OVERVIEW OF MECHANISTIC MODELLING TECHNIQUES

APPROACHES TO MODELLING
Process models are very useful. They can be used for operator training; safety analysis and
design of safety systems; process design and process control systems designs. There are 2 main
approaches to developing process models,

a) empirical or data based modelling

b) building models based on the underlying physics and chemistry governing the
behaviour of the process

The following will discuss differences between the two approaches.

Developing Empirical Models

In empirical modelling, the following procedure is usual

(1) collect data from the process

(2) specify the correlation structure between variables, e.g. polynomials; time-series;
artificial neural networks

(3) use a numerical technique to find parameters for the structure such that the correlation
between the data is maximised

(4) validate the model against an ‘unseen’ data set

(5) if model is not satisfactory, go to step (2)

Thus, we can see that in empirical modelling,

• much depends on the availability of representative data for model building and
validation

• apart from cause-and-effect between variables, not much else is required in terms of
process knowledge

• a trial and error approach is adopted

Developing Mechanistic Models

The development of mechanistic models follow a different procedure:

© 1998-2000 Ming Tham

Department of Chemical and Process Engineering
University of Newcastle upon Tyne

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 (1) use fundamental knowledge of the interactions between process variables to define the
model structure

(2) perform experiments to determine the parameters of the model

(3) collect data from the process to validate the model

(4) if the model is not satisfactory, go to step (1) and re-examine process knowledge

Mechanistic modelling therefore

• does not require much data for model development, and hence is not subject to the
idiosyncrasies in data

• requires a fundamental understanding of the physics and chemistry governing the

process

• can be very time consuming

As an alternative to step (2), once the structure of the model is defined, numerical techniques can
be applied to parameterise the model. In this case, although the structure has been determined
from process knowledge, the modelling procedure becomes an empirical one. The numerical
techniques that are used are also very different from those usually encountered in purely
empirical modelling. They tend to be iterative, and are more complex.

Empirical versus Mechanistic Models

When available, mechanistic models can provide more realistic predictions, and more can be
done with it in terms of analyses. For example, the details contained within a mechanistic model
offer the opportunity to test the sensitivities of the process to meaningful entities such as heat
transfer coefficients; activation energies; catalyst poisoning, etc. With very few exceptions, the
parameters of data based models are just numbers encapsulating combined effects. This it is very
difficult to attach physical meaning to them, and hence such sensitivity studies cannot be
performed.

Thus, while mechanistic models are used to design processes, empirical models are frequently
used as the bases for process controller designs. The argument here is that model based
controllers only require the models to represent with some accuracy, the trends in process
behaviour. Conservative tuning, together with the feedback mechanism are usually sufficient to
overcome any inaccuracies. Nevertheless, if a mechanistic model is available, it will be foolish
to discard it in favour of a data based one.

Another comparison that is always made between the two modelling approaches is that of cost.
Due to the complexity of many processes, mechanistic modelling is indeed very expensive in
terms of human effort and expertise. As the mechanistic modelling approach forces a detailed
examination of fundamental process behaviour, some of the cost is recovered in terms of
increased ‘deep’ knowledge of process behaviour. Such benefits are intangible though, and are
often discounted. In practice, empirical modelling can be expensive as well. It requires large
amounts of ‘representative’ data, and in many instances, these can only be acquired by
© 1998-2000 Ming Tham
Department of Chemical and Process Engineering
University of Newcastle upon Tyne

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perturbing the process via planned experiments. Inevitably production will be disrupted, and the
lost revenue can exceed the cost of hiring someone to develop a mechanistic model. The
advantage with empirical modelling lies in the fact that empirical modelling will deliver some
form of working model in a much shorter time.

The consequence of this is that we have to question what the model is to be used for. If it is to
design control algorithms, then empirical models will do. However, if we need a model to design
a new process; or one that can be used to trouble-shoot a process that is behaving poorly; or a
model that is capable of pointing towards fundamental improvements in process operability, then
it is best to develop a mechanistic model.

MECHANISTIC MODELS
Physical systems obey certain fundamental laws. Mechanistic modelling makes use of these laws
to build a description of processes, i.e. equations of continuity. These are the balance equations
that describe the conservation of mass, and the conservation of energy.

Mass Balance
Mass balances are statements of the principle of conservation of mass. There are two types of
mass balances,

(1) the overall mass balance, and

(2) component balances

and each can be further classified as being ‘steady-state’ or ‘dynamic’ (non-steady state). Since
steady-state balances are special cases of dynamic balances, we shall only consider the latter.

Overall (total) mass balance

The general form of an overall dynamic mass balance is given by the expression:

 Rate of accumulation  Rate of   Rate of 

  =  − 
 of mass in the system  mass flow in  mass flow out

The rate of accumulation term represents the rate of change in the total mass of the system with
respect to time. At steady-state, by definition, there will not be any change, and so this term
becomes zero, that is:

 Rate of accumulation  Rate of   Rate of 

  =0=  − 
 of mass in the system  mass flow in  mass flow out 

and therefore, at the steady-state

 Rate of   Rate of 
  = 
 mass flow in  mass flow out 

© 1998-2000 Ming Tham

Department of Chemical and Process Engineering
University of Newcastle upon Tyne

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Component balance
With chemical engineering systems, it is usual for processes to contain more than one chemical.
If there is no reaction, then the dynamic balance equation for each component in the system is:

 Rate of accumulation   Rate of mass flow  Rate of mass flow

     
 of mass of component i =  of component i  −  of component i 
     
 in the system   into the system   out of the system 

which has a form identical to the overall dynamic mass balance above. With overall mass
balance equations, it is immaterial whether reactions are occurring within the system. With
components, however, mass is not conserved. They can be consumed and generated by chemical
changes. Thus to account for chemical reactions, the relevant expression to use is:

 Rate of accumulation   Rate of mass flow  Rate of mass flow 

     
 of mass of component i =  of component i  −  of component i 
     
 in the system   into the system   out of the system 
 Rate of production  Rate of consumption
   
+  of component i  −  of component i 
   
 by reaction   by reaction 

where there are generation and depletion terms. All the above equations apply at ionic and
atomic levels as well. For example, ionic balances and charge balances are used to characterise
the behaviour of electrochemical reaction systems.

Bear in mind that a component balance can be written for each chemical species in the system.
Thus, if there are N components in a system, there will be N component balances. However,
there is only one overall mass balance equation. Since the sum of the components will give the
total mass in the system, this means that the component balances and the overall mass balance
are related. Thus, it is sufficient to write N-1 component balances and the overall mass balance
to fully describe the mass flows in the system.

Energy Balance
Energy balances are important whenever there are temperature changes, as caused by chemical
reactions; by heating or cooling; by work done on the system; through heat losses from the
system. Like mass balances, there are steady state as well as dynamic energy balances, but
energy balance equations tend to be more complex because of the many factors that can cause
changes in energy content. Energy balances quantifies the principle of conservation of energy,
i.e. the First Law of Thermodynamics, which states that

 Total energy
  = (Internal Energy, U) + (Kinetic Energy, KE) + ( Potential Energy, PE)
 of system 

© 1998-2000 Ming Tham

Department of Chemical and Process Engineering
University of Newcastle upon Tyne

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Thus, for an open system, where flow of material in and out of the system can occur, the energy
balance would be of the following form:

 Rate of accumulation   Flow of U, KE and  Flow of U, KE and 

  =  − 
 of energy in the system  PE into the system   PE out of the system
 Energy added to system   Work done by system 
   
+  by conduction, radiation −  on the surroundings, e.g
   
 and reaction   PV work, shaft work 

In most chemical systems, flow velocities are low and the differences in elevation between inlet
and outlet flows are small. Therefore the KE and PE terms respectively, are negligible compared
to the U terms. The internal energy term, U, depends not only on temperature, but also on the
flows and composition of material. Thus, energy balances are almost always accompanied by
mass balances.

Temperature changes can occur when energy is introduced into system or lost by heat transfer
via conduction and radiation. Reactions can also cause changes in the temperature. For instance,
an exothermic reaction will cause temperature rises while lowering of temperature will occur
due to an endothermic reaction. If the system contains vapour, then there will be work done due
to expansion and compression of gases (PV work). Also, if the system has a stirrer and the
stirred mixture is very viscous, then the temperature changes due to shaft work can be
significant.

Thus, in performing an energy balance, the above factors must be considered carefully, so that an
accurate representation could be derived.

Momentum Balance
Momentum balances are based on Newton’s Second Law of Motion, which states that for a
system with constant mass, the force exerted by that mass is equal to the rate of change of
momentum. Momentum balances are important when modelling systems that involve the flow of
fluids. In chemical engineering flow problems, three forms of forces are encountered, namely
pressure forces, shear or viscous forces and gravitational forces.

• Pressure forces are given by the product of pressure and applied area.

• Shear forces are given by the product of shear stress and applied area.

• Gravitational forces consist of the force exerted by gravity on the fluid and is equal to
the product of the mass of fluid in the control volume times the local acceleration due
to gravity.

The momentum balance is written as:

© 1998-2000 Ming Tham

Department of Chemical and Process Engineering
University of Newcastle upon Tyne

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  Rate of change  Rate of momentum  Rate of momentum  Sum of forces acting
  =  −  + 
 of momentum   into the system   out of the system   on the system 

Note that momentum and forces are vector quantities, that is they have magnitude as well as
direction. Thus, the momentum balance must sum up the effects in 3D space. This is outside the
scope of this course, but suffice it to note that treatment of momentum balances is identical to
those of mass and energy.

© 1998-2000 Ming Tham

Department of Chemical and Process Engineering
University of Newcastle upon Tyne

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