Guidance for the use of the S2S

training & assessment tool

for unexpected reactors
Summary

The S2S assessment tool for unexpected reactors aims to identify how
reactive chemical hazards can exist in process units or plant equipment
outside the reactor. The assessment tool can also be used as a training tool
since it is based on simple concepts, which combine:

 A reaction triangle describing the factors necessary for obtaining a

reaction. The factors considered are temperature, concentration and
residence time.
 Process streams with physical and chemical properties that can be
mapped on the reaction triangle.
 Equipment or unit operations, which determine how process streams
are positioned and moved in the reaction triangle. The design of the
plant should insure that these moves are safe. At the same time,
equipment will have failure modes with possible side effects; these can
cause a shift in the reaction triangle that enables a reaction and may
pose a hazard.

The tool is presented as a program that generates discrete questions to

identify potential hazards and explains the likely mechanisms. It is applicable
both to batch, semi-batch and continuous processes and assumes that the
user has previously identified/characterized the reaction hazards through
literature studies, experiments or the S2S assessment methods.

Introduction

With the improved existing methods for identifying and reducing chemical
reactive hazards in process reactors, a large proportion of runaway accidents
in process industries occur nowadays outside the reactors. The most
commonly accepted reason why these hazards have remained unaddressed
and have lead to accidents, is that they were not expected to happen and
therefore plant equipment or operational procedures were not prepared to
deal with them. Conversely, if an incident is expected a measure will be taken
to prevent it. The unexpected reactor is the term we will use to identify the
reactive hazards that manifest themselves outside the reactor.

Reactive hazards are more difficult to recognize because of the exponential

nature (e.g. the speed of the temperature rise may increase exponentially),
double exponential in some cases (e.g. the resulting vapour pressurization),
of the consequences they may generate. It is not a simple pressure rise with
temperature (as in a normal process hazard), providing enough time for
actuation when noticed; the true hazard of chemical reactivity lies in the
existence of some violent reactions that may not be noticeable at normal
process conditions, but which could be started at a 50 °C higher temperature,
triggering an unforeseen situation with little margin of actuation left.

Assumptions are powerful barriers to identifying hazards. As an example, a

liquid pump is used to transfer a liquid, so when an operator or engineer looks
at that pump he/she has the mental model of a ‘liquid transporter’. However
when blocked-in it just heats the liquid, or when heated it will generate vapour,
or when fed with 2 immiscible liquids it may create an emulsion. The design
and operation of chemical processes are based on many such assumptions
that help to automatically “see” the behaviour and intended operation of the
process but inhibit the creativity to see unexpected things happen. A solution
therefore can be to identify hazards by breaking implicit assumptions when
dealing with these hazards; the goal is therefore to identify what could happen
prior to considering consequence or likelihood.

What is different in the approach developed by the S2S group becomes clear
when it is compared to some other well known methods for identifying
hazards in chemical plants, like for example HAZOP. This is a method that
very systematically tests assumptions by asking ‘what if’ questions. Its
weakness lies in the fact that it is not very efficient in identifying reactive
hazards. The reason for this is that the HAZOP takes a 1-dimensional
approach to hazards: only a single process variable is perturbed at a time: for
example flow, temperature or concentration. Many of these perturbation-
questions (example “what if the flow is higher”) will have no immediate
relevance to reactions and rely on a sound understanding of the equipment
behaviour. Reactive variants of HAZOP have been developed but these also
have a limited reactive context. It is the knowledge of the HAZOP participants
that must provide the context e.g. operation steps, equipment details, control
etc. Thus the HAZOP will be spending much time on potential hazard threats
that will turn out to be non-hazards, product quality, controllability issues and
ordinary non-reactive process hazards.

Development of the method

The method introduced is based on a set of simple questions regarding

reactivity that could be asked to engineers or operators involve in a process,
such as:
 Why is the reaction not taking place at process equipment other than
the reactor?
 What is needed to make such equipment behave as a reactor?
 How can that happen in this process?

The answers received could be structured in a simple way as well:

Structure of knowledge
For a reaction1 to occur a combination of 3 factors needs to be fulfilled:

 Concentration of Reactants
 Temperature of Reactants
 Time for reaction

This can be described in a triangle like the fire triangle.

Concentration

Temperature H T Time

Figure 1. The reaction triangle

The reason why these three factors are chosen is that they also represent the
most important free factors in process operation and design. As with the fire
triangle, a reaction requires an appropriate combination of these three factors:
reducing the contribution of concentration, temperature or residence time in
the triangle will reduce the possibility of a reaction to take place. There are
some special reactions that need a catalyst or high interfacial area between
phases (V/L, L/L, S/L or V/S) in order to obtain sufficient reaction speed.
These factors should be added to the Time-corner, in the sense that they
‘help’ the time factor. They both determine the speed of the reaction and can
be varied independently of the concentration and temperature. More so, they
are frequently used to reduce the time for reactions to complete and could
rightfully take the place in the reaction triangle. The Time corner could then be
replaced by the TIC corner (Time/Interface/Catalyst).

Now let us apply the reaction triangle to equipment examples in a chemical

process: 1) A reactor would evidently be an equipment somewhere near the
middle of the triangle.
2) A feed pre-heater in a process with a fast reaction, for instance, can be
considered as equipment on the temperature-time side of the triangle. This
means that it is supposed to heat a substance to reaction conditions, and it
cannot avoid substantial residence time (typically 1-105% of the reactor time),
so it should have a low concentration of one of two reactants to prevent
unintended reactions. So, what is needed to turn this equipment into an
unintended reactor? The answer would be to increase the missing axis of the
triangle, which is concentration. This situation would be generated by an
unexpected event, maybe backflow from the reactor, maybe product remnants
from another process step in a multipurpose plant.

1
The method implies the assumption of simple reactions such as A+B C and A
C+D
3) A centrifugal pump for a thermally unstable liquid can be designed to
operate in the concentration corner of the triangle. Then two things are
needed to turn the pump into an unexpected reactor: Temperature and Time.
This situation can be achieved by a blocked inlet or outlet (time) and a pump
motor that keeps running and generates heat (temperature).

Like the feed pre-heater and the pump, all unit operations have been
conceptualized with a specific task and are used with assumptions on its
capabilities. Conceptually they can all be positioned on the sides of the
reaction triangle, and will not pose hazards unless they move towards the
middle. There are several ways in which equipment can vary their position in
the reaction triangle: there are outside/process failures (like backflow),
equipment failure modes (e.g. heaters leak and foul) and equipment inherent
side effects (e.g. pumps generate heat). Some of the equipment effects are
specific to the product or process properties; for example, if a thermally
unstable product is involved, it will reduce the temperature margin for safety
operation; a heater or a system using an evaporative coolant/diluent can
evaporate a product and therefore bring the equipment closer to the
concentration corner of the triangle.

Like the fire triangle, the main factors that contribute to the hazard are easily
recognized and provide a simple concept to learn. Unlike the fire triangle
which serves as a tool to solve a single situation, the reaction triangle is
meant as a complete description of the process. It helps understanding how
the process design intends to avoid reaction hazards and how deviations can
break the design intentions.

The goal of the method is therefore to provide a system that will allow the user
to identify the possible ways in which the equipment used in an installation
could ‘move’ process streams with their properties over the triangle map,
hence generating a possible hazardous situation.

Generation of the knowledge base

The generation of a knowledge base using the above concept has been done
according to the following steps.

1) Collection of a list of examples of reactive hazards & incidents outside

the reactor. The list does not need to be complete but serves as a
starting point.
2) Generation of a list of equipment and system properties involved in the
unexpected reactors.
3) Classification of the incidents into physical-chemical mechanisms,
according to the elements included in the reaction triangle.
4) Review of the equipment list and check for each mechanism whether it
could apply. The result of the generated knowledge base looks like a
matrix detailing which equipment could present the specified hazard.

Development of the assessment tool

The method developed has been implemented as an assessment tool based
on a Microsoft Excel® worksheet included in the S2S web portal. The
assessment tool asks a limited number of generic questions and generates a
list of potential reactive hazards that can be further investigated, according to
the steps described in the previous section. General remarks on the nature of
the hazards and their possible consequences are put forward.

For an assessment tool it is important that it is simple to use, yet providing a

clear outcome. The number of difficult questions is reduced by starting with
simple questions first: what equipment is used and what physical and
chemical properties are involved in the process. The tool selects specific
questions based on this information. Lastly, in case the tool determines that a
hazard is likely to be present during the process, further explanations are
given.

For complex processes, it may be helpful to divide the process in sections,

thus reducing the amount and type of information handled each time. This is
because, in complex processes, the process intent varies between the
process steps and it will be easier to follow the assessment questions and
recommendations when concentrating on a single process step.
It must be stressed that it is not the aim of the tool to cover all the hazards
related to reactivity in a process plant, but to provide basic guidance towards
commonly unnoticed hazards. At the same time, it is not intended to provide
specific safety measures related to the hazards identified. It should be the
user, by means of his/her knowledge of the particular process and plant
possibilities, to come up with the most feasible solutions in order to perform
the process under safety conditions.

The assessment tool can be used by a person with some knowledge of the
process chemistry and physics. However, in case any doubt should arise by
the use of the method, the advice of an expert in the field of chemical
reactivity and process safety should be asked. It must also be kept in mind
that this method is a part of the S2S package of assessment tools that covers
other aspects of chemical reactivity, as well as other hazards like fire or
explosions. These tools should be used whenever necessary; particularly the
reactivity assessment tool should be used in case of doubt regarding stability,
compatibility and reactivity of the substances and mixtures involved in the
process.

8 June 2006