CHEM-C2120

Process simulation basics

Sarwar Golam, D.Sc. (Tech.), Pekka Oinas, prof.
April 26, 2016

Key learning objectives

Understand:
Simulation in general
Flowsheeting program
Structure of simulation program
Simple simulation models:
Flash
Reactors

SIMULATION: GENERAL AND HISTORY

SIMULATION comes from a Latin word meaning
imitation or pretending.
PROCESS SIMULATION means computerized:

estimation of required physical properties

calculation of mass and energy balances,
sizing of equipment (often preliminary)
Question: How these factors are related to each other ?
sometimes:
- calculation of dynamics
- calculation of cost and profitability
- calculation of emissions
- calculation of batch process schedules
3

For simulation a mathematical model is required. This

lecture does not discuss modeling but the use of models
i.e. simulation.
Steps from modeling to simulation:
1. Modeling (writing a mathematical model)
2. Solving of the mathematical model
3. Implementing the model as computer a program
4. Testing and verification of the model
5. Using the model for simulation
6. Using of simulation results for design etc.
Generally the science of using computers in process design and analysis is
called either: Computer Aided Process Engineering (CAPE) or Process
Systems Engineering (PSE).
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FLOWSHEETING
Means, simulation of material and energy balances of processes
in steady state condition (time independent).

Fig. Flowsheet, evaporator section in a sugar factory

OTHER TYPES SIMULATION & COMPUTING

Dynamic simulation time dependent
Equipment simulation detailed equipment dimensioning
Computational fluid dynamics (CFD) - computing hydrodynamics in vessels etc.
Soft computing non-first principle models (fuzzy, neuro
etc.)
Knowledge-based systems modeling of knowledge and
expertise (e.g. expert systems)
Chemometry - analysis of experimental data
Regression fitting of data to equations
Operation planning production optimization and scheduling

HISTORY
Analog simulation
Simulation was done by analog computers (1955) using
electronic components (e.g. resistors or light bulbs) connected by
wires to mimic different math operations
Example: A complex system of water pipelines was simulated by electric
bulbs connected by wires. Electric current corresponds water flow rate.

Digital simulation
Digital simulation starts later when digital computers became
more common and powerful.
First simulation programs: 1958 Flexible flowsheet (M.W. Kellogg Co.)
In 1980s simulation programs were implemented to personal computers
and graphical user interfaces became a standard.
In 2000's more detailed or dynamic process simulation became practical
(Aspen plus, Aspen Dynamics, Pro II, ChemCad, Dynsim, etc.).
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WHY SIMULATION IS USED

Simulation is an alternative to:

experimentation
shortcut calculations (i.e simple models) by spreadsheets
Experimentation is slow and expensive. Shortcut calculation is
inaccurate.
Benefits:
save time and money
quicker process design and development
lower development costs
quicker entrance to markets

better processes by better design with more detailed models

(no need for 'short-cut' models)
safety enhanced by possibility to check abnormal (e.g.
hazardous) situations.
8

Simulation has made possible the modern strategy in process

development:
1. First, the missing information's that prevents modeling of the
whole process?
2. To fill the missing information's, experimentation is done in
small scale to find the physical & chemical phenomena (often
each phenomenon separately).
3. Simulation model is tuned by fitting the parameters of model
from experiments to get more exact results and to take into
account the non-idealities.
4. Process scale up and design is done by simulation. The results
of models are verified by experiments.
The traditional approach was to scale up processes via several
experimental scales: lab, bench, pilot, test plant, which is time
consuming, expensive and since the number of experiments is
limited; leads to sub-optimal results.
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Types of knowledge and models

Theoretical knowledge: based on scientific principles. It
is used in mechanistic models.
For example: Q = kA DTm and 1/k = 1/ki + 1/ko ; where heat
transfer coefficients ki and ko are calculated from equations.

Empirical knowledge: based on experiments and observations.

It is used in empirical models.
For example: polynomial model Q=ax2+bx+c (parameters
a, b, c fitted from experiments).

Experiencebased knowledge: gained through work experience

and engineering practice (so called 'silent knowledge`,
expertise).
It can be modelled to some extent with knowledge-based
models such as a fuzzy models or expert systems.
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Most typical type of model used is a mixed (semiempirical) model in

which the model comes from theory but the parameters are fitted from
experiments. Example, the Arrhenius equation for reaction rate
constants k = Ae-E/RT

Fig: Types of knowledge and models in process design

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Modeling in the plant life cycle

Plant life cycle goes through steps of process development,
design, investment, operation, retrofit (design & investment for
modification), operation, etc.
Life-cycle modeling means that the simulation model is
developed throughout the project and used in all the phases of
the plant life cycle.
For example design model can be used in operation for operator
support or for process optimization => better operation in
operation. The benefit is also that the modeling work can be
reused => cost savings.

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USE OF SIMULATION IN PROCESS DESIGN

Start

Creation of process concept

Simulation
Evaluation
Decision making

Optimization
of parameters
Optimization
of structure

Process
ready

Fig. Steps of conceptual process design

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Conceptual process design

Means creation of process concept (operations used and
their connectivity). It is divided into following phases:
Process synthesis (creating structure of process, operations,
connections)
Process analysis (calculation by flowsheet simulation, mat.
& heat balances, equipment sizing, emissions )
Evaluation (evaluation of performance criteria; costs,
profitability and EHS etc.)
Decision making if the process is ok or if it has to be
changed.(comparison of the alternatives based on criteria
and weighted scores methods)
Optimization (by changing parameters (T, p or flow rates)
and structure for best process alternatives)
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STUCTURE OF SIMULATION PROGRAM

USER

OTHER
PROGRAMS

USER INTERFACE

INPUT
DIAGNOSTICS

SOLVING
ALGORITHM

CALCULATION
DIAGNOSTICS

UNIT OPERATION
MODELS

PHYSICAL
PROPERTY
MODELS

COSTING

PHYS. PROP.
DATABANKS

OTHER
PROGRAMS

Figure. Structure of a simulator

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COMPONENTS OF A SIMULATOR
Interface
User input; graphical
User output: graphical / text based
Interface to other programs (equipment design etc)

Unit models
calculation models of unit operations as subroutines

Solving algorithm (solver):

Type varies in different simulator types
Simultaneous or sequential modular

Diagnostics for
Input (if input given is complete)
Calculation (if calculation is convergence, if not; info on
possible errors and guidelines for troubleshooting
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 Physical property package

Estimation models for pure component
Equations for calc. mixture properties from pure component
values
Physical property databank (for pure components)
Constants
- Critical properties Tc, Pc

- Molecular weight, etc.

Temperature or composition dependent parameters

- Correlation constants for polynomial correlations etc.

Cost models
EHS models (environmental etc. models)
Interface to other simulators (model sharing)
In CAPE Open project the aim is to develop methods, how programs
share unit models, physical property models and solvers.
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SIMULATION PROGRAMS
Steady state flowsheet simulation is common in the process
industry, universities and other research organizations.
Mosts commonly used software:
Aspen plus: Used in chemical, petrochemical and biochemical process industries
PRO II: Used in chemical, petrochemical and bio-chemical
process industries
CHEMCAD: Used in chemical, petrochemical and biochemical process industries
SuperPro Designer: Used the in biotechnology and
environmental technology
Balas: Used in the pulp and paper technology
HSC: Used in the metalurgical industries
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THE PHASES OF MAKING A SIMULATION FILE

1. Define the system of units you use
2. Define the components in your system. It is best to order the
components in volatility order, starting with the lightest
component.
3. Select the thermodynamic and transport property methods.
For many problems, a predefined method set may be
selected.
4. Draw the flowsheet and connect the unit operations with
streams. Select the unit operations needed for the flowsheet
calculations and position them on the Main Window draw
area. Connect the unit operations with streams.
5. Supply data for the feed streams (and recycle streams). You
must supply thermal conditions, flowrates, and compositions
for all external feed streams to the flowsheet.
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6. Supply operating conditions for the unit operations. Doubleclick on the icon for each unit operation to access its data
entry windows. The color codes tell you what data you must
supply and what data have defaults.
7. Run the process simulation.
8. Analyze the simulation results. Use the many convenient
report and plotting features.

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MODELING LEVELS
Following levels of modeling can be used in general:
1. General models: General models include mixer, splitters,
dividers etc., which present only simple mass balance
operations such as 'add two streams together' etc.
2. Unit operation models: Unit operation models are typical
models used in flowsheeting programs. They represent a unit
operation & phenomenon such as heat exchange or flash, not
equipment.
3. Detailed equipment models: Detailed equipment models,
such as a tray column or detailed heat exchanger model.
Sometimes even commercial models of equipment are
included (such as column packings etc.).

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PHYSICAL PROPERTY CALCULATIONS

In simulation the pure component properties are calculated
based on databank information of components, then properties
of mixtures are calculated from pure properties by using mixing
rules.
Calculation steps:
1. databank (constants; Tc, pc, etc.)
2. property estimation routines for pure components
-> pure component physical properties
3. mixing rules
-> mixture physical properties

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1. Estimation methods:
a) Equilibrium properties
- VLE / LLE

distribution coefficient

- enthalpy

for phases

Ki = yi / xI
liquid, gas

- entropy

liquid, gas

- density

liquid, gas

b) Transport properties
viscosity
diffusivity
thermal conductivity
surface tension

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2. Data Bank
Constant properties:

Acentric factor
Chemical formula
Critical values: Zc, Tc, Pc, Vc
Heat of formation
Normal boiling point
Molecular weight
Standard Density
Structural components of molecule

Temperature and pressure dependent properties

Gibbs energy
Ideal gas enthalpy
Latent heat
Liquid density
Saturated liquid enthalpy
Vapor pressure

others
flash point
melting point

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Example on component database information

===================================================================
COMPONENT

COMP. TYPE

PHASE

MOL. WEIGHT

DENSITY
KG/M3

--------

-----------

H2O

MEOH

COMPONENT

-----------

-----------

-----------

LIBRARY

VAP/LIQ

18.015

998.566

LIBRARY

VAP/LIQ

32.042

795.604

NBP

CRIT. TEMP.

C
-------1

H2O

MEOH

COMPONENT

CRIT. PRES.

C
-----------

CRIT. VOLM.

KPA
-----------

M3/KG-MOL

-----------

-----------

100.000

374.200

22119.199

.0554

64.700

239.430

8095.870

.1180

ACEN. FACT.

HEAT FORM.

G FORM.

KJ/KG-MOL

KJ/KG-MOL
-----------

---------

-----------

-----------

H2O

.34800

-241997.00

-228796.00

MEOH

.56870

-200987.00

-162322.00

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Unit Operation: FLASH

Due to:
Pressure change
Temperature change
Heat flow
A vapor-liquid equilibrium is formed (i.e. saturated liquid and
vapor phases).
Saturated vapor pressure and temperature is calculated.
V

L
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FLASH ALTERNATIVES:
Bubble point
Dew point
Isothermal (t- const.)
Adiabatic (Q = 0)
Isentropic
Specified
BUBBLE POINT:

Concentration of first bubble formed

Specify either pressure or temperature
Gas outlet rate is zero !
(kuplimispiste)

DEW POINT:

Concentration of first condensed drop

Specify either pressure or temperature
Liquid outlet is zero!
(kastepiste)
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Figure. Bubble and dew point curves. For benzene (bp 78oC) and toluene (bp 92oC)
mixture. Points b and c are in equilibrium at 91oC.
In Figure; when subcooled liquid is heated from 80 C (a), first bubble vaporizes at
91 C (= bubble point). The composition of liquid is (b) and the bubble (= vapor) is
(c). Both have the same temperature.
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ISOTHERMAL:

Choose temperature and pressure;

Heating duty Q is calculated

ADIABATIC:

Choose temperature or pressure and duty

(Q = 0 for adiabatic)

ISENTROPIC FLASH:

Simulates isentropic operations, in which

the calculations follow a line of constant
entropy.
Select temperature or pressure.

STREAM SPECIFICATION FLASH:

Choose either pressure or temperature and
supply a value for a performance
specification for the product stream
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VLE MODELS IN GENERAL

VLE estimation methods are classified to:
1. IDEAL MODELS
Ideal gas:

pV = nRT and

Ki = pio /p

2. EQUATION OF STATE (EOS) MODELS

a) Z-correlations for ideal gas equation
pV = nRT Z

(Z is compressibility; available from charts)

b) Antoine equation
ln p = A - B / (T + C ) Empirical parameters A, B, C.
c) Cubic equation of state
Z3- Z2 + Z(a-b-c2) - ab = 0
a and b are calculated from critical values of the compound. From the
equation we get three roots for compressibility factor Z. One for liquid,
another for vapor phase and third for nothing.
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3. ACTIVITY COEFFICIENT METHODS

For nonideal liquids. (g 1). Typical activity coefficient methods
NRTL (three parameters A, B, C)

UNIQUAC

UNIFAC (no

Wilson (two binary parameters A and B)

4. SPECIAL MODELS
Special models are available for some special chemical systems:
alcohols
sour water NH3, H2S, CO2, H2O
amines (MEA, DEA etc.)
glycol (TEG, etc.).

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Typical VLE methods available in simulators

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APPLICATION GUIDELINES
Vapor phase
Ideal:
Non-ideal:

ideal gas equation of state

cubic EOS (SRK, PR, etc.),
Poynting correction for pressure

Liquid phase
Ideal
Non-ideal

Activity coefficient g =1
Activity coefficient methods; g 1

Often in using activity coefficient methods, the non-ideality of

vapor phase has been more or less included into the activity
coefficient (liquid phase).
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SELECTION OF THE VLE METHOD

Rules of thumb:
Nonpolar
Light hydrocarbons

-> PR, SRK

Heavier hydrocarbons + H2

-> GS

Polar
Parameters or data available

-> activity coefficient models

No data, low p and T

-> UNIFAC

Special methods are needed for:

- Polymers
- Electrolyte solutions
- Compounds with vapor phase association (HAc)
- Organics with electrolytes
- pH dependent solutions
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SELECTION GUIDE FOR VLE METHODS

POLAR
N

Y
BINARY PARAMETERS AVAILABLE

HYDROCARBON
C1- C6

HYDROGEN + > C6

Y
GS

EXPERIMENTAL DATA?

P < 10 bar ?

SRK, PR
N

UNIWAALS or
MAKE MEASUREMENTS

ACTIVITY COEFFICIENT
METHODS

UNIFAC

LLE ?

FITTING

N
WILSON, NRTL
UNIQUAC

Y
NRTL
UNIQUAC

DIMERIZATION IN GAS PHASES ? =>

HAYDEN OCONNELL
ELSE; IDEAL OR SRK GAS PHASE
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REACTORS
BASIC REACTOR SIMULATION MODELS:
1. BATCH / SEMIBATCH
2. CONTINUOUS
a) KINETIC:
- CSTR (continuous stirred tank)
- Plug flow (tubular)
b) EQUILIBRIUM:
- Gibbs
- Equilibrium
3. CONVERSION
4. REACTIVE DISTILLATION
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REACTOR MODELS IN PRO/II SIMULATOR

1. CONVERSION REACTOR

Conversion is given by the user: Conversion = A+ BT + CT2

2. KINETIC REACTORS

Arrhenius equation constants, phase and comp. orders are given.

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3. CSTR (CONTINUOUS STIRRED TANK)

Kinetic. Volume of reactor required.

4. PLUG FLOW (TUBULAR)

Kinetic. Tube dimension data needed:

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5. EQUILIBRIUM REACTOR
Equilibrium data defined as:

Temperature approach defined

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6. GIBBS REACTOR

Gibbs Reactor simulates a chemical reactor by solving the

heat and material balances based on minimizing the free
energy of the components in the reaction.
Gibbs reactor determines the distribution of components
which is expected at chemical equilibrium for the system:
K = exp (-DG / RT)
where DG is the Gibbs energy of reaction, K = equilibrium
constant.
Therefore Gibbs reactor does not need extent of reaction
data by the user.

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REACTOR DESIGN BY SIMULATION

Most flowsheet simulators have only ideal reactors.
Phases of reactor design by simulation:
1. Gibbs
- heat of reaction
- max yield / equilibrium composition
- by products
2. Kinetic experiments in lab
- kinetic equation and parameters
3. Simulation with kinetic reactors (CSTR, Plug, Batch)
-> volume + dimensions
4. Simulation as part of the total system
-> total yield / selectivity + optimization

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REACTOR DESIGN BY SIMULATION

Figure. Reactor as part of total process

(separation and reactor must be optimized together !)
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