–93. DOI:
10.1016/S0098-1354(01)00750-5.
Dimitriadis, V. D., Hackenberg, J., Shah, N., & Pantelides, C.
C. (1996). A case study in hybrid process safety verification.
Computers & Chemical Engineering, 20, S503–S508. DOI:
10.1016/0098-1354(96)00093-2.
Eizenberg, S., Shacham, M., & Brauner, N. (2006). Combin-
ing HAZOP with dynamic simulation-Applications for safety
education. Journal of Loss Prevention in the Process Indus-
tries, 19, 754–761. DOI: 10.1016/j.jlp.2006.07.002.
Göring, M. H., & Schecker, H. G. (1993). HAZEXPERT - an
integrated expert system to support hazard analysis in pro-
cess plant design. Computers & Chemical Engineering, 17,
429–434. DOI: 10.1016/0098-1354(93)80262-L.
Graf, H., & Schmidt-Traub, H. (2001). An integrated approach
to early process hazard identification of continuous and batch
plants with statechart modelling and simulation. Comput-
ers & Chemical Engineering, 25, 61–72. DOI:10.1016/S0098-
1354(00)00633-5.
Güttinger, T. E., & Morari, M. (1997). Predicting multiple
steady states in distillation: Singularity analysis and reac-
tive systems. Computers & Chemical Engineering, 21, S995–
S1000. DOI:10.1016/S0098-1354(97)87632-6.
Kubíček, M. (1976). Algorithm 502: Dependence of solu-
tion of nonlinear systems on a parameter [C5]. ACM
Transaction on Mathematical Software, 2, 98–107. DOI:
10.1145/355666.355675.
Labovský, J., Jelemenský, Ľ., & Markoš, J. (2006). Safety anal-
ysis and risk identification for a tubular reactor using the
HAZOP methodology. Chemical Papers, 60, 454–459. DOI:
10.2478/s11696-006-0082-0.
View publication stats
57
Mohl, K.-D., Kienle, A., Gilles, E.-D., Rapmund, P., Sund-
macher, K., & Hoffmann, U. (1999). Steady-state multiplic-
ities in reactive distillation columns for the production of
fuel ethers MTBE and TAME: theoretical analysis and ex-
perimental verification. Chemical Engineering Science, 54,
1029–1043. DOI: 10.1016/S0009-2509(98)00327-3.
Molnár, A., Markoš, J., & Jelemenský, Ľ. (2005). Some con-
siderations for safety analysis of chemical reactors. Chem-
ical Enginnering Research and Design, 83, 167–176. DOI:
10.1205/cherd.03284.
Mushtaq, F., & Chung, P. W. H. (2000). A systematic HAZOP
procedure for batch processes, and its application to pipeless
plants. Journal of Loss Prevention in the Process Industries,
13, 41–48. DOI: 10.1016/S0950-4230(99)00054-6.
Parmar, J. C., & Lees, F. P. (1987). The propagation of faults in
process plants: Hazard identification. Reliability Engineering,
17, 277–302. DOI:10.1016/0143-8174(87)90093-X.
Rehfinger, A., & Hoffmann, U. (1990). Kinetics of methyl ter-
tiary butyl ether liquid phase synthesis catalyzed by ion ex-
change resin. I. Intrinsic rate expression in liquid phase ac-
tivities. Chemical Engineering Science, 45, 1605-1617. DOI:
10.1016/0009-2509(90)80013-5.
Schrans, S., de Wolf, S., & Baur, R. (1996). Dynamic simulation
of reactive distillation: An MTBE case study. Computers &
Chemical Engineering, 20, S1619–S1624. DOI: 10.1016/0098-
1354(96)00275-X.
Shimada, Y., Suzuki, K., & Sayama, H. (1996). Computer-aided
operability study. Computers & Chemical Engineering, 20,
905–913. DOI: 10.1016/0098-1354(95)00187-5.
Srinivasan, R., Dimitriadis, V. D., Shah, N., & Venkatasubra-
manian, V. (1997). Integrating knowledge-based and math-
ematical programming approaches for process safety verifi-
cation. Computers & Chemical Engineering, 21, S905–S910.
DOI: 10.1016/S0098-1354(97)87617-X.
Švandová, Z., Kotora, M., Markoš, J., & Jelemenský, L.
(2006). Dynamic behaviour of a CSTR with reactive distil-
lation. Chemical Engineering Journal, 119, 113–120. DOI:
10.1016/j.cej.2006.03.032.
Švandová, Z., Markoš, J., & Jelemenský, L. (2005a). HAZOP
analysis of CSTR with the use of mathematical modelling.
Chemical Papers, 59, 464–468.
Švandová, Z., Jelemenský, Ľ., Markoš, J., & Molnár, A. (2005b).
Steady states analysis and dynamic simulation as a com-
plement in the HAZOP study of chemical reactors. Pro-
cess Safety and Environmental Protection, 83, 463–471. DOI:
10.1205/psep.04262.
Weatherill, T., & Cameron, I. T. (1989). A prototype expert
system for hazard and operability studies. Computers &
Chemical Engineering, 13, 1229–1234. DOI: 10.1016/0098-
1354(89)87028-0.