Process Simulation

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Chemical Engineering Design

Process Simulation
Once we have established the block flow and started filling in the main
vessels, heat exchangers, pumps, etc. we want to develop a mass and
energy balance for the process so we can start evaluating the process in
more detail
The simulation is also the starting point for equipment design, as it will
set the flow rates and duties for process equipment
In most companies, mass and energy balances are developed using a
process simulator such as AspenPlus, ChemCad, ProII or UniSim. Each
program has its own idiosyncracies, but they have many common
features. Examples will be given in both AspenPlus and UniSim.
Note that the simulation should come after you know whats in the PFD,
but often its an iterative process to get both

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Chemical Engineering Design

Process Simulation
Structure of process simulators
Components and physical property models
Modeling reactors
Modeling separations
User models
Recycles & convergence
Optimization
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Chemical Engineering Design

Structure of Process Simulators

Equipment
sub-routines

Convergence &
optimization
sub-routines
Physical
property data

Executive Program

Thermodynamics
sub-routines

Cost data

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Graphical User
Interface (GUI)

The user manipulates the

program through a GUI that is set
up to look similar to a PFD
The executive program
determines the calculation
sequence and calls the other
subroutines
Chemical Engineering Design

Example: UniSim Simulation of GE

LM6000 Engine

Features that will be described are common to most other simulators

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Chemical Engineering Design

Using the GUI: Basis Environment

Click here

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Chemical Engineering Design

Basis Environment

Enter
components

Enter
reactions

Select
property
package

Specify
stoichiometry

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Chemical Engineering Design

Basis Environment

Enter
reactions

Specify conversion

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Chemical Engineering Design

Using the GUI: Object Palette

Click here

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Chemical Engineering Design

Object Palette

Unit
operations
General
reactors
Separator
models

Spreadsheet

User can
select
operations
from the
palette and
drag and
drop to the
PFD

Adjust, Set,
Recycle

Dynamics functions
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Chemical Engineering Design

Using the GUI: Workbook View

Click here
Brings up all the basic
stream data such as
temperature, pressure,
flow rates, etc. in one
screen

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Chemical Engineering Design

Windows Can Be Configured to Show

PFD & Workbook

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Chemical Engineering Design

Editing the Flowsheet in the GUI

Right click on any vessel or stream

icon and you get a menu that allows
you to select from similar icons,
hide the stream or operation, rotate
it, rename it and generally tidy up
the drawing to look more like a
proper PFD
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Chemical Engineering Design

Sub-Flowsheets

You can define a sub-flowsheet

and use it as a way of grouping
several operations away from
the main flowsheet. This is
particularly useful when you
need several unit operations to
model a single piece of process
equipment.
Sub-flowsheet

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Chemical Engineering Design

Generating Mass & Energy Balance

Reports
Report manager is on the Tools menu

Define a report

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Select all streams,

conditions and
composition only

Chemical Engineering Design

UniSim Design Stream Report

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Chemical Engineering Design

Process Simulation
Structure of process simulators
Components and physical property models
Modeling reactors
Modeling separations
User models
Recycles & convergence
Optimization
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Chemical Engineering Design

Entering Components: Pure Components

Pure components
Component library has thousands of pure components
Mostly organic compounds, but some inorganic compounds

Rules for selecting pure components

Always include any compound that has a specified limit in the product
Always include any compound that has a specified limit in any process feed
Always include anything formed in side reactions or consecutive reactions
Always include anything with significant HS&E concerns
Usually include anything that is present at >2% (by mole or mass)
Usually do not include isomers unless required by the process
Usually try to have < 40 pure components

What is the basis for these rules?

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Chemical Engineering Design

Pseudocomponents
Crude Oil Boiling Curve
Volume % distilled

100

50

0
50

1050

Temperature (F)

Petroleum fractions can contain ~ 104 to 106

components, many isomers, many compounds that
cannot be isolated and identified
Instead, use a pseudocomponent that represents all the
compounds that boil in a given temperature range
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Chemical Engineering Design

Pseudocomponents
Crude Oil Boiling Curve
Volume % distilled

100

50

0
50

1050

Temperature (F)

Example: this pseudocomponent represents all

compounds that boil between 300F and 350F, making up
roughly 8 vol% of the feed
Simulators have default pseudocomponents, but user may
need to add more around critical cut points
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Chemical Engineering Design

Solids and Salts

Solids
Some simulators recognize solid phase pure components when they are
formed
Phase equilibrium with solid phase is often not well predicted: check the
model carefully against the literature
Solid phases of mixed composition usually have to be defined as user
components (e.g.: cells, catalysts, coal, paper fibers, etc.)
Some of the simulation programs have good models for solid handling
operations, including modeling the effect of particle size distribution

Salts
Ionic compounds in the presence of water must be treated as electrolytes
and require special phase equilibrium models

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Chemical Engineering Design

User Components
Users occasionally need to add components that
are not included in the component library
Examples:

Complex molecules for pharmaceutical APIs

Specialty chemicals
Proprietary compounds
Advanced solvents
Electrolytes

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Chemical Engineering Design

Defining User Components

In the Basis environment, select
Hypo Components

Create Hypo
Component

Enter or estimate
properties

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Chemical Engineering Design

Defining User Components Using

UNIFAC Groups

Select UNIFAC groups

to build up the molecular
structure. The program
will then estimate
properties using group
contribution methods

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Chemical Engineering Design

Physical Property Models

All the simulation programs have a range of physical
property models
Model selection depends on the system chemistry see
Chapter 4
Be careful: if the physical property database does not have
the model parameters then they may be estimated using
methods such as UNIFAC, but estimated parameters should
be confirmed experimentally
Models are often inaccurate when predicting LLE, SLE, SSE
When user components are present, models will be near
useless unless some experimental data is fitted
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Chemical Engineering Design

Phase Equilibrium Model Selection

Chapter 4 has a chart to help with model selection:
N
Y

Start

T < 250 K

Use G-S

Y
Y

H2
present

Use P-R
or R-K-S

Hydrocarbon
C5 or lighter

N
Use B-W-R
or L-K-P

Use G-S

Sour Water

Y
Electrolytes

Y
P < 200 bar

N
0<T<750K

Use R-K-S

N
Y

P < 350 bar

N
Need more
experimental
data

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Use
electrolyte

N
Y

Use sour
water system

H2
present

T < 250 K

Use G-S
or P-R

Polar or
Hydrogen
bonding

P < 4 bar
T < 150C
Y

i
experimental
data
Y

Use UNIFAC to
estimate
interaction
parameters

Two
Liq phases

N Use Wilson, NRTL

or UNIQUAC

Y
Use NRTL
or UNIQUAC

Select model that

gives best fit to
data

Chemical Engineering Design

Physical Property Example

(Based on a real classroom incident)

I couldnt get that ethanol

water distillation to meet
specifications using the
Wilson equation, but it
worked just fine when I
switched it to ideal
solution!

Why?
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Chemical Engineering Design

Process Simulation
Structure of process simulators
Components and physical property models
Modeling reactors
Modeling separations
User models
Recycles & convergence
Optimization
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Chemical Engineering Design

Reactor Models

CSTR, PFR

Gibbs reactor

Solves for defined reactions in sequence to specified conversion function

Yield reactor

Calculates equilibrium only for defined reactions

More useful than Gibbs, as all species seldom reach equilibrium

Conversion reactor

Brings all species present to equilibrium at specified temperature or duty

Be very careful to define all possible species if this is what you want

Equilibrium reactor

OK if you know the kinetics and dont have many side reactions or contaminants
Can be combined to model real types of mixing

Allows user to specify any kind of yield pattern

Allows reactions of pseudocomponents, solids, changes in particle size
distribution, etc.

Real reactors can often be built from a combination of model reactors, e.g.
conversion then equilibrium

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Chemical Engineering Design

Example: Steam Methane Reforming

Furnace
Reactor

Shift
Reactor(s)

Compression

PSA
H2

Steam

CO2

Methane

Fuel

CO2 Removal

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Chemical Engineering Design

Steam Methane Reforming Chemistry

Methane reforming:
CH4 + H2O CO + 3 H2
Conversion of methane is typically about 95 to 98%
Strongly endothermic
Conversion increases with temperature, steam to methane ratio

Partial oxidation:
CH4 + 0.5 O2 CO + 2 H2
Strongly exothermic
Reduces hydrogen yield and requires expensive oxygen feed

Water gas shift reaction

CO + H2O CO2 + H2
Equilibriates rapidly at temperatures >450 C
Weakly exothermic
Equilibrium favors hydrogen at low temperature
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Chemical Engineering Design

Autothermal Reforming Process

Feed methane, steam and oxygen to reactor
Partial oxidation reaction provides heat to drive
conversion of steam reforming reaction
Reduces cost of reforming furnace

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Chemical Engineering Design

AspenPlus Simulation of Autothermal

Methane Reforming Process

RGibbs

REquil

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Chemical Engineering Design

Autothermal Reforming Reactor Model

Results

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Chemical Engineering Design

Process Simulation
Structure of process simulators
Components and physical property models
Modeling reactors
Modeling separations
User models
Recycles & convergence
Optimization
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Chemical Engineering Design

Distillation Models
Shortcut columns
Assume constant relative volatility
Useful for setting up problems, getting initial estimates of minimum reflux and number of
trays and checking feasibility of specs
Not good for non-ideal mixtures
Use to initialize complex columns

Rigorous Columns

Solve stage-to-stage
Allow column sizing
Can be used for absorbers, strippers, distillation, extraction, etc.
Allow intermediate condensers, reboilers, side streams, side strippers, etc.

Prebuilt complex columns

For Petroleum fractionation
Can be customized to different configurations

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Chemical Engineering Design

Distillation Example
(Example 4.6)

Separate 225 metric tons per hour of an equimolar

mixture of benzene, toluene, ethylbenzene (EB),
orthoxylene (OX) and paraxylene (PX)
Feed is a saturated liquid at 330 kPa
Toluene recovery in distillate should be > 99%
EB recovery in bottoms should be > 99%

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Chemical Engineering Design

UniSim Shortcut Model

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Chemical Engineering Design

Shortcut Column Specifications

Note:
Toluene mole
fraction in
bottoms = 1/300
= 0.0033
Ethylbenzene
mole fraction in
distillate = 1/200
= 0.005

External reflux ratio = 1.15 minimum reflux

(as an initial estimate)
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Chemical Engineering Design

Shortcut Column Results

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Chemical Engineering Design

UniSim Rigorous Model

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Chemical Engineering Design

Rigorous Column Specifications

From shortcut model

Component
recovery can
be specified

With good estimate of reflux ratio and number of trays, convergence is fast
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Chemical Engineering Design

Generating Column Profiles

It is often useful to plot column composition profiles to see whether the
column is efficient

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Chemical Engineering Design

Column Composition Profiles

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Examples of Bad Profiles

Feed tray too high

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Feed tray too low

Chemical Engineering Design

Examples of Bad Profiles

Toluene in bottoms

Reflux too low

(toluene recovery 72%)

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Reflux too high

(toluene recovery 100%)

Chemical Engineering Design

Examples of Bad Profiles

Too few trays: toluene recovery = 24.5%

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Chemical Engineering Design

Column Sizing in UniSim

Tray sizing is
under
tools/utilities
Default options
(shown) may
need changing
Column must
be converged
with the utility
enabled

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Chemical Engineering Design

Column Sizing Results

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Chemical Engineering Design

Common Causes of Column

Convergence Problems
Infeasible specifications
Make sure specs on distillate or bottoms purity can be achieved (see Section 17.6.2)
Make sure that specifications can mass balance with two products

Poor initialization
Use shortcut column to confirm R > Rmin, N > Nmin
Remember stage efficiency is typically 0.7 or less
Remember to allow for some pressure drop across the trays

Poor initial estimates

Most simulation programs default to the Inside-Out algorithm, which is very fast
when given good initial estimates. Use simple specs (e.g. distillate flow rate and
reflux ratio) to converge an initial simulation, upload the column temperature profile
from this as initial estimates and then change to the real specs and the column
should converge quickly.

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Chemical Engineering Design

Complex Columns: AspenPlus PetroFrac

Model of Crude Distillation

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Chemical Engineering Design

Other Separation Models

Some simulation programs include models for
other separations such as extraction,
crystallization, solids separations, etc.
All simulators have a Component Splitter
model
Allows user to specify recovery of each component
Can be used to model any kind of separation process

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Chemical Engineering Design

Process Simulation
Structure of process simulators
Components and physical property models
Modeling reactors
Modeling separations
User models
Recycles & convergence
Optimization
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Chemical Engineering Design

User Models
User may need to add custom models to the
simulation
Detailed reactor models
Novel unit operations

Most simulators support two ways of doing this:

Spreadsheet tool
Custom model operation

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Chemical Engineering Design

UniSim Spreadsheet
The UniSim
spreadsheet
can be used
to build
simple user
models of
operations
that are not
on the palette
Allows import
and export
from cells to
streams
Functionality
is basic
AspenPlus
has full MS
Excel
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Chemical Engineering Design

UniSim User Unit Operation

Define
connections
to PFD

Select from
palette

Enter code

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Chemical Engineering Design

Process Simulation
Structure of process simulators
Components and physical property models
Modeling reactors
Modeling separations
User models
Recycles & convergence
Optimization
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Chemical Engineering Design

Processes With Recycle

Feed B
Feed A

1
3

Recycle
of B

Reactor

Lights
5

Product

How do we break the recycle loop to solve in

sequential mode?
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Chemical Engineering Design

Possible Tear Strategy

Iterate to convergence

Estimate
Feed B
Feed A

Update

3a

3b

Recycle
of B

Reactor

Lights
5

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Product

Chemical Engineering Design

Tearing at the Reactor Outlet

Feed B
Feed A

1
3

Recycle
of B

Reactor

Lights
5a

5b

Product

Which tear point is likely to converge better?

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Chemical Engineering Design

Convergence Problems
Results that are unconverged or converged with
errors cannot be used for design
If convergence is slow then:
Check specifications are feasible
Use hand calculations or simplified models

Try increasing number of iterations

Try a different algorithm
Default method is usually Bounded Wegstein can change bounds on
acceleration parameter see Ch4
Try Newton method if there are many recycles or specifications to meet

Try to find a better initial estimate

Use hand calculations or a simplified model to initialize the problem

Try to find a better tear stream

Creep up on the solution
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Chemical Engineering Design

Model Simplification Techniques

Complex models with many rigorous columns and
recycles can be difficult to converge
A simplified model can be used to initialize tear streams
in the complex model
Models can be simplified by:
Using fewer components
Using simpler unit operations (e.g. replace columns with
separators)
Eliminating complex user models (replace reactor models with
Yield or Conversion reactor)
Reducing the number of specifications (allow some variables to
remain not quite converged)
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Chemical Engineering Design

Gas Recycle
Make-up
gas

Purge

Feed
Reactor
Product

Dont forget the purge stream

No purge, no converge!
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Chemical Engineering Design

Process Simulation
Structure of process simulators
Components and physical property models
Modeling reactors
Modeling separations
User models
Recycles & convergence
Optimization
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Chemical Engineering Design

Setting Constraints Using Controllers

An Adjust controller can be used to
control the air flow to give a target
turbine inlet temperature

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Chemical Engineering Design

Adjust Specifications

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Chemical Engineering Design

Adjust Solving Parameters

The
parameters
tab can be
used to set
bounds to
give the
desired
solution

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Chemical Engineering Design

Flowsheet Optimization
Most of the simulators allow optimization inside
the program
AspenPlus manual recommends:
1. Converge the flowsheet first
2. Carry out a sensitivity analysis and only optimize the variables that have
high impact on the objective function
3. During the sensitivity analysis, see if the optimum is broad or sharp

Off-line optimization (or near optimization) is

usually much easier see Ch12.

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Chemical Engineering Design

Tips for Process Simulation

For a good (i.e. useful) process simulation, you must
have:
Good component properties
A good phase equilibrium model
Flowsheet design that respects the 2nd law of thermodynamics

It is not essential to have

Reaction kinetics
Detailed models of every unit operation

Benchmark the simulation against lab, pilot plant or

operating plant data whenever possible to increase your
confidence that what you see in the virtual world agrees
with reality

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Chemical Engineering Design

Questions ?

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Chemical Engineering Design