Process Modeling

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 Outline of this lecture
• Introduction and outline of the course
• Need for process modeling
• Statistical and mechanistic models
• Rate laws and adjustable parameters
• Selection of variables
• Model application areas
 Learning outcomes for this lecture
• Understand what is mathematical modeling and
how it is related to physical problems
• Recognize the need for modeling, estimate
necessary model complexity
• Understand how models are built from balances
and constitutive equations
• Understand the basis of rate laws and adjustable
parameters in them
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 Model generation
• Why a model is needed?
– To make quantitative predictions about system behaviour
– To back up financial or other decisions
– To optimize a new or existing process
– To operate efficiently and safely an existing process
– For illustration / teaching

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 The idea of a (mathematical) model

Real world 1 Mathematical 2 Mathematical 3 Interpretation

problem problem solution

1. Reality to mathematics
2. Mathematical solution
3. Interpreting the model outputs
4. Using the results in the real world
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 Model building steps
• Build a sketch and define quantities

1st step: a Black box

• What does a black box model mean?

• What do we have to know about the system inputs, states,
outputs and disturbances?
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 Model building steps
• Build a sketch and define quantities

1st step: a Black box

xin xout

xout = f(xin)
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 Model building steps
2nd step: assume something related to spatial or
temporal variations.

E.g. Plug flow dx/dh = f(x)

xin xout

D
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L
 Model building steps
• 3rd step: Assume Vapor phase (V) Dry catalyst (D)

detailed small scale

xD
phenomena and apply kVD
HD
VD
it in the big scale hVD cD
TD
model xV
HV
xVI xLI

VV hDW
TV

• E.g. Phases around a

xL xW
small catalyst particle kV kL
HL
VL kLW
HW
VW
in a trickle bed reactor hV hL TL hLW
cW
TW

• Multiscale modeling
TI
Liquid phase (L) Wet catalyst (W)
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 Box colors
• ”Black box” models:
– Empirical
– Process fundamentals are not necessary
– Based on observed input and output variables
– Purely mathematical (as an opposite to a physical
model) form where some parameters (coefficients)
are identified based on observed variables. These
coefficients typically have no physical meaning
– Often polynomials, could be neural networks etc.
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 Box colors
”White box” models

– Based on first principles: Conservation laws etc.

– ”transparent”, the model is understandable to a
knowledgeable process engineer
– No process or other data required (theoretically)
– Usually complex models
– In principle excellent extrapolation (scale-up) properties
– Can predict new phenomena (in principle)
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 Box colors
”Gray box” models

– In practice, purely ”white” or ”black” box models

are rare
– Mechanistic first principle building blocks bring
reliability in scale-up and extrapolation, and
functional dependencies to the expressions
– a priori knowledge about the model is used as well
to determine the structure and some of the
parameter values 12
 Model building steps
• Select variables
– input
– output
– model state
– independent (dimensions etc.)

• Input and output are usually quite clear. Model

state variables are sometimes difficult, and care
should be taken with independent variables
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 Selection of variables
• For example, energy variables: Temperature or
enthalpy?
• Temperature is easier to comprehend and is anyway
needed
• Enthalpy is sometimes better:
– T can be evaluated if H is known, but not always vice
versa (Example?)
– If T=300K and you add a stream with T=400K, the result
is not a system at T=700K. If H=1 kJ and you add H=2
kJ, the system has H=3 kJ
What is the formal difference between these variables?
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 Selection of variables
Formally balances are based on extensive variables, so those
should be the primary variables

For which of the following a balance can be written?

1. Amount of moles of a certain ion
2. Temperature
3. Pressure
4. Mechanical energy
5. Entropy
6. Volume
7. Number of particles with characteristic diameters
between L and L+dL 15
 Selection of variables

dc dn
r or  rV
dt dt
Ideally mixed
batch reactor
• What are these describing?
• Which one is based on conserved property
(extensive variables)

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 Selection of variables
concentration is not a conserved
property (extensive variable), but
amount of moles is.

dn dcV 
 rV n=cV  rV
dt dt
dc
This reduces to r
dV dc dt
c  V  rV only if volume does not change
dt dt
(or the first term is negligible)
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 Balances and closures
Physically correct models (not black box) are based on
balances (material, energy, momentum etc...)

In these balances, there are unknown rates (mass &

heat transfer, reaction etc...)

These rates are typically modeled with ”closures”

(closing the set of equations), or ”constitutive
equations”
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 Balances and closures

dn
Material balance  rV
dt

Ideally mixed
batch reactor

How do we know by looking at these equations that ideal

mixing is assumed?
What to do if it is not a valid assumption?
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 Balances and closures

dn
Material balance  rV
dt

• Why this is not ”closed”?

• What ”closures” or constitutive equations would be
needed to ”close” or be able to solve this
• Which adjustable parameters there could be?

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 Balances and closures

dn
Material balance  rV
dt

Reaction rate needs  E 

r  k r exp  c A c B
a model (closure)  RT 
Where to get all these
variable values?

These typically contain unknown (adjustable)

parameters. What to do with them? 21
 Independent variables
(dimensions)
Those dimensions that affect results must be
taken into the model
Nodal points where
the solution is calculated
1D # of variables  N

2D # of variables  N2

etc…. Symmetries help a lot! 22

 Model building steps continue
• List parameters that are important. Look for
nonlinearities (in the parameters or in the
model)
• Draw a sketch of expected behavior
• Write balances and constitutive relations. Check
sign conventions (direction of transfer that is
positive, whether component is produced or
consumed in a reaction etc.)
• Derive a set of equations that can be solved and
introduce initial and boundary conditions
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• Solve the model
• Interpret results

Then…
• Improve the model if it is not good enough
• Carry out sensitivity analysis
• Carry out optimization
• Test the model at extreme conditions (near the
applicability limits of the variables)
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 Model application areas

In which fields of chemical engineering or process

technology mathematical models could be used?

Discuss with a friend next to you

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 Model application areas
• Process design
– Feasibility analysis of novel designs
– Technical, economic, environmental assesment
– Effects of process parameter changes on
performance
– Optimization using structural and parametric
changes
– Analysing process interactions
– Waste minimization in design
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 Model application areas
• Process control
– Examining regulatory control strategies
– Analysing dynamics for setpoint changes or
disturbances
– Optimal control strategies for batch operations
– Optimal control for multi-product operations
– Optimal startup and shutdown policies

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 Model application areas
• Trouble-shooting
– Identifying likely causes for quality problems
– Identifying likely causes for process deviations

• Process safety
– Detection of hazardous operating regimes
– Estimation of accidental release events
– Estimation of effects from release scenarios

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 Model application areas
• Operator training
– Startup and shutdown for normal operations
– Emergency response training
– Routine operations training

• Environmental impact
– Quantifying emission rates for a specific design
– Dispersion predictions for air and water releases
– Characterizing social and economic impact
– Estimating acute accident effects (fire, explosion) 29
 Summary
• Reality → Mathematical model → Model solution →
Interpretation → Application to reality
• Different box colors exist
• Carefully think about:
– Variables (state) needed in the model
– Independent variables (dimensions) as the model easily
gets too complicated
– Balance equations that the model is based on
– Rate laws and other necessary relations to close the model
• Mathematical models are needed in many parts of
Chemical Engineering 30
George E.P. Box:

”Essentially, all models are wrong,

but some are useful”

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