Modeling, Simulation and Optimization for

Chemical Engineering
Part 2: Simulation

Lecture 6: Introduction to Process Simulation and Numerical Methods

Ho Chi Minh City University of Technology

 Contents
• Process
simulation
• Process simulation means
• Simulation
methods
• Solution of solving the equations of a
model equation
• Simulation study
• Numerical
Methods
process model to find the
values of the system properties
that are unknown

• These values tell us about

the effects of a process

Lecture 6: Introduction to Process Simulation and Numerical Methods

 Contents
• Process
simulation
• Simulation
methods Why do Process Simulation?
• Solution of
model equation
• Simulation study
Mimic / predict the behavior of a process system by mathematical models.
• Numerical
Methods
Chemical process simulation
‒ mimic operations in a chemical process

What-if evaluation / scenario analysis

‒ low cost, risk-free experimentation

Lecture 6: Introduction to Process Simulation and Numerical Methods

 Contents
• Process
simulation Why do Process Simulation?
• Simulation
methods
• Solution of Given partial information about a chemical process, use mathematical models to obtain all
model equation
• Simulation study the remaining information needed to describe the process fully.
• Numerical
Methods • Input information:
‒ Process flow diagram (operation types and sequence)
‒ Equipment parameters (number of stages, size,
operating pressure, pressure drop, etc.)
‒ Process inputs (T, P, flows, etc.)

• Output information:
‒ Process outputs (T, P, flows, composition, phases, etc.)

Lecture 6: Introduction to Process Simulation and Numerical Methods

 Contents
• Process
simulation
Why do Process Simulation?
• Simulation
methods
• Solution of Non-reactive process
model equation
• Simulation study
• Numerical
Methods
Recycle
Gas
Ammonia Ammonia
Reactor Condenser
Outlet

Liquid
Ammonia

Lecture 6: Introduction to Process Simulation and Numerical Methods

 Contents
• Process
simulation
Why do Process Simulation?
• Simulation
methods
• Solution of Reactive processes
model equation
• Simulation study
• Numerical
Methods

Gas
Feed
Ammonia
Synthesis
Reactor
Ammonia
Reactor
Outlet

Lecture 6: Introduction to Process Simulation and Numerical Methods

 Contents
• Process
simulation
• Simulation
Many methods are used to solve the mathematical equations of
methods
• Solution of
models
model equation
• Simulation study
• Numerical
Methods

providing exact solutions, but difficult or complex

Analytical
problems, can be soled manually
Simulation
Methods providing approximate solutions, but have sufficient
Numerical accuracy for engineering problem, cannot be
solved manually

Lecture 6: Introduction to Process Simulation and Numerical Methods

 Contents
• Process
simulation
Example 1:
• Simulation
methods
• Solution of
Simulation of a pump
model equation
• Simulation study
• Numerical
Consider a pump to deliver fluid with the following conditions:
Methods
Suction side: Discharge side:
Fluid: Gasoline Pressure: 450 kPa
Flow: 100 kg/h Pump Efficiency: 70%
Pressure: 105 kPa
Temperature: 27oC
Simulate the pumping process and determine:
(1) power to pump the fluid, and (2) the temperature of fluid outlet
Lecture 6: Introduction to Process Simulation and Numerical Methods
 Contents
• Process
simulation
Example 1:
• Simulation
methods
• Solution of Since gasoline is a complex mixture of hydrocarbon, we are going
model equation
• Simulation study to simplify the problem by estimating the composition of the fluid
• Numerical
Methods as pure octane, C8H18, instead.
We also need a to predict the thermophysical property of
octane. Here we usually use Peng-Robinson equation of
state.

Alternatively, we can also build a simple models to predict

the thermodynamic properties of liquid octane.
Lecture 6: Introduction to Process Simulation and Numerical Methods
 Contents
• Process
simulation Example 1:
• Simulation
methods
• Solution of
model equation
The process of pumping liquid
• Simulation study
• Numerical
p2 = 450 kPa
Methods Gasoline (octane) T2 = ?
m = 100 kg/h
p1 = 105 kPa
T1 = 27oC  = 70%
Wp = ?

From thermophysical properties model:  = 705 kg/m3

cp = 2.55 kJ/kg•K
Lecture 6: Introduction to Process Simulation and Numerical Methods
 Contents
• Process
simulation Example 1:
• Simulation
methods
• Solution of For liquid pumping, the power required:
model equation

Wp = VP/
• Simulation study
• Numerical
Methods
= 69.91 kJ/h

From the enthalpy change:

Wp = mh
h = 0.6991 kJ/kg

Since h = cpT, then T = 0.27oC

Therefore T2 = 27.3oC
Lecture 6: Introduction to Process Simulation and Numerical Methods
 Contents
• Process
simulation
• Simulation
Find the root of f(x) = x−5
methods
• Solution of
model equation
• Simulation study
• Numerical
Analytical solution:
Methods f(x) = x−5 = 0
add +5 to both sides to get the answer x = 5

Numerical solution:
Let's guess x = 1: f(1) = 1 − 5 = −4; A negative number.
Let's guess x = 6: f(6) = 6 − 5 = 1; A positive number.
The answer must be between them.

Lecture 6: Introduction to Process Simulation and Numerical Methods

 Contents
• Process
simulation
• The mathematical equations / model are coded using the
• Simulation
methods
• Solution of
syntax of programming language
model equation
• Simulation study
• Numerical
Methods
• Equations are solved using the codes and methods to
solve the equations are coded separately

• User defined variables must be defined in limits only, no extra

input must be provided

Lecture 6: Introduction to Process Simulation and Numerical Methods

 Contents
• Process • Solving the model does not mean that the model has been developed
simulation
• Simulation successfully
methods
• Solution of
model equation
• Simulation study
• It is important to estimate various parameters using the model and
• Numerical
Methods compare them with experimental data

• A satisfactory agreement between the experimental data and model

prediction is called ‘model validation’

• A model is ready to use for simulation studies only after successful

validation

• Some parameters needs to be used as these adjust the models near to

the experimental data
Lecture 6: Introduction to Process Simulation and Numerical Methods
 Contents
• Process
simulation
• Model is used several times with an aim to study the
• Simulation
methods
• Solution of
effect of operating parameters on the performance
model equation
• Simulation study
• Numerical of the process
Methods

• The optimum operating conditions can also be determined

• Results can be presented in various ways either using the
simulation software or external software to process the
data

Lecture 6: Introduction to Process Simulation and Numerical Methods

 Contents
• Process To solve the mathematical equations with fast speed, software /
simulation
• Simulation
methods
• Solution of
programming languages are used.
model equation
• Simulation study
• Numerical
Methods
Availability • With passage of time improved softwares/ languages
are available

• Commercial Packages needs to be purchased or use

Cost open source things
Software
Selection
Parameters Trained
• Any person is available who can use
• Sometimes users deny a preferred software just
Personnel because he does not know that software

• Chosen software can serve or not your purpose

Suitability • Flexible in use, like solve algebraic, differential
equations etc.

Lecture 6: Introduction to Process Simulation and Numerical Methods

 Contents
• Process
simulation
• Simulation
Thermodynamic models are used to represent
methods
• Solution of
the phase equilibrium behavior and energy level
model equation
• Simulation study of pure compound and mixture systems.
• Numerical
Methods

Lecture 6: Introduction to Process Simulation and Numerical Methods

 Contents
• Process
simulation
• Simulation
methods In many cases, simulation results DO NOT reflect
• Solution of
model equation
what is really happening in a plant
• Simulation study
• Numerical
Methods
WHY?
• Improperly selected thermodynamic models
• Inadequate model parameters
• Incorrect hypothetical components generation
• Problems with plant data consistency

Lecture 6: Introduction to Process Simulation and Numerical Methods

 Contents
• Process Example:
simulation
• Simulation • A mixture of Ethane and Propane at 30 atm
methods • The PR Equation of State most closely represents the true phase behavior of the system
• Solution of
model equation
• Simulation study
• Numerical
Methods

• Peng Robinson • Vapor Pressure • NRTL Ideal

EOS model
• Dew point 50.1 C • Dew point 54.3 C
• Good predictions
at low pressures

Lecture 6: Introduction to Process Simulation and Numerical Methods

 Contents
• Process
simulation
• Simulation
Aspen HYSYS contains over 30 thermodynamic models
methods • Equations of State
• Solution of
model equation
• Simulation study
• Activity Coefficient Models
• Numerical
Methods
• Vapor Pressure Models
• Semi-Empirical Models
• Specialty Models
– Steam Tables
– Amines Package
– Clean Fuels Package
– Glycol Package
– OLI
– Neotec Black Oil
– Infochem Multiflash
– etc.

Lecture 6: Introduction to Process Simulation and Numerical Methods

 Contents
• Process
simulation
• Peng-Robinson (PR)
• Simulation
– Most enhanced model in Aspen HYSYS
methods – Largest applicability range in terms of T and P
• Solution of – Special treatments for some key components
model equation
• Simulation study
– Largest binary interaction parameter database
• Numerical
Methods • PRSV
– Modified PR model
– Better representation of vapor pressure of pure components and
mixtures
–Extends applicability of the original PR model to moderately
non-ideal systems

• SRK
– Modified RK model
– Can provide comparable results to PR in many cases, but with a lot
less enhancement in Aspen HYSYS

Lecture 6: Introduction to Process Simulation and Numerical Methods

 Contents
• Process
simulation • PR-Twu
• Simulation
methods
• Solution of
model equation • SRK-Twu
• Simulation study
• Numerical
Methods
• Twu-Sim-Tassone (TST)
– Modified equations of state models for hydrocarbon systems-non
ideal systems (used for glycol package)

• Generalized Cubic Equation of State (GCEOS)

– Provides a framework which allows users to define and implement their
own generalized cubic equation of state including mixing rules
and volume translation

Lecture 6: Introduction to Process Simulation and Numerical Methods

 • MBWR
Contents – Modified BWR model
• Process – Having 32 parameters, this model works extremely well with a number of
simulation pure components within specified T and P ranges
• Simulation
methods Lee-Kesler-Plöcker
• Solution of
model equation •– Also a modified BWR model
• Simulation study – Can be used for non-polar substances and mixtures
• Numerical
Methods
• BWRS
– Modified BWR to handle multi components
– Requires experimental data

• Zudkevitch Joffee
• – Modified RK model with better prediction of VLE for hydrocarbon systems, and systems
containing hydrogen
Kabadi-Danner
• – Modified SRK model with the enhancement to improve the VLE calculations for H2O-
hydrocarbon systems, particularly in dilute regions
Sour PR/Sour SRK
– Used for sour water systems containing H2S, CO2, and NH3 at low to moderate
pressures
Lecture 6: Introduction to Process Simulation and Numerical Methods
 Contents
• Process
simulation • Modified Antoine Model
• Simulation
methods
–Applicable for low pressure systems that behave ideally
• Solution of
model equation
• Simulation study
• Numerical
Methods
• Braun K10 Model
– Strictly applicable to heavy hydrocarbon systems at low pressures

• Esso K Model
–Also strictly applicable to heavy hydrocarbon systems at low pressures

Lecture 6: Introduction to Process Simulation and Numerical Methods

 Contents
• Process
simulation
• Simulation
methods
• Chao-Seader model
• Solution of – Applicable to hydrocarbon systems in the range of T=0-500C,
model equation
• Simulation study
and P<10,000 kPa
• Numerical
Methods

• Grayson-Streed model
– An extension to the Chao-Seader model with special emphasis
on H2
– Recommended for heavy hydrocarbon systems with high H2 content,
such as hydrotreating units

Lecture 6: Introduction to Process Simulation and Numerical Methods

 Contents
• Process
simulation
• Simulation
methods
• Glycol Package
• Solution of
model equation
– For accurate representation of TEG circulation rates, purities of lean
• Simulation study
• Numerical
TEG, dew points and the water content of the gas stream used in
Methods natural gas dehydration process

• Clean Fuels
– For systems containing thiols and hydrocarbons

• OLI
– For electrolyte systems

Lecture 6: Introduction to Process Simulation and Numerical Methods

 Contents • Based on TST Equation of State
• Process
simulation
• Simulation • Internally combines the equation of state with an interaction coefficients
methods method (NRTL) and Some proprietary modifications
• Solution of
model equation
• Adequately predicts phase equilibrium systems containing TEG and
• Simulation study water.
• Numerical
Methods

• PR
• Still applicable because of its internal fit of BIP’s to accurately predict
natural gas dehydration absorbers and TEG solutions regeneration.
• But was giving strange behavior outside normal gas dehydration
operating conditions.
• Use PR for MEG and DEG

Lecture 6: Introduction to Process Simulation and Numerical Methods

 Contents
• Process
simulation
• Simulation • Amines Models
methods
• Solution of – For modeling sour system sweetening processes using amines (DEA,
model equation
• Simulation study
TEA, MEA, MDEA, DGA and DIPA)
• Numerical
Methods

• Steam Table Models

– ASME Steam – ASME 1967 Steam Tables
– NBS Steam – NBS 1984 Steam Tables

Lecture 6: Introduction to Process Simulation and Numerical Methods

 Contents
• Process
simulation
• Simulation • Amine Package
methods
• Solution of
– Only applicable to the systems containing specified amines in
model equation fixed amine concentration, temperature, and pressure ranges
• Simulation study
• Numerical
Methods

• DBR Amine Package

– Incorporates the latest AMSIM version 7.2 from Schlumberger
through COMThermo
• Kent Eisenberg – Based on regression to experimental data
• Lee Mather – Based on stronger thermodynamic foundation:
recommended
• Solvents: DEPG

Lecture 6: Introduction to Process Simulation and Numerical Methods

 Contents
• Process
simulation
• Simulation • Hydrocarbon systems – PR, SRK or any other EOS*
methods
• Solution of
model equation • Hydrate inhibition – PR (special fit of BIP)
• Simulation study
• Numerical
Methods • Natural gas dehydration with TEG – Glycol package

• Sour gas sweetening with amines

• Utility systems using H2O – Steam Table

Lecture 6: Introduction to Process Simulation and Numerical Methods

 Contents
• Process
simulation
• Hydrocarbon systems up to distillate range hypo-
• Simulation components – PR, SRK or any other EOS*
methods
• Solution of
model equation
• Simulation study • Vacuum columns – GS, PR or BK10
• Numerical
Methods
• Sour gas sweetening with Amines

• Sour water treatment process – Sour PR/SRK

• Clean fuels for sulfur components and hydrocarbons

• High H2 content systems – GS, PR

• Utility systems using H2O – Steam Table

Lecture 6: Introduction to Process Simulation and Numerical Methods

 Contents • CombinestheEquationof StatewiththeAPI Sour Model
• Process
simulation
• Simulation (Wilson)
methods
• Solution of
model equation
• Simulation study
• Numerical
• Will accurately predict desorption of H2S, NH3 and CO2
Methods
from sour waters

• The only limitation is that it does not report pH or any ionic

species in water solution, i.e., CO2, not CO3=, etc.

• Takes into account any change in acidity of water solution,

i.e., the addition of NaOH to the system

Lecture 6: Introduction to Process Simulation and Numerical Methods

 Contents
• Process
simulation
• Simulation
methods
• Solution of
model equation
• Simulation study
• Numerical
Methods

Lecture 6: Introduction to Process Simulation and Numerical Methods

 Contents
• Process
simulation
• Simulation
methods
• Solution of
model equation
• Simulation study
• Numerical • Use BWRS, GCEOS, Glycol Package, Kabadi-Danner, Lee-
Methods Yes Kesler-Plocker, MBWR, Peng-Robinson, PR-Twu, PRSV, Sour
High Pressure SRK, Sour PR, SRK, SRK-Twu, or Zudkevitch-Joffee.
(> 10 bar)
No • Use Chien Null, Extended NRTL, General NRTL, Margules,
NRTL, UNIQUAC, van Laar or Wilson.

Lecture 6: Introduction to Process Simulation and Numerical Methods

 Contents
• Process
simulation
• Simulation
methods
• Solution of
model equation
• Simulation study
• Numerical • Use Braun K10, Antoine or Esso Tabular if there are no light
Methods Yes hydrocarbons
Vacuum
Conditions • Use Chao-Seader, Peng-Robinson, SRK
• If the system contains high concentrations of Hydrogen or Water
No
use Grayson Streed.
• If water solubility in the hydrocarbon phase or hydrocarbon
solubility in the water phase is important, use Kabadi-Danner.

Lecture 6: Introduction to Process Simulation and Numerical Methods

 Contents
• Process • For understanding chemical process, modeling equations
simulation
• Simulation need to be solved.
methods
• Solution of
model equation
• The solution of linear is easy, however for non-linear it is
• Simulation study
• Numerical difficult.
Methods
• Two ways to solve: Analytical & Numerical
• Typical Chemical process is composed of ODE & algebraic
equations
• ODEs are balance equations and parameter relationship
equations are algebraic

Lecture 6: Introduction to Process Simulation and Numerical Methods

 Contents
• Process
simulation
• Simulation
methods
Iterative
• Solution of Convergence
model equation
• Simulation study
• Numerical
Methods
Numerical
Numerical Integration for
Methods ODEs

Numerical
Solution for PDEs

Lecture 6: Introduction to Process Simulation and Numerical Methods