c 2006 Institute of Chemistry, Slovak Academy of Sciences

DOI: 10.2478/s11696-006-0082-0

Safety Analysis and Risk Identification for a Tubular Reactor Using

the HAZOP Methodology*
J. LABOVSK, . JELEMENSK**, and J. MARKO

Institute of Chemical and Environmental Engineering, Faculty of Chemical and Food Technology,
Slovak University of Technology, Radlinskho 9, 812 37 Bratislava, Slovak Republic
e-mail: ludovit.jelemensky@stuba.sk
Received 6 April 2006; Revised 6 July 2006; Accepted 1 August 2006

A model approach to Hazard and Operability (HAZOP) analysis is presented based on the mathematical modeling of a process unit where both the steady-state analysis, including the analysis of
the steady states multiplicity and stability, and the dynamic simulation are used. Heterogeneous
tubular reactor for the ethylene oxide production from ethylene and oxygen was chosen to identify potential hazards for real system. The computer code DYNHAZ was developed consisting of a
process simulator and a generator of the HAZOP algorithm.
Keywords: reactor safety, hazard analysis, dynamic simulation, multiple steady states, HAZOP
methodology

INTRODUCTION
The identication of various potential hazards inherent in a modern chemical plant is a task focused on
determining a possible combination of events that can
lead into an unsafe or undesirable operating state of
the studied process. These potential hazardous faults,
not identied beforehand, may cause several consequences, not only for the process itself (loss of production or integrity of the process), but also for the
safety of the operational sta. Furthermore, it should
be taken into account that the reactors representing
the heart of chemical plants are often operated at extremes of pressure and temperature to achieve optimal performance, thus making them more vulnerable
to equipment failures.
The number of basic reactor types is really large.
Nowadays, examination of the reactor safety is very
often based on the expert experience based on the
knowledge of the applied or similar reactor operation.
Naturally, such experience is valid only in the tight
regions of the reactor operational conditions and design parameters. To analyze process hazards and to
improve the reactor safety, the experts systematically

ask questions such as: What can go wrong?, How

likely is it to happen?, How could they be averted
or mitigated?, How safe is safe enough?, etc.
The answers to these and other related questions
are the source of root causes in the process of hazards
identication in a chemical plant. This is, however, a
complex and time-consuming task. One of the most effective techniques to solve this problem is the Hazard
and Operability (HAZOP) analysis [1]. During such
a study, a multidisciplinary team uses a prescribed
protocol to methodically evaluate the signicance of
deviations from the normal operation of the plant design conditions. HAZOP is a very detailed and complex method. On the other hand, due to its non formal
and creative character, one essential drawback of the
HAZOP study is the possibility that hazards or dangerous consequences may be overlooked. Thus, there
is enough motivation to develop computer-based approaches for hazard identication.
In the last 20 years a lot of research eort was dedicated to the development of computer-based analysis
methods roughly distinguishing an expert and modelbased approaches. A typical expert approach for the
HAZOP study, which usually comprises three or four

*Presented at the 33rd International Conference of the Slovak Society of Chemical Engineering, Tatransk Matliare,
2226 May 2006.
**The author to whom the correspondence should be addressed.

454

Chem. Pap. 60 (6) 454459 (2006)

SAFETY ANALYSIS AND RISK IDENTIFICATION FOR A TUBULAR REACTOR

knowledge bases and an interface engine, was proposed

by Shimada et al. [2]. The knowledge bases present the
expert knowledge about the technology, e.g. specic
parameters, specication of chemicals, reactions, and
plants topology. Each process variable of equipment
is examined in a sequence by searching the generic
knowledge base. Resulting from this search the operability study is generated. Other expert approaches
with additional facilities have been developed by authors [35].
In contrast to the knowledge-based approach, the
model-based approach has gained more importance in
the last years. It describes the chemical plant behavior
using a mathematical model and only focuses on the
model examination. This procedure holds promise of
greatly reducing the time and eort required in HAZOP, making the study more smooth and detailed,
and minimizing the inuence of human factors. As the
rst, Parmar and Lees [6] attempted to automate the
HAZOP study by using qualitative propagation equations for initiation and termination events. Another
approach was developed employing the Petri Net philosophy [7].
For all model-based methods, the implementation
formalism is the basis for simulation or analysis identication algorithm. The authors [8, 9] used a set of
qualitative equations derived from a quantitative description of the plant behavior. A hybrid model was
presented in [10] using a continuous description of differential equations supplemented with discrete controller actions. Graf and Schmidt-Traub [11] used a
combination of expert and model-based approaches
with the aim to take advantage of the qualitative modeling of chemical plants and the methods for logical
controller verication. Other model-based approaches
were published in [1217]. In the recent years, the dynamic simulation of chemical processes has also been
extensively used in the model-based approach [7, 18].
The model-based approach with a set of mathematical equations derived from the quantitative description of a chemical plant seems to be the most
straightforward procedure. However, it is not the easiest way due to the diculties encountered in solving
the complex and nonlinear set of dierential and also
partial dierential equations. Although mathematical
models of chemical processes are increasingly becoming available, the important problem of safety assessment and improvement is still addressed mostly using qualitative models and techniques. The latter ones
typically require a considerable eort providing little
quantitative information on any problem identied.
In safety analysis of a reactor, it is very important
to know the boundary between the normal operational
and potentially hazardous conditions (high temperature, high pressure), which can lead to a breakdown
of the reactor. Such undesirable situation may occur
after small disturbances in the process parameters.
Therefore, it is very important to know the inuence

Chem. Pap. 60 (6) 454459 (2006)

of all process parameters on the reactor behavior. Of

course, many methods like the parametric sensitivity
and continuation of the chosen parameter may provide
this partial information.
Presented study was aimed to develop a modelbased approach including the HAZOP methodology
based on a very complex mathematical model of tubular heterogeneous reactor. In the hazard identication
process, both the steady-state analysis and the dynamic simulation were provided. Combination of the
standard identication method, like HAZOP, together
with the mathematical modeling, has the potential to
become a very practical and robust tool for the reactor
safety analysis. To simulate a real industrial system,
the reactor for ethylene oxide production from ethylene and oxygen has been chosen. For this purpose the
computer code DYNHAZ was developed comprising a
process simulator and a generator of the HAZOP algorithm.
THEORETICAL
The rst step in the development of dynamic simulation approach based on the process modeling and
the HAZOP methodology for the risk identication
and safety analysis was the deduction of suciently
complex, universal, and easy to solve mathematical
model.
For tubular reactors continuous models are very
often used. The simplest one-dimensional model of
a heterogeneous tubular reactor, taking into account
temperature and concentration dierences between
the uid bulk and the catalyst surface, was given e.g.
in [19]

Ci
Ci
2 Ci
+w
DEZ
= kF aV (CiS Ci )
t
z
z 2
C p

(1)

NI


T
2T
T
+w
EZ 2 =
Ci Cpi
t
z
z
i=1

= hF aV (T S T )

4UW
(T TW )
dR

(2)

where Ci represents the concentration of component

i in the uid phase, CiS concentration of the component i in the solid phase, T reactor temperature, T S
catalyst temperature, catalyst porosity, C p medium
heat capacity of the bed, medium density of the bed,
w supercial uid velocity, NI number of components,
Cpi mole heat capacity of the component i, DEZ axial
dispersion coecient, kF mass transfer coecient between the uid bulk and catalyst particle, aV external
particle surface area per unit of the reactor volume,
EZ axial heat conductivity, hF heat transfer coecient between the uid bulk and catalyst particle, UW
overall heat transfer coecient, dR reactor diameter,
TW wall temperature, z axial position in the reactor,
and t time.
455

J. LABOVSK, . JELEMENSK, J. MARKO

For the solid phase

kF aV (CiS Ci ) =
hF aV (T S T ) =

NR

NR

ji Vj (C S , T S )

(3)

j=1

r Hj Vj (C S , T S)

(4)

j=1

where ji are stoichiometric coecients, Vj rate of

chemical reaction, r Hj reaction enthalpy for the reaction j, and NR total number of reactions.
The enthalpy balance for the cooling medium is
dened as
dTC
dR UW
=
(TC TW )
dz
m
C CpC

(5)

C cooling
TC being the cooling medium temperature, m
medium ow rate, and CpC mole heat capacity of the
cooling medium.
Boundary conditions are represented by the following equations
z = 0 t 0, t :
dCi
dz
NI
N
I




dT
wF
CiF Cpi T F = w
Ci Cpi T EZ
dz
i=1
i=1
wF CiF = wCi DEZ

(6)

TC = TCF
z = L t 0, t :
dT
dCi
=0
=0
dz
dz
and initial conditions are written in the form
z 0, L t = 0 :
CiS = Ci0 T S = T 0

(7)

where wF is the supercial uid velocity at the reactor inlet, CiF is concentration of component i in the
feed, T F feed temperature, TCF cooling medium inlet
temperature, L reactor length, Ci0 initial concentration of component i in the solid phase, and T 0 initial
temperature of the catalyst.
Generally, the mathematical model of any heterogeneous gas-solid reactor consists of material and enthalpy balances of the uid and the solid phase, kinetic equations, and enthalpy balance of the cooling
medium. From this set of equations, it is necessary to
extract all variables, which should be used for generation of the HAZOP deviations. For example, from
eqn (1) the concentration as the rst variable could
be extracted. However, it cannot be used directly to
generate the HAZOP deviations, because the fundamental meaning of the mole concentration may be interpreted in the HAZOP study in several ways. Of
course, it is possible to use the mole concentration
456

directly in the HAZOP analysis, however, as the keyword. One should be aware that the concentration of
component i depends on the feed ow and the feed
composition. Therefore, only one variable from eqn
(1) can be interpreted in the HAZOP study as the
keyword choosing from the terms ow of the component i, feed ow, feed composition, or concentration
of the component i.
These are the typical keywords employed in the
HAZOP analysis. This heuristic algorithm has to
be applied for all variables found in the mathematical model of the reactor. During this procedure a large
number of duplicate consequences are obtained for different faults leading to the deviations.
Then, the HAZOP deviations are generated using the same procedure as in the classical HAZOP
study, i.e. by combining the keywords with the HAZOP guidewords, e.g. the keyword Flow of component
i can be used for the generation of four deviations:
more (higher) ow of component i
less (lower) ow of component i
no ow of component i
reverse ow of component i
The set of partial dierential equations (1), (2),
and (5) was discretized using the method of nite differences. For the time integration, implicit schemes
and backward dierential formulas up to the 5th order with a step controller were used. For solving sparse
linear equations the LAPACK library was used.
Once all possible deviations have been generated,
the self-numerical simulations take place. At this
point, a serious dilemma appears. How to nd the consequence of the deviation more flow of component i?
The only feasible solution is to perform a set of several dynamic simulations, where the deviation from
the keyword is created within the range of 100 %
from the design value of the keyword. The deviations
could be simulated either as a step change or a continuous change of the keyword value.
The dynamic simulation provides important information for the reactor safety on the temperature
and concentration proles in the reactor, position and
value of the hot spot temperature, temperature and
concentration gradients between the uid and the solid
phases, and changes in selectivity and conversion as
the system response to the perturbation assumed.
Although this information is essential for the examination of reactor safety, it is not always sucient
enough. Therefore, during each simulation, additional
mathematical analysis must be performed. The rst
additional analysis is the identication of the multiple
steady states and their stability, i.e. the study of safe
operating conditions and conditions, at which the reaction system is switched from one steady state to another qualitatively dierent steady state [2022]. The
second additional analysis is the parametric analysis
used to identify the conditions, at which the reactor
run-away may occur [23].

Chem. Pap. 60 (6) 454459 (2006)

SAFETY ANALYSIS AND RISK IDENTIFICATION FOR A TUBULAR REACTOR

Table 1. Selected Results of the Dynamic Simulations Focused on the Identication of the Maximum Reactor Temperature
100 % 50 % 20 % 10 % 5 % 1 %

Deviation

Inlet oxygen concentration

495.58
Inlet ethylene concentration
517.50
Inlet feed temperature

Cooling medium inlet temperature

Cooling medium ow rate

Feed mass ow

Reactor pressure

501.57 508.82
517.52 517.53
514.52 514.64
346.45 436.42
570.81* 520.25
511.07 515.39
532.69* 521.27

512.66
517.56
515.00
468.09
518.72
516.38
519.19

514.74
517.57
515.56
485.92
518.11
516.94
518.33

516.95
517.57
516.88
506.26
517.68
517.45
517.72

1%

5%

10 %

20 %

50 % 100 %

518.24 521.37 527.54 543.80* *

*
517.58 517.58 517.59 517.60 517.63 517.66
518.49 535.03*541.47* *
*
*
545.17*565.13*575.12* *
*
*
517.48 517.11 516.69 515.97 514.49 513.09
519.47 519.92 520.43 521.26 524.13
*
517.43 516.89 516.27 515.17 512.98 510.85

* Potentially dangerous situation, which may lead to the reactor run-away behavior. At normal operational conditions, the maximum
reactor temperature is about 517.6 K.
Table 2. Example of the Derived HAZOP Deviations and the Corresponding Consequences for the Partial Oxidation of Ethylene
to Ethylene Oxide
Deviation

Extent

Consequence

No oxygen flow
100 %
Not dangerous, but a technological problem, conversion is too low (zero)
Lower oxygen flow 50 %; 1 % Not dangerous, but a technological problem, conversion is too low
Higher oxygen flow
1 %; 100 %
May be dangerous if the deviation is higher than 20 %, possible run-away and explosion

Such a huge amount of information cannot be used

directly. Therefore, all the results should be heuristically interpreted and translated into the form of purposeful HAZOP consequences. Finally, a complete set
of automatically generated HAZOP deviations along
with the most important consequences is inserted into
the HAZOP tables. The data comprised in the HAZOP tables could be a very useful starting point for
the examination of reactor safety and might be considered a very ecient screening of the reactor behavior
and safety.
RESULTS AND DISCUSSION
Case Study Partial Oxidation of Ethylene to
Ethylene Oxide
The principles of the safety analysis, based on the
combination of mathematical modeling and the HAZOP methodology were applied on the model system
constituted of a tubular reactor used for partial oxidation of ethylene to ethylene oxide. The kinetic data
and transport parameters for the chosen model reactor
were taken from [24]. At standard operating point, the
oxygen and ethylene inlet concentrations were 14 mol
m3 and 220 mol m3 , respectively. The inlet temperature of the cooling medium was 495 K and the
cooling medium ow rate was 0.9 kg s1 . The tubular
reactor length was 12 m and the diameter 0.0508 m.
The reaction takes place in an excess of ethylene
V1

O2 + 2C2 H4 2C2 H4 O

(A)

Two main by-products, CO2 and H2 O, are formed

according to the following reaction scheme
V2

O2 + 1/3C2 H4
2/3CO2 + 2/3H2 O

Chem. Pap. 60 (6) 454459 (2006)

(B)

The reaction rates in eqns (3) and (4) were also

taken from [24]


V1 = k1 CO k1 = 5.7 104 exp 59860 R
(8)
2
T
V2 = k2 CO2



R
k2 = 4 108 exp 89791
T

(9)

In this simplied example, the algorithm used only

seven dierent HAZOP process words:
Oxygen inlet concentration
Ethylene inlet concentration
Inlet feed temperature
Cooling medium inlet temperature
Cooling medium ow rate
Feed mass ow rate
Reactor pressure
For all these keywords and the HAZOP guidewords, a set of realistic deviations was generated.
Then, the computer code performed a set of dynamic
simulations. Some of the results presenting the maximum temperatures in the reactor after a step change
of the keyword values are shown in Table 1. These
data represent only a part of the information necessary
for the assessment of reactor safety. However, from
the simulation results partial information could be
extracted allowing to formulate purposeful HAZOP.
Taking into account the rst line in Table 1, it was
possible to generate three HAZOP deviations shown
in Table 2.
Based on the heuristic interpretation of the dynamic simulation results the consequences of these
three deviations were generated.
The possible hazard consequence of the latter deviation would be the increase of the reactor temperature
457

J. LABOVSK, . JELEMENSK, J. MARKO

Fig. 1. Dynamic evolution of the temperature prole along the reactor for dierent positive deviations from the input oxygen
molar ow rate: a) 1 %, b) 5 %, c) 20 %, and d) 23 %.

600

-3

CC H O / (mol m )

TC / K

550

2
450

10

20

30

-3

40

50

C0 / (mol m )
2

Fig. 2. Locus of the run-away eect for the cooling medium

temperature vs. oxygen inlet concentration plot: circle corresponds to the normal reactor operation point,
dashed line limits the region of the possible reactor runaway exceeding the temperature of 700 K (region 1),
and dotted line represents the border of the region of
operational conditions, at which the conversion is lower
than 80 % of the normal ethylene conversion (region 2).

over the safe value of 544 K. The dynamic evolution

of the temperature prole along the reactor for dierent values of this deviation is depicted in Fig. 1. The
simulation data show, that the consequence of a slight
increase of the deviation above 20 % would cause the
reactor temperature run away due to the ethylene ox458

500

10
F

15

20

25

-3

CO /(mol m )
2

Fig. 3. Locus of the steady states for the outlet ethylene oxide concentration vs. inlet oxygen concentration plot
assuming a constant inlet temperature of the cooling
medium.

ide auto-ignition at temperatures exceeding 700 K.

Furthermore, DYNHAZ is able to calculate the locus of the process variables, at which the run away
eect could occur. In Fig. 2 dashed line represents the
locus of the run-away for the chosen pair of process
variables. One can appreciate that the position corresponding to the normal operating conditions is very
close to the run-away line. Thus, already a relatively
small positive deviation of the oxygen concentration
or the cooling medium temperature from the normal

Chem. Pap. 60 (6) 454459 (2006)

SAFETY ANALYSIS AND RISK IDENTIFICATION FOR A TUBULAR REACTOR

operating point would shift the studied system to a

dangerous state.
In Fig. 3 the locus of steady states for the inlet oxygen concentration and the outlet ethylene oxide concentration is depicted. The locus of the reactor steady
states was calculated by a continuation algorithm in
the DYNHAZ code exhibiting a single steady state for
the whole investigated region.
All derived HAZOP deviations along with their
consequences were analyzed in a similar way by 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 Slovak Scientific Grant Agency VEGA, Grant No. 1/1377/04.

SYMBOLS
aV
Ci
CiF
CiS
Ci0
Cp
Cp
dr
DEZ
k
hF
r H
kF
L
m
C
NI
NR
R
T
TF
TC
TCF
TS
T0
t
U
w
z

external particle surface area per unit of

the reactor volume
m2 m3
concentration of component i in the uid
phase
mol m3
concentration of component i in the
feed
mol m3
concentration of component i in the solid
phase
mol m3
initial concentration of component i in the
solid phase
mol m3
mole heat capacity of the uid J mol1 K1
medium heat capacity of the
bed
J mol1 K1
reactor diameter
m
axial dispersion coecient
m2 s1
reaction rate constant
s1
heat transfer coecient between the uid
bulk and catalyst particle
W m2 K1
reaction enthalpy
J mol1
mass transfer coecient between the uid
bulk and catalyst particle
m s1
reactor length
m
cooling medium ow rate
kg s1
number of components
number of reactions
gas constant
J mol1 K1
reactor temperature
K
feed temperature
K
cooling medium temperature
K
cooling medium inlet temperature
K
catalyst temperature
K
initial temperature of the catalyst
K
time
s
overall heat transfer
coecient
J s1 m2 K1
supercial uid velocity
m s1
axial position in the reactor
m

Chem. Pap. 60 (6) 454459 (2006)

Greek Letters

EZ
i

Vj

stoichiometric coecient
axial heat conductivity
mole density
porosity
rate of chemical reaction

W m1 K1
mol m3
mol m3 s1

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