Aspen Adsim

Aspen Adsim
2004.1
Adsorption Reference Guide

Who Should Read this Guide 2
Who Should Read this Guide
This guide contains reference information for use by experienced users of the
Aspen Adsim application.
The guide also describes the following Aspen Adsim features:
Numerical methods for solving the partial differential equations.
Estimation module.
Cyclic Organizer.
Flowsheeting strategies.

General Information 3
General Information
This section provides Copyright details and lists any other documentation
related to the Aspen Adsim 2004.1 release.
Copyright
Version: 2004.1
April 2005
Copyright 1991-2005 Aspen Technology, Inc, and its applicable
subsidiaries, affiliates, and suppliers. All rights reserved. This Software is a
proprietary product of Aspen Technology, Inc., its applicable subsidiaries,
affiliates and suppliers and may be used only under agreement with
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Related Documentation
In addition to this document, the following documents are provided to help
users learn and use the Aspen Adsim applications.

Title Content
Aspen Adsim 2004.1 Library Reference Guide Describes the models, streams,
procedures and submodels available in
Aspen Adsim.
AES 2004.1 Installation Guide Full installation procedures for both
server and client.
Aspen Engineering Suite 2004.1 Whats New
Guide
An overview of new features and
functionality within this release.

Technical Support 7
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Technical Support 8
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Contents 9
Contents
GENERAL INFORMATION................................................................................. 3
Copyright................................................................................................................ 3
Related Documentation............................................................................................. 6
TECHNICAL SUPPORT...................................................................................... 7
Online Technical Support Center ................................................................................ 7
Phone and E-mail ..................................................................................................... 8
INTRODUCING ASPEN ADSIM ....................................................................... 17
1 GAS ADSORPTION PROCESSES.................................................................. 18
About Gas Adsorption Processes............................................................................... 18
Bed Model Assumptions for Gas Adsorption Processes ................................................. 19
About Aspen Adsim's Bed Models ............................................................................. 20
Bed Model Ports................................................................................................ 20
Configure Form (Gas) ............................................................................................. 21
Configure Form (gas): Bed Type.......................................................................... 22
Configure Form (gas): Spatial Dimensions ............................................................ 24
Configure Form (gas): Internal Heat Exchanger..................................................... 25
Configure Layer Form (gas) ..................................................................................... 26
General Tab (gas) .................................................................................................. 26
General Tab (gas): Discretization Method to be used.............................................. 26
General Tab (gas): Number of Nodes ................................................................... 27
General Tab (gas): Number of Radial Nodes.......................................................... 27
General Tab (gas): Flux Limiter to be used ........................................................... 27
General Tab (gas): Gas Model Assumption............................................................ 27
Material/Momentum Balance Tab (gas) ..................................................................... 28
About Axial Dispersion in Gas Adsorption Processes ............................................... 28
Material/Momentum Balance Tab (gas): Material Balance Assumption....................... 29
Material/Momentum Balance Tab (gas): Momentum Balance Assumption .................. 31
Material/Momentum Balance Tab (gas): 2-D Dispersive Properties ........................... 33
Kinetic Model Tab (gas) .......................................................................................... 37
Kinetic Model Tab (gas): Film Model Assumption.................................................... 37
Kinetic Model Tab (gas): Kinetic Model Assumption ................................................ 37
Contents 10
Kinetic Model Tab (gas): Form of Lumped Resistance Model .................................... 50
Kinetic Model Tab (gas): Molecular Diffusivities ..................................................... 51
Kinetic Model Tab (gas): Form of Mass Transfer Coefficients.................................... 52
Kinetic Model Tab (gas): Apply Cyclic Correction.................................................... 55
Kinetic Model Tab (gas): Estimated Mass Transfer Coefficient Assumption ................. 56
Gas Adsorption Layer (gas): Particle Material Balance, Number of Nodes................... 56
Kinetic Model Tab (gas): Particle Material Balance, Effective Diffusivity ..................... 56
Isotherm Tab (gas) ................................................................................................ 57
About Adsorption Isotherms for Gas Adsorption Processes ...................................... 57
Guidelines for Choosing Aspen Adsim Isotherm Models (gas)................................... 58
About Multi-Component Mixture Isotherms (gas) ................................................... 58
Isotherm Tab (gas): Isotherm Assumed for Layer .................................................. 61
Isotherm Tab (gas): Adsorbed Solution Theory...................................................... 70
Isotherm Tab (gas): Isotherm Dependency........................................................... 70
Energy Balance Tab (gas)........................................................................................ 70
Energy Balance Tab (gas): Energy Balance Assumption .......................................... 70
Energy Balance Tab (gas): Consider Heat of Adsorbed Phase................................... 71
Energy Balance Tab (gas): Heat of Adsorption Assumption...................................... 72
Energy Balance Tab (gas): Form of Heat Transfer Coefficient................................... 73
Energy Balance Tab (gas): Form of Gas Thermal Conductivity ................................. 75
Energy Balance Tab (gas): Heat Transfer to Environment........................................ 76
Energy Balance Tab (gas): Form of Gas-Wall Heat Transfer Coefficient ..................... 78
Reaction Tab (gas) ................................................................................................. 79
About Gas Adsorption with Reaction Processes ...................................................... 79
Reaction Tab (gas): Reactions Present ................................................................. 80
Reaction Tab (gas): Homogeneous Rate Dependency ............................................. 80
Reaction Tab (gas): Number of Homogeneous Reactions......................................... 81
Reaction Tab (gas): Heterogeneous Rate Dependency ............................................ 81
Reaction Tab (gas): Number of Heterogeneous Reactions ....................................... 81
Reaction Tab (gas): Are Solid Reactants Present.................................................... 82
Reaction Tab (gas): Solid Reactant List ................................................................ 82
Procedures Tab (gas).............................................................................................. 82
Gas Adsorption: Summary of Mass and Energy Balance Equations................................. 82
Gas Adsorption: Mass Balance for Gas Phase......................................................... 83
Gas Adsorption: Mass Balance for Additional Solid Phase ........................................ 83
Gas Adsorption: Gas Phase Energy Balance........................................................... 84
Gas Adsorption: Solid Phase Energy Balance......................................................... 84
Gas Adsorption: Wall Energy Balance................................................................... 85
Gas Adsorption: Summary of Factors that affect the Mass Balance Equations............. 85
Gas Adsorption: Defining the Mass Balance for Additional Solid Phases ..................... 87
Gas Adsorption: Summary of Factors that affect the Energy Balance ........................ 87
Contents 11
Gas Adsorption: Defining the Energy Balance in the Gas Phase................................ 87
Gas Adsorption: Defining the Energy Balance for the Solid Phase ............................. 90
Gas Adsorption: Defining Energy Balance for the Wall ............................................ 92
Gas Adsorption: Explanation of Equation Symbols....................................................... 93
2 GAS CYCLIC STEADY STATE MODELING..................................................... 99
Introduction .......................................................................................................... 99
What is CSS Modeling? ........................................................................................100
Discretization Techniques for Time and Space ...........................................................103
Connectivity between CSS Models ...........................................................................103
Bed Model Details .................................................................................................104
Material Balance ..............................................................................................104
Momentum Balance..........................................................................................105
Kinetic Model ...................................................................................................106
Energy Balance................................................................................................109
Adsorption Equilibrium Models ................................................................................112
Introduction ....................................................................................................112
Mathematical Equation Form for Extended Langmuir 1...........................................113
Mathematical Equation Form for Loading Ratio Correlation 1...................................117
Mathematical Equation Form for Extended Dual-Site Langmuir 1.............................122
Mathematical Equation Form for Extended Dual-Site Langmuir 2.............................123
I.A.S.T. (Ideal Adsorbed Solution Theory)............................................................123
Pure Isotherm List for the IAST Calculation of CSS................................................125
Langmuir 1 .....................................................................................................126
Langmuir 2 .....................................................................................................126
Langmuir 3 .....................................................................................................127
Langmuir 4 .....................................................................................................128
Langmuir 5 .....................................................................................................129
Dual-Site Langmuir 1........................................................................................130
Dual-Site Langmuir 2........................................................................................130
Sips (Langmuir-Freundlich) 1.............................................................................131
Contents 12
Henry 1 ..........................................................................................................136
Henry 2 ..........................................................................................................136
Henry 3 ..........................................................................................................137
Henry 4 ..........................................................................................................137
Freundlich 1 ....................................................................................................138
Toth 1 ............................................................................................................139
BET 1.............................................................................................................139
User Guidelines.....................................................................................................140
How to Create a CSS Simulation Flowsheet ..........................................................140
How to Create a Dynamic Simulation Flowsheet using CSS Models ..........................158
How to Convert a CSS Flowsheet to a Dynamic Flowsheet ......................................174
How to Convert a Dynamic Flowsheet into a CSS Flowsheet ...................................177
Developers Tips to Get Better Convergence Property in CSS Simulation...................180
3 ION-EXCHANGE PROCESSES.....................................................................184
About Ion-Exchange Processes...........................................................................184
Bed Model Assumptions for Ion-Exchange............................................................185
Configure Form (ionx).......................................................................................185
Configure Layer Form (ionx) ..............................................................................185
General Tab (ionx) ...........................................................................................186
General Tab (ionx): Discretization Method to be Used............................................186
General Tab (ionx): Number of Nodes .................................................................186
Material/Momentum Balance Tab (ionx)...............................................................186
Material/Momentum Balance Tab (ionx): Material Balance Assumption.....................186
About Axial Dispersion in Ion-Exchange Processes ................................................188
Deciding When to Use Axial Dispersion in Ion-Exchange Processes ..........................188
Kinetic Model Tab (ionx)....................................................................................189
Kinetic Model Tab (ionx): Film Model Assumption..................................................189
Kinetic Model Tab (ionx): Kinetic Model Assumption ..............................................190
Kinetic Model Tab (ionx): Form of Lumped Resistance ...........................................190
Kinetic Model Tab (ionx): Form of Mass Transfer Coefficient ...................................191
Isotherm Tab (ionx) .........................................................................................191
About Adsorption Isotherms for Ion-Exchange Processes .......................................191
Isotherm Tab (ionx): Isotherm Assumed for Layer ................................................192
Summary of Mass Balance Equations for Ion-Exchange Processes ...........................194
Explanation of Equation Symbols for Ion-Exchange Processes.................................195
4 LIQUID ADSORPTION PROCESSES ...........................................................197
About Liquid Adsorption Processes......................................................................197
Bed Model Assumptions for Liquid Adsorption.......................................................198
Contents 13
Configure Form (liq) .........................................................................................198
Configure Layer Form (liq).................................................................................198
General Tab (liq)..............................................................................................199
General Tab (liq): Discretization Method to be Used ..............................................199
General Tab (liq): Number of Nodes....................................................................199
Material/Momentum Balance (liq) .......................................................................199
Material/Momentum Balance Tab (liq): Material Balance Assumption .......................199
Material/Momentum Balance Tab (liq): Pressure Drop Assumption...........................201
Material/Momentum Balance Tab (liq): Velocity Assumption ...................................202
Material/Momentum Balance Tab (liq): Overall Material Balance Assumption.............202
Kinetic Model Tab (liq) ......................................................................................202
Kinetic Model Tab (liq): Film Model Assumption ....................................................203
Kinetic Model Tab (liq): Kinetic Model Assumption.................................................203
Kinetic Model Tab (liq): Form of Mass Transfer Coefficient......................................204
About Adsorption Isotherms for Liquid Adsorption.................................................205
Guidelines for Choosing Aspen Adsim Isotherm Models ..........................................205
The Ideal Adsorbed Solution Theory (IAS) ...........................................................206
Isotherm Tab (liq): Isotherm Assumed for Layer...................................................206
Energy Balance Tab (liq) ...................................................................................212
Energy Balance Tab (liq): Energy Balance Assumption...........................................212
Energy Balance Tab (liq): Consider Heat of Adsorbed Phase ...................................214
Energy Balance Tab (liq): Heat of Adsorption Assumption ......................................214
Energy Balance Tab (liq): Form of Heat Transfer Coefficient ...................................215
Energy Balance Tab (liq): Form of Fluid Thermal Conductivity.................................216
Energy Balance Tab (liq): Heat Transfer to Environment ........................................217
Procedures Tab (liq) .........................................................................................219
Liquid Adsorption: Summary of Mass and Energy Balance ......................................219
Liquid Adsorption: Mass Balance.........................................................................219
Liquid Adsorption: Solid Phase Energy Balance .....................................................220
Liquid Adsorption: Fluid Phase Energy Balance .....................................................220
Liquid Adsorption: Wall Energy Balance...............................................................220
Liquid Adsorption: Explanation of Equation Symbols..............................................221
5 NUMERICAL METHODS .............................................................................224
About Numerical Methods..................................................................................224
Choosing the Discretization Method ....................................................................225
About the Discretization Methods........................................................................225
Upwind Differencing Scheme 1...........................................................................227
Upwind Differencing Scheme 2...........................................................................228
Central Differencing Scheme 1...........................................................................228
Central Differencing Scheme 2...........................................................................229
Leonard Differencing Scheme.............................................................................229
Contents 14
Quadratic Upwind Differencing Scheme ...............................................................230
Mixed Differencing Scheme................................................................................232
Biased Upwind Differencing Scheme....................................................................233
Fromms scheme..............................................................................................234
Flux Limited Discretization Scheme.....................................................................235
6 ESTIMATION WITH ASPEN ADSIM............................................................236
Two Estimation Tools in Aspen Adsim 2004.1 .......................................................236
About the Estimation Module .............................................................................236
Defining Estimated Variables in the Estimation Module ..........................................238
Steady-State Estimation Using the Estimation Module ...........................................239
Manually Entering Steady-State Experimental Data...............................................239
Steady-State Experimental Data from the Clipboard..............................................240
Dynamic Estimation Using the Estimation Module .................................................242
Manually Entering Dynamic Experimental Data .....................................................243
Dynamic Experimental Data from the Clipboard....................................................244
Performing Estimation Using the Estimation Module ..............................................247
Converting Estimation Module Data ....................................................................247
Recommendations When Using the Estimation Module...........................................247
7 CYCLIC OPERATION .................................................................................249
Cyclic Operations in Aspen Adsim 2004.1.............................................................249
About the Cycle Organizer .................................................................................249
Opening the Cycle Organizer..............................................................................250
Cycle Organizer Window....................................................................................250
Step Control ....................................................................................................252
Time Driven Step .............................................................................................252
Discrete Event Driven Step................................................................................252
Step Variables .................................................................................................256
Adding Step Variables.......................................................................................256
Removing Step Variables...................................................................................257
Changing Step Variable Values...........................................................................257
Interaction Control ...........................................................................................258
Defining a Step Interaction................................................................................258
Deleting Interaction Steps .................................................................................259
Adding Extra Interaction Steps...........................................................................259
Interacting Steps and Time Controls ...................................................................259
Additional Cycle Controls...................................................................................260
Maximum Cycles Box........................................................................................260
Record Initial and Record Frequency Boxes..........................................................261
Take Snapshot Box...........................................................................................261
Cyclic Steady State Testing Box .........................................................................261
Contents 15
Additional Step Controls....................................................................................262
Execute End of Step Script Box ..........................................................................262
Take Snapshot at End of Step Box......................................................................262
Generating Cyclic Tasks ....................................................................................263
Activating and Deactivating Cyclic Tasks..............................................................263
Cyclic Reports..................................................................................................264
Preparing Aspen Adsim for Cyclic Reporting .........................................................264
Cyclic Stream Reports.......................................................................................265
Cyclic Recovery Reports ....................................................................................266
8 FLOWSHEETING .......................................................................................268
About Model Types ...........................................................................................268
General Model Types ........................................................................................269
Reversibility ....................................................................................................269
About Flowsheets in Aspen Adsim.......................................................................272
Connectivity on Flowsheets................................................................................273
Templates.......................................................................................................274
Demonstrations ...............................................................................................274
Types of Flowsheet in Aspen Adsim.....................................................................275
Types of Flowsheet: Simple Flowsheet ................................................................275
Intermediate Flowsheet.....................................................................................276
Full Flowsheet..................................................................................................277
Single Bed Approach.........................................................................................278
Pressure Interaction Diagram.............................................................................278
Interactions.....................................................................................................281
Specifications for Flowsheets .............................................................................283
Solver Options.................................................................................................283
Run Time Options.............................................................................................285
Model Specification...........................................................................................286
Consistency and Problem Definition Checks..........................................................287
Physical Properties ...........................................................................................288
Use of User Fortran ..........................................................................................289
Using a Physical Properties Application ................................................................290
Switching Between Methods...............................................................................290
Connecting to Aspen Dynamics Flowsheets ..........................................................291
Typical Workflows ............................................................................................291
Valid Flowsheet Combinations ............................................................................293
Connecting to a Single Bed Approach Flowsheet ...................................................296
9 REFERENCE LIST FOR ADSORPTION PROCESSES......................................298
INDEX ..........................................................................................................299
Contents 16

Introducing Aspen Adsim 17
Introducing Aspen Adsim
Aspen Adsim simulates gas processes with adsorption only, or adsorptive
reaction gas processes where both reaction and adsorption occur
simultaneously.
Gas-phase adsorption is widely used for the large-scale purification or bulk
separation of air, natural gas, chemicals and petrochemicals.
1 Gas Adsorption Processes 18
1 Gas Adsorption Processes
This chapter contains information on:
About Gas Adsorption Processes.
Bed Model Assumptions for Gas Adsorption Processes.
About Aspen Adsim Bed Models.
Configure Form.
Configure Layer Form.
General Tab.
Material/Momentum Balance Tab.
Kinetic Model Tab.
Isotherm Tab.
Energy Balance Tab.
Reaction Tab.
Procedure Tab.
Summary of Mass and Energy Balance Equations.
Explanation of Equation Symbols.
About Gas Adsorption
Processes
Gas-phase adsorption is widely used for the large-scale purification or bulk
separation of air, natural gas, chemicals and petrochemicals, where it is often
better to use gas-phase adsorption rather than the older unit operations of
distillation and absorption.
Adsorbent attracts molecules from the gas, removing the molecules from the
gas phase and concentrate on the surface of the adsorbent. Many process
concepts have been developed to allow:
Efficient contact of feed gas mixtures with adsorbent to carry out desired
separations.
Efficient regeneration of the adsorbent for subsequent reuse.
For gas phase applications, most commercial adsorbents are pellets, beads, or
other granular shapes, typically about 1.5 to 3.2 mm in diameter. These
adsorbents are usually packed into fixed beds through which the gaseous feed
mixtures are passed. Normally, the process is cyclic. When the bed capacity is
exhausted, the feed flow is stopped to finish the loading step of the process.
The bed is then treated to remove the adsorbed molecules in separate
regeneration steps, then the cycle is repeated.
Gas phase adsorption processes have seen a growth in both variety and scale,
especially since 1970. This is due mainly to improvements in adsorbents, for
example the discovery of porous adsorbents with a large surface area, such
as zeolites. These advances have encouraged parallel inventions of new
process concepts. Increasingly, the development of new applications requires
close cooperation in adsorbent design and process cycle development and
optimization.
Bed Model Assumptions for Gas
Adsorption Processes
Aspen Adsim simulates gas processes with adsorption only, or adsorptive
reaction gas processes where both reaction and adsorption occur
simultaneously.
For gas processes, the bed model makes the following assumptions:
Isothermal or non-isothermal conditions apply. Terms in the energy
balances include:
Thermal conductivity of gas and thermal conductivity of solid.
Compression.
Gas-solid heat transfer.
Heat of adsorption.
Enthalpy of adsorbed phase.
Heat exchange with environment.
Wall energy terms.
Enthalpy of mixing is negligible.
Plug flow or plug flow with axial dispersion occurs.
The system is fully mixed in the radial direction. Alternatively, radial
dispersion and thermal conduction are used to account for radial material
and temperature distributions.
The gas phase is ideal or non-ideal, the non-ideal behavior needing a
compressibility factor.
Gas phase pressure is either constant (with velocity either constant, or
varying according to mass balance and only applicable for breakthrough
simulations), or the pressure varies according to a laminar or turbulent
flow momentum balance.
Mass transfer is described using a lumped overall resistance, or by a
model that accounts separately for micropore and macropore effects. The
driving force is based on a liquid or solid film, and is either linear,
quadratic, or user-specified. Mass transfer coefficients are either constant,
or vary with local conditions. A limited rigorous particle material balance
functionality is provided.
Adsorption isotherms are either applicable for single or multi-component
adsorption. IAS theory can be used for pure component isotherms.
About Aspen Adsim's Bed
Models
The table shows the classifications of adsorption bed models:

Name Type
Model type Flow setter under compressible flow
conditions.
Flow type Reversible.
Time dependency Dynamic.
Reversible models handle forward or reverse flow in the bed. They contain
dummy variables associated with the input and output streams.
The adsorption bed models are usually flow setters, but within the bed they
can be both flow setters and pressure setters. This is because they determine
internal pressure profiles and gas velocity profiles, provided the general
compressible flow model is used.
The nature of the process and its operating conditions determine the type of
model to use. For example, a bulk separation process such as producing
oxygen-rich gas from air requires a different model to that for a purification
process for removing trace impurities.
The adsorption column models use a set of partial differential equations to
represent the momentum, heat, and material balances across the column.
You can add further relationships, which are specific to the various options.
Bed Model Ports
Bed models contain an input and an output port. Each port has associated
variables that correspond to the material connection stream variables, and
which allow for reversible flow.
Configure Form (Gas)
On the Configure form of the bed model:
1 Enter the number of layers within the bed (one or more).
2 Enter the bed type: Vertical, Horizontal or Radial.
See Configure Form for Gas Process Bed Model, later.
3 For vertical beds only, define the spatial dimensions of the bed model: 1-D
or 2-D.
See Configure Form for Gas Process Bed Model: Spatial Dimensions, later.
4 For vertical and horizontal beds, specify whether an internal heat
exchanger is present.
See Configure Form for Gas Process Bed Model: Internal Heat, and See
Configure Form for Gas Process Bed Model: Spatial Dimensions, later.
5 In the Description box for each layer, type a brief name or description.
6 Click Configure to open the
Configure Layer Form (gas) dialog box.
7 Click Specify to open the Specify form for the layer model.
Configure Form (gas): Bed Type
To choose the bed type:
In the Bed Type box, choose vertical, horizontal or radial bed orientation.

Vertical Bed Type
Typically, you use a vertical orientation for an adsorption bed. Vertical
columns prevent variation in flow width because the flow is along the column
axis.
Horizontal Bed Type
Occasionally, you may need to choose horizontal orientation, for example,
when a vertical bed may cause fluidization of the bed. Horizontal beds allow a
much greater inflow area, keeping gas superficial velocities below the
fluidization velocity.
In the horizontal column orientation, the flow through the adsorbent packing
is still vertical, but is now at right angles to the column axis so there is
variation in the effective flow area of the column with height above the
column base. The height of the start of the (first) adsorbent layer above the
column base is the same thickness as the empty dead space and supporting
grating.
L
H
0,1
H
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H
0,2
H
B,2
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B
z
W(z)
Layer 1
Layer 2

The effective width W(z) of the bed is given as:
( ) | |
5 . 0
4 ) ( z D z z W
B
=
Where:
B
D = Column diameter
z = Height of adsorbent above column base
The effective cross-sectional flow area of the bed is the product of the width
and the total horizontal length of the bed, that is, W(z)L.
Radial Bed Type
Use a radial bed type when the flow through the bed is in the radial direction,
from a central core to the outer circumference of the packed bed.
Product
Feed
Adsorbent
Layer 1
Inner Core
Bed Shell
Adsorbent
Layer 2

The volumes of the central core and the bed shell are the dead volumes of the
column. The positive radial co-ordinate runs from the center of the bed to the
outer circumference.
Configure Form (gas): Spatial
Dimensions
If you select a vertical bed type, you need to specify either one- or two-
dimensional spatial discretization:
One-dimensional discretization Spatial derivatives are evaluated in axial
(flow) direction only.
Two dimensional discretization Second order spatial derivatives are
evaluated in both the axial and radial direction, allowing the calculation of
radial composition and temperature distributions.
Configure Form (gas): Internal Heat
Exchanger
The adsorption columns used in some temperature swing adsorption
processes are equipped with internal heat exchangers to improve adsorbent
regeneration. Aspen Adsim can simulate this configuration through the
following sub-options:
None, that is, no heat exchanger
1-Phase, internal
1-Phase, jacket
Steam-Water, internal
Steam-Water, jacket
The heat exchanger operates either as a jacket encircling the adsorption
column or is integrated into the packed bed of the adsorbent. The heat
exchange medium remains in the phase it is supplied in, or is condensed in
order to use its heat of evaporation to heat the bed.
Heat Exchange
Jacket
Internal Heat
Exchanger

Configure Layer Form (gas)
Use the options in the Configure Layer Form to specify the bed layers.
The form has the following tabs:
General tab
Material/Momentum Balance tab
Kinetic Model tab
Isotherm Tab
Energy Balance tab
Reaction tab
Procedures tab
General Tab (gas)
Use the General tab to specify the numerical options for solving the partial
differential equations, and to select the gas model assumption.
General Tab (gas): Discretization
Method to be used
These discretization methods are available for gas phase adsorption
processes:
UDS1
UDS2
CDS1
CDS2
LDS
QDS
MIXED
Flux Limiter
BUDS
FROMM
General Tab (gas): Number of Nodes
In the Number of Nodes box, choose an appropriate number of axial nodes for
your chosen discretization method.
General Tab (gas): Number of Radial
Nodes
The Number of Radial Nodes option is available only if you selected a vertical
bed with a 2-D spatial dimension.
Choose an appropriate number of radial nodes. The derivatives in the
component material balances and the gas phase energy balances are second
order in radial co-ordinates, and are approximated by central differences.
General Tab (gas): Flux Limiter to be
used
If flux limiter is your discretization method, choose from:
van Leer
OSPRE
SMART
General Tab (gas): Gas Model
Assumption
Gas flowing through the packed bed can be ideal or non-ideal. The gas model
defines the relationship between pressure, temperature and molar density:
g g
T R Z P = (overall) or
i g i
c T R Z Py = (component)
Where:
P = Pressure
Z = Compressibility factor
R = Universal gas constant
g
T = Gas phase temperature
g
= Molar gas phase density
i
y = Mole fraction of component i
i
c = Molar concentration of component i
In the Gas Model Assumption box, choose from:
Ideal Gas Law (where Z=1)
Fixed Compressibility (where Z is constant)
User Procedure Compressibility (where Z is supplied through a user
Fortran subroutine interfaced by the procedure pUser_g_Compressibility,
or calculated using a selected physical properties package)
User Submodel Compressibility (where Z is supplied through the user
submodel gUserCompressibility)
Material/Momentum Balance
Tab (gas)
Use the Material/Momentum Balance tab to specify the material and
momentum balances, and the 2-D dispersive properties.
About Axial Dispersion in Gas
As a fluid flows through a packed column, axial mixing tends to occur. This
reduces the efficiency of separation so should be minimized in column design.
However, if axial dispersion occurs, the model must account for its effects.
In gases, there are three main sources of axial dispersion:
From wall effects, due to non-uniformity of packing either at the wall (wall
effects) or in the core section of the packing (channeling). You can avoid
this type of dispersion by having a sufficiently large ratio of bed-to-particle
diameters.
From molecular diffusion effects.
From turbulent mixing effects arising from the splitting and recombining of
flows around the adsorbent particles.
In general, the molecular diffusion and turbulent mixing effect are additive
and proportional to the second order spatial concentration derivative, so they
can be lumped together into a single effective dispersion coefficient,
i
E .
The dispersion term in the material balance is typically expressed as:
2
2
z
c
E
k
zk i

Where:
i
= Interparticle voidage
zk
E = Axial dispersion coefficient of component k
The type of flow determines whether this term is included or omitted in the
material balance.
It is useful to work out the Peclet number Pe using a dispersion coefficient
(effective bulk diffusivity
z
E ), typical bed velocities (
g
), and bed height
(
b
H ):
Pe
v H
E
g
b
z
=
The Peclet number quantifies the degree of dispersion introduced into the
system. It is dimensionless so is more convenient to use for this purpose than
the dispersion coefficient.
The following table shows the effect of different values of Peclet number:

If the Peclet
number is
The effect of axial dispersion on bed
performance is
0 Infinite: the bulk gas is perfectly mixed and the gas is
homogeneous through the entire bed.
< 30 Significant.
> 100 Very slight: The bed operates under near plug flow
conditions.
Zero: The bed operates under plug flow conditions.

Note: The numerical methods used to model the spatial
derivatives in the general equations can also introduce an
artificial form of dispersion.
Material/Momentum Balance Tab
(gas): Material Balance Assumption
The Material Balance Assumption option is available unless you previously
chose vertical bed and two-dimensional bed discretization. Choose from these
options:
Convection Only
Convection with Constant Dispersion
Convection with Estimated Dispersion
Convection with User Submodel Dispersion
Convection with User Procedure Dispersion
Material Balance Assumption (gas): Convection Only
The Convection Only option drops the dispersion term from the material
balance, so the model represents plug flow with a zero dispersion coefficient
(infinite Peclet number). Because the dispersion term is missing, you need not
supply the dispersion coefficient.
Material Balance Assumption (gas): Convection with Constant
Dispersion
The Convection with Constant Dispersion option assumes that the dispersion
coefficient is constant for all components throughout the bed. You supply its
value.
Material Balance Assumption (gas): Convection with Estimated
Dispersion
The Convection with Estimated Dispersion option assumes that the dispersion
coefficient varies along the length of the bed. Aspen Adsim estimates the
values during the simulation.
Aspen Adsim estimates the components' dispersion coefficients using the
following correlation, (Kast, 1988):
|
|
.
|
\
|
+
+ =
p g
mk i
i
p g
mk zk
r v
D
r v
D E
2
49 . 9 1
73 . 0

Where:
g
= Gas velocity
mk
D = Molecular diffusivity
zk
E = Axial dispersion coefficient
i
p
r = Particle radius
Material Balance Assumption (gas): Convection with User
Submodel Dispersion
If you choose Convection with User Submodel Dispersion, the (varying)
dispersion coefficient is estimated using the user submodel gUserDispersion.
Material Balance Assumption (gas): Convection with User
Procedure Dispersion
If you choose Convection with User Procedure Dispersion, the (varying)
dispersion coefficient is estimated through a user-supplied Fortran subroutine,
which Aspen Adsim interfaces through the procedure pUser_g_Dispersion.
(gas): Momentum Balance Assumption
Use the Momentum Balance Assumption box to specify how the adsorption
bed layer model treats gas velocity and pressure. Base your choice on the
plant operating conditions and the envisaged scope of the simulation
(constant pressure models are only applicable for breakthrough
investigations).
Choose from:
Constant pressure optionsThe bed is driven by gas superficial velocity
and the pressure is assumed constant in the bed. The bed is velocity-driven,
and no momentum balance is needed. These models are applicable only for
breakthrough investigations.
The constant pressure options are:
Constant Pressure and Velocity
Constant Pressure with Varying Velocity
Pressure driven optionsThe velocity is related to the overall or internal
pressure gradients. In such cases, velocity and pressure gradient are related
through a momentum balance. The pressure-drop relationships apply to local
conditions inside the bed, so the momentum equations for entire beds can be
used to determine local pressure gradients. No simplifying assumptions are
made regarding the gas densities, gas velocities, or pressures.
The pressure driven options are:
Darcy's Law
Karman-Kozeny Equation
Burke-Plummer Equation
Ergun Equation
Momentum Balance Assumption (gas): Constant Pressure and
Velocity
Use the Constant Pressure and Velocity option only when using a simple
flowsheet to simulate the breakthrough behavior of an adsorption column.
The gas velocity and pressure are constant along the bed, whilst the gas
density is essentially constant along the bed. These assumptions are valid
only when dealing with the removal of trace components from a bulk carrier
gas.
Momentum Balance Assumption (gas): Constant Pressure with
Varying Velocity
Use the Constant Pressure with Varying Velocity option only when using a
simple flowsheet to simulate the breakthrough behavior of an adsorption
column.
Gas density is constant along the bed, so the pressure does not vary axially.
Superficial velocity varies along the bed due to the rate at which the gas is
adsorbed onto the solid, or desorbed from it.
This option is applicable to bulk separation applications, in which case the
axial velocity profile is determined by an overall material balance rather than
an axial pressure gradient.
Momentum Balance Assumption (gas): Darcy's Law
Use this option to apply a linear relationship between the gas superficial
velocity and the pressure gradient at a particular point in a bed.
Darcy's law states that pressure drop is directly proportional to flow rate. You
have to set the proportionality constant. The relationship is given as:
g p K
z
P
=
Where:
p
K = Darcys law proportionality constant
g
= Gas velocity
Momentum Balance Assumption (gas): Karman-Kozeny
Equation
Choose this option to use the Karman-Kozeny equation to relate velocity to
pressure drop. This is the laminar component of the Ergun equation:
( )
g
i p
i
v
r
z
P
3 2
2 3
2
) 1 ( 10 5 . 1

u

For details of the Karman-Kozeny model see Bird et al. (1960).
Where:
= Shape factor
u = Dynamic gas viscosity
Momentum Balance Assumption (gas): Burke-Plummer
Equation
This option uses the Burke-Plummer equation to relate velocity to pressure
gradient:
2
3
5
2
) 1 (
10 75 . 1
g
i p
i g
v
r
M
z
P

Where:
M = Molecular weight
The equation is valid for fully turbulent conditions when the particle Reynolds
number Re is:
1000
2
> =
u
g p g
v r M
Re
For details of the Burke-Plummer model, see Bird et al. (1960).
Momentum Balance Assumption (gas): Ergun Equation
This option uses the Ergun equation, which combines the description of
pressure drops by the Karman-Kozeny equation for laminar flow and the
Burke-Plummer equation for turbulent flow.
( )
|
|
.
|
\
|
+

=
2
3

5
3 2
2 3
2
) 1 (
10 75 . 1
2
) 1 ( 10 5 . 1
g
i p
i
g g
i p
i
v
r
M v
r
z
P

It is valid for both laminar and turbulent flow, and is the most popular option.
For details of the Ergun model, see Bird et al. (1960).
Set Variables for Pressure-Drop Options (gas)
This table shows the variables you need to specify for the pressure drop
options:

Equation Symbol Variable Definition
p
K
Kp Proportionality constant
Sfac Sphericity
p
r
Rp Particle radius
i

Ei Interparticle voidage
(gas): 2-D Dispersive Properties
The 2-D Dispersive Properties option is available only if you selected vertical
bed and two-dimensional discretization. The axial dispersion is calculated
from:
2
2
z
c
E
k
zk i

Additionally, a radial dispersion term is also evaluated:
|
.
|
\
|
r
c
r
r r
E
k
rk i
1

If you later specify the process as non-isothermal, equivalent dispersive
terms are evaluated for the gas and solid phase energy balances. Namely:
Gas phase thermal conduction in axial direction:
2
2
z
T
k
g
gz i

Gas phase thermal conduction in radial direction:
|
|
.
|
\
|
r
T
r
r r
k
g
gr i
1

Solid phase thermal conduction in axial direction:
2
2
z
T
k
s
sz

Solid phase thermal conduction in radial direction: |
.
|
\
|
r
T
r
r r
k
s
sr
1

Choose from:
Fixed
Estimated
2-D Dispersive Properties (gas): Fixed
Choose this option if the dispersive properties are constant throughout the
packed bed. You must supply values for:

zk
E : The dispersion coefficient of component k for the axial direction.

rk
E : The dispersion coefficient of component k for the radial direction.
For non-isothermal operation, you must give values for the following thermal
conductivities:

g
k : The effective thermal conductivity of the gas phase.

s
k : The effective thermal conductivity of the solid phase.
2-D Dispersive Properties (gas): Estimated
Choose this option when variables such as pressure, temperature and velocity
are changing significantly through the column. These variables influence the
values of dispersion coefficients and thermal conductivities.
The axial dispersion coefficient is estimated using the following correlation,
(Kast, 1988):
|
|
.
|
\
|
+
+ =
p g
mk i
i
p g
mk zk
r v
D
r v
D E
2
49 . 9 1
73 . 0

Where:
g
= Gas Velocity
mk
D = Molecular diffusivity of component k
zk
E = Axial dispersion coefficient of component k
i
p
r = Particle radius
The radial dispersion coefficient is evaluated according to (Carberry, 1976):
4
g p
rk
v r
E =
Where:
rk
E = Radial dispersion coefficient of component k
Assuming the analogy between mass and heat transfer is valid, the effective
gas phase thermal conductivity in the axial direction is:
( )
=
=
nc
i
i i z pg g gz
y E C k
1
,

Where:
gz
k = Effective gas phase thermal conductivity in axial direction
g
= Molar gas density
pg
C = Molar specific heat capacity at constant volume
The effective gas phase thermal conductivity in the radial direction comprises
a static and a dynamic contribution (Froment and Bischoff, 1990). The two
contributions are additive. Assuming the validity of the analogy between heat
and mass transfer, the dynamic contribution to the effective radial gas phase
thermal conductivity is:
( )
=
=
nc
k
k rk pg g i
dyn
gr
y E C k
1

Where:
dyn
gr
k = Dynamic contribution to the effective gas phase thermal
conductivity in radial direction
As the adsorbent (a solid) is not in motion, it has no dynamic contribution to
its effective thermal conductivity in the radial direction.
The static contribution of the gas phase effective thermal conductivity in the
radial direction is:
( )
rg p g i
stat
gr
r k k 2 + =
Where:
0 . 1 = = Factor
( )
3
3
100
1
1 2
1
10 227 . 0
|
.
|
\
|
T
p
p
rg
= Radiation contribution
p = Emissivity
g
k = Thermal conductivity of the gas.
The total effective radial gas phase thermal conductivity is now given by:
stat
gr
dyn
gr gr
k k k + =
The effective radial solid phase thermal conductivity comes from:
( )
s
p rs
g
i stat
sr sr
k
r
k
k k

+
+
= =
2
1
1

Where:
3
3
100 2
10 227 . 0
|
.
|
\
|
T
p
p
rs
= Radiation contribution
28 . 0 = = Function of the packing density
3
2
= = Factor
s
k = Thermal conductivity of the solid
Aspen Adsim assumes that the effective solid thermal conductivity in the axial
direction is not a function of any process variables, so
s
k is constant through
the simulation.
Kinetic Model Tab (gas)
Use the Kinetic Model tab to specify the model kinetics, such as resistances,
diffusivities and mass transfer coefficients.
Kinetic Model Tab (gas): Film Model
Assumption
In the Film Model Assumption box, choose from:
Solid, where the mass transfer driving force is expressed as a function of
the solid phase loading.
Fluid, where the mass transfer driving force is expressed as a function of
the gas phase concentration.
Kinetic Model Tab (gas): Kinetic Model
Assumption
Typically, several mass transfer resistances occur in gas phase adsorption
processes:
Mass transfer resistance between the bulk gas phase and the gas-solid
interface.
Mass transfer resistance due to the porous structure of the adsorbent. In
cases where the adsorbent has two distinct pore size regions, such as
macropores and micropores, the resistance can be subdivided to account
separately for each region.
You can consider mass transfer resistances in one these ways:
Lumped Resistance Separate mass transfer resistances are lumped as a
single overall factor, or one resistance dominates all others.
Micro & Macro Pore The effects of the individual resistances to mass
transfer in the micro- and macropores can be accounted for individually.
Particle MB Where all components are adsorbed and the adsorbent has
a homogenous pore structure, you can use a rigorous particle material
balance to determine the loading profile inside the adsorbent.
Particle MB 2 Where inert components are present, or the radial gas
phase concentration profiles in the pores of the adsorbent particles are to
be accounted for in addition to the loading profiles. The adsorbent should
possess a homogenous pore structure. This option performs a rigorous
particle material balance for both the adsorbed and the gas phases.
In the Kinetic Model Assumption box, choose from these options:
Lumped Resistance
Micro and Macro Pore Effects
Particle MB
Particle MB 2
User Procedure
User Submodel
Kinetic Model Assumption (gas): Lumped Resistance
Here, the separate resistances to mass transfer is lumped as a single overall
factor, or one mass transfer resistance dominates the others.
Kinetic Model Assumption (gas): Micro and Macro Pore Effects
Two concentration gradients greatly affect the diffusion rate:
Within the pores of the solid.
Within the void spaces between the particles (that is, within the
crystallines).
Under practical conditions in gas separation, pore diffusion limits the overall
mass transfer rate between the bulk flow and the internal surface of a
particle. This gives importance to the effect of pore diffusion on the dynamics
of absorbers.
The following table shows the difference between modeling macropore and
micropore resistance in composite and uniform adsorbents:

Pore structure Example(s) Micropore
diffusional
resistance
Macropore
diffusional
resistance
Uniform Activated carbon alumina
silica molecular sieve
carbon
High Negligible
Composite Zeolites High High
When modeling adsorbents with uniform pore structure, you can usually
discount any macropore diffusional resistance. However, when modeling
composite adsorbents, both resistances can be significant and should be
accounted for.
Qualitatively, a higher pore diffusion rate results in a sharper and steeper
concentration wave front, giving a better separation. Quantitative prediction
of behavior requires the simultaneous solution of the mass balance within the
particle, as well as for the bulk flow in the bed.
Solving the mass balance equation within the particle is usually complex.
However, you can simplify the mass balance equation in two ways:
Use expressions that relate the overall uptake rate to the bulk flow
concentration:
( )
i s i ads
c f
t
w
J
i
= =
,

Where:
s
= Adsorbent bulk density
i
w = Loading of component i due to adsorption
i ads
J
,
= Mass transfer rate of component i
If you know the concentration profile within the particle, you can make
considerable savings in numerical computation because integration along
the radial distance in the particle is no longer necessary. Several
researchers have recently shown that profiles obtained by exact numerical
solutions of both Pressure Swing and Thermal Swing Adsorption processes
are usually parabolic in shape, so you can model pore diffusion by
assuming a parabolic concentration profile within the particle.
The model developed for particle diffusion accounts for both interparticle
(macropore) and intraparticle (micorpore) diffusion effects. The model
assumes that material flows first from the bulk gas to the macropores
(crystallines), and then from the macropores to the solid surface via the
micropores:
r
P
2r
c
Interpellet
porosity
Micropore
Bulk Gas Macropore
Solid
Surface
Bulk:
c
bk
,
B
, w
bk
Macropores:
w
msk
, c
msk
Interpellet
Voidage:
i
Pellet
(macroparticle)
Intrapellet
Porosity
P
Solid
Microporous
Particles: w
k
, c
k
c
bk
,
B
, w
bk
c
msk
, (1-
i
)
P
, w
msk
i
c
k
, w
k
* *
* * *
*

The material balance model assumes that:
Radial concentration profile within the particle is parabolic.
Concentration profile within the particle is radially symmetric.
Radial dispersion is negligible.
Gas Phase
The component balance in the bulk gas phase is of the form:
( )
( ) ( ) 0 1 1 =
t
c
t
w
t
c
z
v c
msk
p i
k
s p
bk
B
g bk

[Convection] + [accumulation] + [mass transfer (accumulation) to micropore]
+ [mass transfer (accumulation) to macropore]
In the given example, the gas phase material balance is written for a
convection only situation in a vertical, one-dimensional adsorption layer.
Macropore (Crystalline)
The material balance in the macropore is given as:
Fluid Film Model:
( ) ( ) ( )
msk bk mac
k
s p
msk
p i
c c K
t
w
t
c
=
1 1
[accumulation] + [mass transfer to micropore] = [rate of mass transfer from
bulk gas]
Solid Film Model:
( ) ( ) ( ) ( )
* *
1 1 1
msk bk mac s p
k
s p
msk
p i
w w K
t
w
t
c
=

Micropore (Particle)
Fluid Film Model:
( ) ( )
*
1
k msk mic
k
s p
c c K
t
w
=

[accumulation] = [rate of mass transfer from macropore]
Solid Film Model:
( ) ( ) ( )
k sk mic s p
k
s p
w w K
t
w
=
*
1 1
[accumulation] = [rate of mass transfer from macropore]
Specifying Particle Resistance Coefficients
If you choose Micro & Macro Pore Effects, you must specify the values of the
macropore and micropore resistances:
mac
K and
mic
K . The following options
are available in the Form of Mass Transfer Coefficient field.
Constant
This option forces the particle resistance coefficients to be constant
throughout the bed. Set the coefficients in the variable arrays Kmac and
Kmic.
The macropore constant
mac
K is given by:
2
0 . 15
P
efP
mac
r
D
K =
Where:
efP
D = Component diffusivities in macropores
p
r = Particle radius
The micropore constant
mic
K is given by:
2
0 . 15
c
efc
mic
r
D
K =
Where:
efc
D = Component diffusivities in micropores
c
r = Microparticle radius
Estimated
This option uses a submodel in which Aspen Adsim automatically estimates
the coefficients.
User Procedure
If you choose this option, the bed model is written so that the component
rates of mass transfer are related to local conditions in the bed through the
procedure type pUser_g_Kinetic.
) , , , , , (
g i s i g
i
v w T c P T f
t
w
=

Note: Langmuir adsorption kinetics is quite a popular option, and
can be applied with such a procedure.
User Submodel
The name of the submodel is gUserKinetic.
Kinetic Model Assumption (gas): Particle MB
This option determines the loading and gas phase concentration profiles inside
an adsorbent particle, by rigorously solving the particle material balance for
both phases. For this to work, the following conditions must be met:
Adsorbent has a uniform pore structure.
Effective gas phase diffusion coefficient is calculated from the molecular
and the Knudsen diffusion coefficients.
Effective diffusivities for the gas and adsorbed phase are independent of
the location inside the particle.
The Particle Material Balance option considers two mass transfer resistances:
The intraparticle mass transfer resistance, which is the diffusional
resistance inside the particle pore structure, caused by both gas and
adsorbed phase diffusion.
The interparticle mass transfer resistance, which is the resistance to mass
transfer posed by the boundary layer between particle surface and bulk
gas.
The following figure illustrates these resistances:

r
r
p
Bulk
Gas
Boundary
Layer
Adsorbent
Particle (Uniform
Pore Structure)
c
i
c
i
*
w
i
*
w
i
(r)
0
0
=
= r
i
r
w
J
i
p
r r
i
r
w
=
( ) ( )
*
i i f
r r
i
ei s i
c c k a
r
w
D a J
p
=
=
=
1

The particle material balance is expressed as:
0
2
2
2
=
r
w
r
w
r
D
t
w
k k
ek
k

Where:
k
w = Loading
ek
D = Effective adsorbed phase diffusion coefficient
r = Radial particle co-ordinate
The effective diffusion coefficient is assumed constant throughout the particle.
It is calculated from the particle location inside the adsorber (axial and radial
column co-ordinate) using the procedure pUser_g_De or submodel
gUserEffDiff.
The boundary conditions for this partial differential equation come from both
the symmetry condition at r=0:
0
0
=
= r
i
r
w

and the material flux through the boundary layer at
p
r r = :
( ) ( )
*
1
k k fk i
r r
k
ek s
c c k a
r
w
D a
p
=
=

Where:
a = Specific particle surface
s
= Bulk density of solid
i
fk
k = Boundary layer mass transfer coefficient
k
c = Gas phase concentration
*
k
c = Interface gas phase concentration
The gas phase composition and the loading are coupled by the condition that
thermodynamic equilibrium has been achieved at the interface between gas
phase and particle:
( )
* *
i eq
r r
i i
c f w w
p
= =
=

Where:
eq
f = Isotherm equation
*
i
w = Loading at
p
r r =
The boundary layer mass transfer coefficient is expressed using the following
Sherwood number correlation:
6 . 0 3 / 1
1 . 1 2 Re Sc Sh
i i
+ =
Where:
mi
p fi
i
D
r k
Sh
2
= = Sherwood number
M D
Sc
g mi
i
u
= = Schmidt number
u
g p g
M r v
Re
2
= = Reynolds number
mi
D = Mean molecular diffusion coefficient
u = Gas phase dynamic viscosity
g
M = Mean molecular weight
g
= Superficial velocity
Kinetic Model Assumption (gas): Particle MB 2
This option determines the loading and gas phase concentration profiles inside
an adsorbent particle, by rigorously solving the particle material balance for
both phases. For this to work:
Adsorbent has a uniform pore structure.
Effective gas phase diffusion coefficient is calculated from the molecular
and the Knudsen diffusion coefficients.
Effective diffusivities for gas and adsorbed phase are independent of the
location inside the particle.
The Particle Material Balance 2 option considers two mass transfer
resistances:
The intraparticle mass transfer resistance, which is the diffusional
resistance inside the particle pore structure, caused by both gas and
adsorbed phase diffusion.
The interparticle mass transfer resistance, which is the resistance to mass
transfer posed by the boundary layer between particle surface and bulk
gas.
The following figure illustrates these resistances:
r
r
p
Bulk
Gas
Boundary
Layer
Adsorbent
Particle (Uniform
Pore Structure)
c
i
c
i
*
w
i
*
w
i
(r)
0
0
=
= r
i
r
w
J
i
p
r r
i
r
w
=
( )
( )
( )
3
0
2
3
0
2
*
,
3
1
3
1
p
r
p
i
p
p
r
i
s i
i i f
r r
p
i
i p
r r
i
ei
s
r
dr r
t
c
r
dr r
t
w
J
c c k
r
c
D
r
w
D
p p
p p

=
=
= =

p
r r
p
i
r
c
=
0 =
=
p
r r
p
i
r
c
(r) c
p
i

The particle material balance is given by:
0
2
1
2
1
2
2
2
2
=
r
w
r
w
r
D
r
c
r
c
r
D
t
w
t
c
k k s
ek
p
k
p
k
pk
k s
p
k
p

Where:
p
= Intraparticle voidage
s
= Bulk density
k
w = Loading
p
k
c = Gas phase concentration
ek
pk
D = Effective pore gas phase diffusion coefficient
r = Radial particle co-ordinate
The effective adsorbed phase diffusion coefficient is assumed constant
through the particle. You calculate it from the particle location inside the
adsorber (given by the axial and radial column co-ordinate), using the
procedure pUser_g_De or the submodel gUserEffDiff.
The effective pore gas diffusion coefficient is calculated from the molecular
diffusion coefficient and the Knudsen diffusion coefficient:
|
|
.
|
\
|
+ =
mi Ki p pi
D D
Tort
D
1 1 1

and
5 . 0
97
|
|
.
|
\
|
=
i
Pore Ki
M
T
r D
Where:
Tort = Tortuosity of adsorbent
pi
D = Effective pore gas diffusion coefficient
Ki
D = Knudsen diffusion coefficient
mi
D = Molecular diffusion coefficient of component i in the mixture
Pore
r = Pore radius in adsorbent
T = Adsorbent temperature
i
M = Molecular weight of component i
The boundary conditions for this partial differential equation come from both
the symmetry condition at r=0:
0
0
=
= r
i
r
w

and
0
0
=
= r
p
i
r
c

and the material flux through the boundary layer at
p
r r = :
( )
( )
( )
3
0
2
3
0
2
*
,
3
1
3
1
p
r
p
i
p
p
r
i
s i
i i fi
r r
p
i
i p
r r
i
ei
s
r
dr r
t
c
r
dr r
t
w
J
c c k
r
c
D
r
w
D
p p
p p

=
=
= =

Where:
s
= Bulk density of solid
p
fi
k = Boundary layer mass transfer coefficient
i
c = Bulk gas phase concentration
*
i
c = Interface gas phase concentration
p
i
c = Pore gas phase concentration
i
w = Loading
i
J = Material flux
p
r = particle radius
pi
D = Effective gas phase pore diffusion coefficient
ei
The gas phase concentration and the loading are coupled by the condition
that thermodynamic equilibrium has been at each radial location inside
particle, so:
( )
p
i eq i
c f w =
Where:
eq
f = Isotherm equation
p
i
c = Pore gas phase concentration
i
w = Loading
These calculations give the isotherm correlation at each radial node, which
increases the computational effort.
The boundary layer mass transfer coefficient is given by the following
Sherwood number correlation:
6 . 0 3 / 1
1 . 1 2 Re Sc Sh
i i
+ =
Where:
mi
p fi
i
D
r k
Sh
2
= = Sherwood number
M D
Sc
g mi
i
u
= = Schmidt number
u
g p g
M r v
Re
2
= = Reynolds number
mi
D = Mean molecular diffusion coefficient
u = Gas phase dynamic viscosity
g
M = Mean molecular weight
g
= Superficial velocity
Kinetic Model Assumption (gas): User Procedure
With this option, the bed model relates component rates of mass transfer to
local conditions in the bed through the procedure pUser_g_Kinetic.
) , , , , , (
g i s i g
i
v w T c P T f
t
w
=

Kinetic Model Assumption (gas): User Submodel
With this option, the bed model relates component rates of mass transfer to
local conditions in the bed through the submodel gUserKineticModel.
) , , , , , (
g i s i g
i
v w T c P T f
t
w
=

Kinetic Model Tab (gas): Form of
Lumped Resistance Model
Use the Lumped Resistance option to select the overall form of the mass
transfer rate model. This option determines how the model relates the mass
transfer rate due to adsorption (
i ads
J
,
), to the local gas and solid states. The
mass transfer rate is related to the adsorbent uptake, as follows:
i ads
i
s
J
t
w
,
=

If you chose Lumped Resistance as the kinetic model assumption, in the Form
of the Lumped Resistance Model box, you need to choose between the
following driving force expressions:
Linear
Quadratic
Form of Lumped Resistance Model (gas): Linear
The mass transfer driving force for component i is a linear function of the gas
phase concentration (fluid film) or solid phase loading (solid film).
Fluid:
( )
*
i i gi
i
s
c c MTC
t
w
=

Solid:
( )
i i si
i
w w MTC
t
w
=
*

Form of Lumped Resistance Model (gas): Quadratic
The mass transfer driving force is a quadratic function of the fluid film
concentration or solid film loading.
Fluid:
( ) ( )
i
i i
gi
i
s
c
c c
MTC
t
w
2
2
* 2

Solid:
( ) ( )
i
i i
si
i
w
w w
MTC
t
w
2
2
2
*

Kinetic Model Tab (gas): Molecular
Diffusivities
This option applies if you previously selected one of the following options:
Particle MB as your kinetic model assumption.
Estimated as your form of mass transfer coefficient.
In either case, mean gas phase molecular diffusivities are required for the
calculation of film mass transfer coefficients. These mass transfer coefficients
describe the resistance against mass transfer posed by the boundary layer
surrounding the adsorbent particle.
r
P
2r
c
Interpellet
porosity
Micropore
Bulk Gas Macropore
Solid
Surface
Bulk:
c
bk
,
B
, w
bk
Macropores:
w
msk
, c
msk
Interpellet
Voidage:
i
Pellet
(macroparticle)
Intrapellet
Porosity
P
Solid
Microporous
Particles: w
k
, c
k
c
bk
,
B
, w
bk
c
msk
, (1-
i
)
P
, w
msk
i
c
k
, w
k
* *
* * *
*

Typically, the mass transfer coefficients are evaluated from Sherwood or
Colburn j-factor correlations.
Values and estimation equations for diffusion coefficients for various gases
are given by Bird et al. (1960) and Reid et al. (1977), for example.
Molecular Diffusivities (gas): Fixed
The mean molecular diffusion coefficients are fixed for each component. You
supply a value for each component into the array Dm(*) of the adsorbent
layer model.
Molecular Diffusivities (gas): User Procedure
You supply the mean gas phase diffusion coefficients using a Fortran
subroutine, which Aspen Adsim interfaces through the procedure
pUser_g_Diffusivity.
Kinetic Model Tab (gas): Form of Mass
Transfer Coefficients
If you selected either Lumped Resistance or Micro & Macropore for your
kinetic model assumption then, in the Form of Mass Transfer Coefficients box,
choose from these options:
Arrhenius
Constant
Estimated
Pressure Dependent Arrhenius
User Procedure
User Submodel
Form of Mass Transfer Coefficients (gas): Arrhenius
This option evaluates the mass transfer coefficient as a function of
temperature from an Arrhenius type equation:
|
.
|
\
|
=
RT
E
k MTC
acti
i i
exp
0

To use this option, you must supply the pre-exponential factor
i
k
0
and the
activation energy
acti
E for each component i, as fixed variables in the Specify
table for the adsorbent layer.
Form of Mass Transfer Coefficients (gas): Constant
Here, the mass transfer coefficient for each component is constant throughout
the bed. You must supply a constant value of mass transfer coefficient for
each component in the Specify table for the adsorbent layer.
Form of Mass Transfer Coefficients (gas): Estimated
If you have selected Lumped Resistance as your kinetic model assumption,
and Estimated in the Form of Mass Transfer Coefficients box, choose the
Estimated Mass Transfer Coefficient Assumption from:
Micro and Macro Pores Considered
Macropore Only
Methods exist in the literature for estimating the mass transfer coefficient as
a function of the supplied isotherm. One such method is based on the Henry's
Coefficient. These methods rarely provide exact values; they are
approximations that serve only as rough guides. They usually need to be fine-
tuned. You can fine-tune the values by adjusting the estimated values until
the timing and shape of the simulated breakthrough curves match the
experimentally measured breakthrough curves.
In general, the adsorption rate model for component i can be expressed as:
( ) ( )
* *
i i Ki i i i i
i
c c K k w w k
t
w
= =

The effective mass transfer coefficient is given as a lumped term comprising
the external film resistance term, the macropore diffusion term, and the
micropore diffusion term:
ci Ki
c
pi p
p
fi
p
i
D K
r
K
r
k
r
k 15 15 3
1
2
2
+ + =

The Henry's coefficient
Ki
K is obtained from the isotherm as:
i
i
i
i
Ki
P
w
RT
c
w
K
=
* *

The dimensionless Henrys coefficient,
Ki
K , is obtained by:
i
s
Ki Ki
K K
=
The film resistance coefficient
fi
k is obtained from the Sherwood number as:
p
mi
i fi
r
D
Sh k
2
=
Where:
i
Sh =
6 . 0 3 / 1
1 . 1 0 . 2 Re Sc
i
+
Re = Reynolds number
i
Sc = Schmidt number = ( )
s mi
D u
The macropore diffusion coefficient
pi
K is obtained from:
|
|
.
|
\
|
+ =
mi Ki pi
D D
Tort
K
1 1 1

The Knudsen diffusion coefficient
Ki
D is:
5 . 0
97
|
|
.
|
\
|
=
i
Pore Ki
M
T
r D
Where:
g
= Gas density
ci
D = Micropore diffusion coefficient
Ki
D = Knudsen diffusion coefficient
mi
D = Multi-component molecular diffusion coefficient
p
e = particle (macro) porosity
i
k = effective mass transfer coefficient
Ki
K = Henry's coefficient
fi
k = Film resistance coefficient
pi
K = Macropore diffusion coefficient
w = Loading
R = Universal Gas Constant
c
r = Radius of crystalline or primary micropore
p
r = Particle radius
Tort = Tortuosity factor
u = Dynamic viscosity
To include the effect of the micropore resistance in the estimated values for
the mass transfer coefficients:
Give values for the micropore diffusion coefficients and the radius of the
primary micropore.
To ignore the micropore effect:
In the Estimated Mass Transfer Coefficient Assumption box, select
Macropore only.
Form of Mass Transfer Coefficients (gas): Pressure Dependent
Arrhenius
This option is based on the Arrhenius model, but also accounts for changes in
total pressure. As such it is especially suitable for PSA systems. The model
was found to represent experimental data well.
|
.
|
\
|
=
RT
E
P
k
MTC
acti Pi
i
exp
0

You have to supply the pre-exponential factor
Pi
k
0
and the activation energy
acti
E for each component i, as fixed variables in the Specify table for the
adsorbent layer.
Form of Mass Transfer Coefficients (gas): User Procedure
Here, the mass transfer coefficients are estimated using a Fortran subroutine,
which Aspen Adsim interfaces through the procedure pUser_g_MTC.
Form of Mass Transfer Coefficients (gas): User Submodel
If you choose this option, the mass transfer coefficients are estimated and
then returned through the submodel gUserMTC.
Kinetic Model Tab (gas): Apply Cyclic
Correction
This option is available only if you selected Lumped Resistance as your kinetic
model assumption, and either Constant or Estimated in the Form Of Mass
Transfer Coefficient box. Furthermore, this option applies only to cyclic
processes and especially PSA systems. The Glueckauf (see Yang, 1987 for
example) approximation of a lumped mass transfer coefficient states:
2
,
P
ei
i s
r
D
MTC
=
with =15. Nakao and Suzuki (1983) showed that the value of 15
underestimates the magnitude of the mass transfer coefficient for short
adsorption times. Assuming that an adsorption column is in adsorbing mode
for about half the total time of the adsorption cycle, the following time
constant can be calculated:
Cycle
P
e
t
r
D
2
5 . 0 =
The parameter is a function of :
162.5 : 001 . 0
5.14
: 1 . 0 001 . 0
15 : 1 . 0
=
= <
=

The above equations are evaluated automatically by Aspen Adsim when you
select this option.

Kinetic Model Tab (gas): Estimated
Mass Transfer Coefficient Assumption
This option is available only if you selected Estimated as your estimated mass
transfer coefficient.
Gas Adsorption Layer (gas): Particle
Material Balance, Number of Nodes
This option is available only if you selected Particle MB or Particle MB 2 as
your kinetic model assumption. It determines how many nodes to use for the
central finite difference discretization of the second order derivative in the
particle material balance:
( )
( )
2
1 1 1 1 2
2
2
2
2 1
r
w w w
r
w w
r r
w
r
r r
k k k k k
k
+ +
+
+
|
.
|
\
|

Kinetic Model Tab (gas): Particle
Material Balance, Effective Diffusivity
This option is available only if you selcted Particle MB or Particle MB 2 as your
Kinetic Model Assumption. With this option, the form of the effective adsorbed
phase diffusion coefficient is determined. Choose one of three options:
Fixed
User Procedure
User Submodel
Particle Material Balance, Effective Diffusivity (gas): Fixed
With this option, the effective diffusion coefficients for each component in the
adsorbed phase are given a constant value, which you supply through the
array De(*) of the adsorbent layer model.
Particle Material Balance, Effective Diffusivity (gas): User
Procedure
You supply the mean adsorbed phase diffusion coefficients using a Fortran
subroutine, which Adsim interfaces through the procedure pUser_g_De.
Particle Material Balance, Effective Diffusivity (gas): User
Submodel
You supply the mean adsorbed phase diffusion coefficients through the user
submodel gUserEffDiff.
Isotherm Tab (gas)
Use the Isotherm tab to define the adsorption isotherms to be used in your
gas adsorption process.
The Aspen Adsim isotherm models are expressed as functions of either partial
pressures or concentrations. When you use Aspen Adsim isotherm models for
pure components or for multi-component mixtures, you must supply isotherm
parameters consistent with the functional form. It is imperative that you
convert isotherm parameters to Aspen Adsim's base units of measurement,
which are listed in the following table:

Variable Unit of measurement
Loading (w) kmol/kg
Gas phase concentration (c) kmol/m
3

Pressure (P) bar
Temperature (T) K
About Adsorption Isotherms for Gas
Adsorption is the tendency of molecules from an ambient fluid phase (gas or
liquid) to stick to the surface of a solid. Most of the important industrial
applications of adsorption depend on differences in the affinity of the solid
surface for different components. Adsorption isotherms describe the tendency
for the components to adsorb onto the solid; they describe the amount of
each component adsorbed onto the solid at thermodynamic equilibrium. The
driving force behind all adsorptive gas separation processes is the departure
from adsorption equilibrium, so adsorption isotherms are crucially important
data in the design of adsorbers.
If you know the adsorption isotherms for the components of the feed, you can
create a bed model to predict the performance of the adsorber bed for the
specified operating conditions.
Aspen Adsim has a comprehensive list of adsorption isotherms. You choose
these isotherms from the Configurure Layer forms for the layers making up
the bed model. This section explains these choices for pure component, multi-
component, and user-supplied isotherms.
For more information, see Chapters 2 through 4 in Ruthven, 1984, Chapters 2
and 3 in Yang, 1987, and Chapter 3 in Kast, 1988 (German language).
Guidelines for Choosing Aspen Adsim
Isotherm Models (gas)
Choose a model that is appropriate to the process you are investigating. The
equilibrium specified by the isotherm model affects the driving force for mass
transfer, so you can get significantly different simulation results when using
different models, even if the model parameters are derived from exactly the
same set of data.
The isotherm model parameters are always set variables. You can estimate
these parameters from experimental data, or use published literature values.
Important: The expressions in this section are equilibrium equations.
Depending on the mass transfer rate model you choose, the expressions
compute either:
w*, the loading which would be at equilibrium with the actual gas phase
composition
- or -
c*, the gas phase composition which would be at equilibrium with the
actual loading.
The choice between w* and c* is automatically handled by Aspen Adsim.
Aspen Adsim names the equilibrium variable arrays (of size n or nm) either
Ws or Cs. In bed models, these variables are distributed axially, or axially and
radially, and have indices to identify their location in the bed.
About Multi-Component Mixture
Isotherms (gas)
In adsorber design, you are usually interested in the adsorption equilibria of
mixtures, rather than those of pure components. This is because adsorbed
gas components interact on the solid surface, so individual gas components
adsorb in a different fashion when mixed with other components. Mixture
adsorption equilibria data are not readily available. Although measurements
can be made, they are tedious and time-consuming to perform, so it is
common practice to predict mixture isotherms from pure component
isotherms.
Several methods for predicting mixture isotherms from pure component data
have been proposed recently, including:
Vacancy Solution
Extended Langmuir Approach
Ideal Adsorbed Solution
Real Adsorbed Solution Theory
Most of the physical adsorption models contain two or three parameters, and
the parameters for mixture isotherms are written as a function of the pure
component parameters and the composition of the adsorbed phase.
Vacancy Solution (gas)
The vacancy solution is the least popular of all the methods, but the approach
has been developed in a limited number of cases for some single and multi-
component systems.
Extended Langmuir Approach (gas)
This is an extension of the Langmuir isotherms for single components.
Langmuir models use a weighting factor to account for the inter-species
interaction in mixtures.
The extended Langmuir approach takes a single component gas isotherm
parameter and, depending on the components of the multi-component gas
mixture, calculates a fitting parameter to account for the presence of other
components. The values of the interaction parameters depend on all the
species present. The value of the weighted inter-species interaction
parameter is obtained from mixture experimental data.
Ideal Adsorbed Solution (gas)
Recently, the Ideal Adsorbed Solution Theory (IAS) has become popular for
multi-component mixtures. The method enables you to predict adsorption
equilibria for components in a gaseous mixture. It requires data only for the
pure-component adsorption equilibria at the same temperature and on the
same adsorbent.
The model treats the mixed adsorbate phase as an ideal solution in
equilibrium with the gas phase. The Gibbs approach is used for vapor-liquid
equilibria, in which the fundamental equations of thermodynamic equilibrium
are developed, and applies this to the gas-adsorbed phase equilibria.
At first sight, ideal behavior in the adsorbed phase seems improbable.
However, many systems have shown strong correlation between experimental
data and predictions by IAS theory, including binary and ternary mixtures on
activated carbons, zeolites, and silica gel.
For a full description of the IAS approach, see Chapter 4 of Ruthven (1984) or
Chapter 3 of Kast (1988) (German language).
IAS is available in Aspen Adsim. To use it, choose the appropriate isotherm on
the Isotherm Tab of the layer configuration form.
The basic requirements for thermodynamic equilibrium between two phases
are that the pressure, temperature and chemical potential of each component
are equal in both phases.
The chemical potential for an adsorbed phase can be written as (Kast, 1988):
( ) ( ) ( ) ( ) ( )
i i i i i i ads
x RT P RT T x T u u ln ln , ,
0 0
,
+ + =
The chemical potential for an ideal gas phase is given by:
( ) ( ) P y RT T
i i i gas
ln
0
,
+ = u u
The equilibrium condition is:
i ads i gas , ,
u u =
Assuming ideal behavior in the adsorbed phase (that is, 1 =
i
), an expression
analogous to Raoults law can be derived:
( )
0
i i i
P x P y =
The pressure
0
i
P is a fictitious pure component gas phase pressure, which
gives the same spread pressure in the adsorbed phase as the gas mixture at
pressure P. The relationship between
0
i
P and the spreading pressure
0
i
is
derived using the Gibbs-Duhem equation for a single adsorbed component:
( ) ( ) u
0 0 0 0 0
ln(
i i i i i
P RTd w d w Ad = =
On integrating and using the pure component isotherm to replace
0
i
w :
( )
dP
P
IP P T f
RT
A
i
P
eq
i
=
0
0
0
, ,

The equation set is completed with the following conditions:
=
=
n
i
i
x
1
1
=
=
n
i
i
y
1
1
...
0 0 0
= = =
k j i

The total loading and component loadings are calculated from:
=
=
n
i tot i
i
w w
x
1
0
1

and
tot i i
w x w =
Real Adsorbed Solution Theory (gas)
The derivation of the Ideal Adsorbed Solution Theory (see earlier) assumed
ideal behavior in the adsorbed phase. This assumption resulted in the activity
coefficient of each component being set to unity ( 1 =
i
).
Non-ideal behavior in the adsorbed phase can be accounted for by evaluating
the activity coefficient using a suitable Gibbs excess enthalpy correlation (for
example, Wilson or UNIQUAC). The binary parameters of the
E
g models have
to be determined from suitable experiments (Costa et al., 1981). Once those
parameters are known, AspenTechs Aspen Properties system is used to
supply the value of
i
so that:
( ) =
0
i i i i
P x P y
can be evaluated.
Isotherm Tab (gas): Isotherm
Assumed for Layer
Aspen Adsim enables you to use a number of pure component isotherms and
multi-component isotherms.
In the Isotherm Assumed for Layer box, select from:
Langmuir Models
Freundlich Models
Langmuir-Freundlich Model
Henry's Models
Toth Model
B.E.T. (Brunauer, Emmett & Teller) Models
B.E.T. Multilayer
Dubinin-Astakov Model
Linear Model
Volmer Model
Myers Model
Extended Langmuir Models
Extended Langmuir- Freundlich Model
Dual-Site Langmuir Model
Single Layer B.E.T
Dual Layer B.E.T
User Procedure
User Submodel
IAS
Isotherm Assumed for Layer (gas): Langmuir Models
Langmuir isotherm models typically apply to the adsorption of a single
molecule layer on completely homogeneous surfaces, with negligible
interaction between adsorbed molecules.
There are three standard sub-options for the pure component Langmuir
isotherms supported in Aspen Adsim:
Langmuir 1. The isotherm is a function of a partial pressure or
concentration:
i
i
i
P IP
P IP
w
2
1
1+
= (partial pressure)
or
i
i
i
c IP
c IP
w
2
1
1+
= (concentration)
Langmuir 2. The isotherm is a function of temperature, and one of partial
pressure or concentration:
i
Ts IP
i
Ts IP
i
P e IP
P e IP
w
/
3
/
1
4
2
1+
or
i
Ts IP
i
Ts IP
i
c e IP
c e IP
w
/
3
/
1
4
2
1+
= (concentration)
Langmuir 3. The isotherm is a function of temperature, and one of partial
pressure or concentration. Unlike Langmuir2, the maximum loading,
expressed by ( )
s
T IP IP
2 1
, is a function of temperature, so reflects more
accurately the physical reality of numerous adsorption processes:
( )
i
T IP
i
T IP
s
i
P e IP
P e IP T IP IP
w
s
s
/
3
/
3 2 1
4
4
1+
or
( )
i
T IP
i
T IP
s
i
c e IP
c e IP T IP IP
w
s
s
/
3
/
3 2 1
4
4
1+
= (concentration)
Isotherm Assumed for Layer (gas): Freundlich Models
Aspen Adsim has two sub-options for the pure component Freundlich
isotherms:
Freundlich 1. The isotherm is a function of partial pressure or concentration:
2
1
IP
i i
P IP w = (partial pressure)
or
2
1
IP
i i
C IP w = (concentration)
Freundlich 2. The isotherm is a function of temperature, and one of partial
2 3
/
1
IP
i
T IP
i
P e IP w
s
or
2 3
/
1
IP
i
T IP
i
c e IP w
s
= (concentration)
Isotherm Assumed for Layer (gas): Langmuir-Freundlich Model
This isotherm is a function of temperature, and one of partial pressure or
concentration:
s
s
T IP IP
i
T IP IP
i
i
e
P
IP
e
P
IP IP
w
/
5
/
2 1
6 3
4 3
1+
or
s
s
T IP IP
i
T IP IP
i
i
e c IP
e c IP IP
w
/
5
/
2 1
6 3
4 3
1+
= (concentration)
Isotherm Assumed for Layer (gas): Henry's Models
Aspen Adsim has two sub-options of the pure component Henry's isotherms:
Henry 1. The isotherm is a function of partial pressure or concentration:
i i
P IP w
1
or
i i
c IP w
1
= (concentration)
Henry 2. The isotherm is a function of temperature, and one of partial
i
T IP
i
P e IP w
s
/
1
2
or
i
T IP
i
c e IP w
s
/
1
2
= (concentration)
Isotherm Assumed for Layer (gas): Toth Model
The isotherm is a function of partial pressure or concentration:
2
1
2
2
) ( 1
) (
3
1
IP
IP
i
IP
i
i
P IP
P IP
w
+
or
2
1
2
2
) ( 1
) (
3
1
IP
IP
i
IP
i
i
c IP
c IP
w
+
= (concentration)
Isotherm Assumed for Layer (gas): B.E.T
Use the B.E.T. (Brunauer, Emmett and Teller) type isotherm (or multilayer
Langmuir relation) for gas-solid systems in which condensation is approached,
and hence the number of adsorbed layers is extremely large.
This isotherm is a function of temperature and one of partial pressure or
concentration:
|
|
.
|
\
|
|
|
.
|
\
|
+
|
|
.
|
\
|
=
s
i
s
i
s
i
i
T
IP
P IP
T
IP
P IP
T
IP
P IP
w
6
5
4
3
2
1
exp 1 exp 1
exp
(partial pressure)
or
|
|
.
|
\
|
|
|
.
|
\
|
+
|
|
.
|
\
|
=
s
i
s
i
s
i
i
T
IP
c IP
T
IP
c IP
T
IP
c IP
w
6
5
4
3
2
1
exp 1 exp 1
exp
(concentration)
Isotherm Assumed for Layer (gas): BET Multilayer
The BET Multilayer isotherm is similar to the BET isotherm, but has an
additional parameter,
4
IP , stating the number of layers adsorbed. Physically,
it fills the gap between the Langmuir isotherm (single layer BET) and the BET
isotherm with an infinite number of layers. Use it only for systems where the
operating temperature is below the critical temperature of the adsorbate.
The isotherm is always evaluated as a function of the relative pressure:
sat
i
i
P
P
=
If you selected concentration dependency, the following equation is used to
calculate the partial pressure:
g i i
RT c P =
The saturation pressure
sat
P is calculated according to a base 10 Antoine
equation, using degrees Celsius or Kelvin as temperature units of
measurement. The parameter
8
IP is then a conversion factor for calculating
sat
P in bar.
s
T IP
IP
IP
sat
IP P
+
=
7
6
5
10
8

The kinetic factor b is:
|
|
.
|
\
|
=
s
T
IP
IP b
3
2
exp
The isotherm is:
( )
( )
|
|
.
|
\
|
+
+ +
|
|
.
|
\
|
=
+1
4 4 1
4
4 4
1 1
1 1
1
IP
IP IP
i
b b
IP IP b IP
w

Isotherm Assumed for Layer (gas): Dubinin-Astakov Model
concentration:
| | | |
2
4 3
2
2 1
) / ( exp ) / ( exp IP AA IP IP AA IP w
i
+ =
Where:
|
|
.
|
\
|
=
sat
i
s
P
P
RT AA ln (partial pressure)
or
|
|
.
|
\
|
=
sat
s i
s
P
RT c
RT AA ln (concentration)
and
|
|
.
|
\
|
=
7
6
5
10
8
IP T
IP
IP
sat
s
IP P
IP8 is a conversion factor to convert the resulting partial pressure predicted
by the Log10 base Antoine Equation, into bar (Aspen Adsim's base unit of
measurement for pressure).
Isotherm Assumed for Layer (gas): Linear Model
This isotherm is a function of partial pressure or concentration:
2 1
IP P IP w
i i
+ = (partial pressure)
or
2 1
IP c IP w
i i
+ = (concentration)
Isotherm Assumed for Layer (gas): Volmer Model
The Volmer isotherm expresses concentration as a function of loading:
|
|
.
|
\
|

=
i
i
i
i
i
w IP IP
w IP
w IP IP
w IP
c
1 2
1
1 2
1
exp
Isotherm Assumed for Layer (gas): Myers Model
TheMyers isotherm expresses concentration as a function of loading:
|
|
.
|
\
|
=
1
2 1
exp
IP
w
IP IP c
i
i

Isotherm Assumed for Layer (gas): Extended Langmuir Models
There are three standard sub-options of the extended Langmuir isotherms
supported in Aspen Adsim:
Extended Langmuir 1. This isotherm is a function of partial pressure or
concentration:
( )
+
=
k
k k
i i
i
P IP
P IP
w
2
1
1
(partial pressure)
or
( )
+
=
k
k k
i i
i
c IP
c IP
w
2
1
1
(concentration)
Extended Langmuir 2. This isotherm is a function of temperature, and one
of partial pressure or concentration:
( )
+
=
k
k
T IP
k
i
T IP
i
i
P e IP
P e IP
w
s k
s i
/
3
/
1
4
2
1
(partial pressure)
or
( )
+
=
k
k
T IP
k
i
T IP
i
i
c e IP
c e IP
w
s k
s i
/
3
/
1
4
2
1
(concentration)
Extended Langmuir 3. This isotherm is a function of temperature, and one
of partial pressure or concentration:
( )
=
k
k
T IP
k
i
T IP
i s i i
i
P e IP
P e IP T IP IP
w
s k
s i
/
3
/
3 2 1
4
4
1
) (
(partial pressure)
or
( )
=
k
k
T IP
k
i
T IP
i s i i
i
c e IP
c e IP T IP IP
w
s k
s i
/
3
/
3 2 1
4
4
1
) (
(concentration)
Isotherm Assumed for Layer (gas): Extended Langmuir-
Freundlich Model
concentration:
( )
+
=
k
T IP IP
k k
T IP IP
i i i
i
s k k
s i i
e P IP
e P IP IP
w
/
5
/
2 1
4 3
4 3
1
(partial pressure)
or
( )
+
=
k
T IP IP
k k
T IP IP
i i i
i
s k k
s i i
e c IP
e c IP IP
w
/
5
/
2 1
4 3
4 3
1
(concentration)
Isotherm Assumed for Layer (gas): Dual-Site Langmuir Model
concentration:

+
+
+
=
k
k
T IP
k
i
T IP
i
k
k
T IP
k
i
T IP
i
i
P e IP
P e IP
P e IP
P e IP
W
s k
s i
s k
s i
) ( 1 ) ( 1
/
7
/

5
/
3
/
1
8
6
4
2
(partial pressure)
or

+
+
+
=
k
k
T IP
k
i
T IP
i
k
k
T IP
k
i
T IP
i
i
c e IP
c e IP
c e IP
c e IP
W
k k
s i
s k
s i
) ( 1 ) ( 1
/
7
/

5
/
3
/
1
8
6
4
2
(concentration)
Isotherm Assumed for Layer (gas): Single Layer B.E.T.
This isotherm is an extended B.E.T isotherm with a monolayer. It is
equivalent to the extended Langmuir isotherm. The isotherm is a function of
temperature, and one of partial pressure or concentration:
( )
+
=
k
T IP
k k
T IP
i i i
i
s k
s i
e P IP
e P IP IP
w
/
2
/
2 1
3
3
1
(partial pressure)
or
( )
+
=
k
T IP
k k
T IP
i i i
i
s k
s i
e c IP
e c IP IP
w
/
2
/
2 1
3
3
1
(concentration)
Isotherm Assumed for Layer (gas): Dual Layer B.E.T.
concentration:
( )
( )
( ) ( )
+
+
+
=

k
T IP
k k k
k
T IP
k k
k
T IP
k k i
T IP
i
k
T IP
k k
T IP
i i i
i
s k s k
s k s i
s k
s i
e P IP IP e P IP
e P IP IP e IP
e P IP
e P IP IP
w
/
2 4
/
2
/
2 4
/
2
/
2
/
2 1
3 3
3 3
3
3
1 1
1

(partial pressure)
or
( )
( )
( ) ( )
+
+
+
=

k
T IP
k k k
k
T IP
k k
k
T IP
k k i
T IP
i
k
T k IP
k k
T IP
i i i
i
s k s k
s k s i
s
s i
e c IP IP e c IP
e c IP IP e IP
e c IP
e c IP IP
w
/
2 4
/
2
/
2 4
/
2
/
2
/
2 1
3 3
3 3
3
3
1 1
1

(concentration)
Isotherm Assumed for Layer (gas): User Procedure
You can supply your own proprietary isotherm relationships using a Fortran
subroutine, which Aspen Adsim interfaces through either the procedure
pUser_g_Isotherm_P (partial pressure dependent isotherm) or
pUser_g_Isotherm_C (concentration dependent isotherm).
The functional relationship is:
( ) IP y y P T f w
nc eq i
, ... , ,
1
or
( ) IP c c T f w
nc eq i
, ... ,
1
= (concentration)
You can also supply pure component user-specified isotherms, for use as
multi-component isotherms, using the IAS method. Here, you must supply
two Fortran subroutines:
The first subroutine is interfaced by the procedure pUser_g_Isotherm_Poi.
This procedure relates the fictitious pure component partial pressure
0
i
P
(resulting in the same spread pressure as the mixture at pressure P), to
the loading
0
i
w by means of a pure component isotherm:
( ) IP P T f w
i eq i
, ,
0 0
=
The second subroutine integrates the Gibbs isotherm to give the spread
pressure. It is interfaced by the procedure pUser_g_Gibbs. The
relationship to be evaluated is:
( )
( )
= =
0
0
0
0
, ,
, ,
i
P
eq
i
i
dP
P
IP P T f
g IP P T g
RT
A
with

Isotherm Assumed for Layer (gas): User Submodel
You can supply your own proprietary isotherm relationships using one of
these two submodels:
gUserIsothermPp (partial pressure dependent isotherm)
gUserIsothermC (concentration dependent isotherm)
( ) IP y y P T f w
nc eq i
, ... , ,
1
or
( ) IP c c T f w
nc eq i
, ... ,
1
= (concentration)
Pure component user specified isotherms may be supplied and used as multi-
component isotherms using the IAS method, in which case you must supply
two submodels:
The first submodel is gUserIsothermPoi. This relates the fictious pure
component partial pressure
0
i
P (resulting in the same spread pressure as
the mixture at pressure P), to the loading
0
i
w by means of a pure
component isotherm:
( ) IP P T f w
i eq i
, ,
0 0
=
The second submodel is gUserGibbs. This integrates the Gibbs isotherm to
give the spread pressure. The relationship to be evaluated is:
( )
( )
= =
0
0
0
0
, ,
, ,
i
P
eq
i
i
dP
P
IP P T f
g IP P T g
RT
A
with

Isotherm Assumed for Layer (gas): IAS
The IAS facility in Aspen Adsim lets you calculate competitive,
multicomponent adsorption behavior using pure component isotherms.
Each pure component isotherm has the same expression as its pure
component version. Aspen Adsim's standard pure component isotherms
available with IAS are:
Langmuir models
Freundlich models
Langmuir-Freundlich models
Henry's models
BET multilayer
User-specified isotherms (user procedure or user submodel)
Isotherm Tab (gas): Adsorbed
Solution Theory
If you choose an IAS isotherm, you can then use either the ideal adsorbed
solution theory (IAS) or the real adsorbed solution theory (RAST). The two
options are:
IAS
RAST
With RAST selected and with user procedures supplying the physical
properties, you must write a Fortran procedure to supply the activity
coefficients. The procedure is described by the type pUser_Act_Coeff. The
procedure evaluates
i
as a function of temperature, pressure and the
composition of the adsorbed phase:
( )
nc i
x x p T f ,..., , ,
1
=
Isotherm Tab (gas): Isotherm
Dependency
In the isotherm dependency box, choose from:
Concentration The adsorption isotherm model is a function of
concentration.
Partial Pressure The adsorption isotherm model is a function of partial
pressure.
Energy Balance Tab (gas)
Use the Energy Balance tab to specify how the energy balance is incorporated
into the model for your gas adsorption process.
Energy Balance Tab (gas): Energy
Balance Assumption
In the Energy Balance Assumption box, choose your prefered type of energy
balance, from:
Isothermal
Non-Isothermal with No Conduction
Non-Isothermal with Gas Conduction
Non-Isothermal with Solid Conduction
Non-Isothermal with Gas and Solid Conduction
None
For a vertical bed type with 2-D spatial dimension, the conduction options are
not available as conduction is automatically considered for all dimensions.
Energy Balance Assumption (gas): Isothermal
The Isothermal option completely ignores the energy balance. The gas
temperature
g
T and the solid temperature
s
T are held constant and equal.
Energy Balance Assumption (gas): Non-Isothermal with No
Conduction
This option ignores the axial thermal conduction for the gas and solid phases.
Energy Balance Assumption (gas): Non-Isothermal with Gas
Conduction
This option includes the thermal conduction (axial thermal dispersion) term in
the gas energy balance:
2
2
z
T
k
g
gz i

You need to define the form of the gas thermal conductivity.
Energy Balance Assumption (gas): Non-Isothermal with Solid
Conduction
This option includes the thermal conduction term in the solid energy balance:
2
2
z
T
k
s
sz

You must supply a value for
sz
k in the Specify table for the layer.
Energy Balance Assumption (gas): Non-Isothermal with Gas
and Solid Conduction
This option includes the thermal conduction term for both gas and solid
phases. You must define the form of the gas thermal conductivity. See Energy
Balance Tab: Form of Gas Thermal Conductivity, later.
Energy Balance Tab (gas): Consider
Heat of Adsorbed Phase
Aspen Adsim models also let you include the enthalpy content of the adsorbed
phase in the solid-phase energy balance. The Enthalpy of Adsorbed Phase
term is optional.
If the enthalpy content of the adsorbed phase is significant for your process,
choose this option to include it in the solid phase energy balance. The term
for each component is a function of the loading and the temperature in the
solid phase, the adsorbed phase heat capacity, and the solid density:
t
T
w C H
s
i pai s i
=
The total contribution is the sum for all components: ( ) H
i
i

This equation is quite rigorous, despite neglecting some second order terms
such as enthalpy of mixing.
In the Consider Heat of Adsorbed Phase box, choose from:
None
Constant
User Procedure
User Submodel
Consider Heat of Adsorbed Phase(gas): None
If you choose this option, the enthalpy of adsorbed phase term is ignored in
the solid phase energy balance.
Consider Heat of Adsorbed Phase(gas): Constant
Here, the heat capacities of the adsorbed phase components
pai
C are
constant.
Consider Heat of Adsorbed Phase(gas): User Procedure
With this option, the heat capacities of the adsorbed phase components
pai
C
are calculated using a user-defined subroutine, which Aspen Adsim interfaces
through the procedure pUser_g_Cpa.
Consider Heat of Adsorbed Phase(gas): User Submodel
The heat capacities of the adsorbed phase components
pai
C are calculated
through the user-defined submodel gUserCpa.
Energy Balance Tab (gas): Heat of
Adsorption Assumption
You must include the heat of adsorption in the solid-phase energy balance if it
is significant for the process. The rate of heat generation by adsorption of
each component i per unit mass of solid, depends on the local rate of mass
transfer (the change in the amount of material adsorbed):
i
H
t
w
HT
i
i
=
These rates are held in vectors, HT, and summed for all components to obtain
the total rate of heat generation by adsorption per unit volume of solid:
i
i
HT
s
) (
In the Heat of Adsorption Assumption box, choose from:
None
Constant
User Procedure
User Submodel
Heat of Adsorption Assumption (gas): None
The heat generation by adsorption term is omitted from the energy balance.
Heat of Adsorption Assumption (gas): Constant
With this option, the heat of adsorption is constant for each component i.
Choose it to set the heat of adsorption to constant values, which you supply
in the Specify table for the layer for each component.
Heat of Adsorption Assumption (gas): User Procedure
Here, the heat of adsorption is given by the Fortran procedure pUser_g_DH.
You can vary the heat of adsorption and make it a function of, for example,
local loading, temperature, and pressure. In general terms:
) , , (
ij j sj ij
w P T f H =
Where i designates the component and j designates the node.
Heat of Adsorption Assumption (gas): User Submodel
With this option, the heat of adsorption comes from the submodel gUserDH.
You can vary the heat of adsorption and make it a function of, for example,
local loading, temperature, and pressure. In general terms:
) , , (
ij j sj ij
w P T f H =
Where i designates the component and j designates the node.
Energy Balance Tab (gas): Form of
Heat Transfer Coefficient
If you specify a non-isothermal energy balance, Aspen Adsim generates the
solid and gas-phase energy balances with a film resistance to the heat
transfer between the solid and the gas. Heat transfer is assumed to occur
between the two phases according to the film resistance model:
) ( bed of m per ferred heat trans of rate
3
s g
p
T T a HTC =
If there is no such heat transfer resistance, the gas and solid temperatures
are equal (lumped):
sj gj
T T = for all nodes j = 1, m
To get this condition, set the heat transfer coefficient to a large value (such
as 1).
In the Form of Heat Transfer Coefficient box, choose from:
Constant
Estimated
User Procedure
User Submodel
Form of Heat Transfer Coefficient (gas): Constant
Choose this option to make the heat transfer coefficient a constant value,
which you set through the variable HTC in the Specify table for the layer.
Form of Heat Transfer Coefficient (gas): Estimated
The heat transfer coefficient is estimated as follows:
1 Calculate the Reynolds number:
u
g g p
v M r
Re
2
=
If the calculated value falls below 1E-10, it is reset to this value.
2 Calculate the Prandl number:
M k
C
Pr
g
pg
u
=
If the calculated value falls below 1E-10, it is reset to this value.
3 Calculate the j-factor:
If Re < 190 then
51 . 0
66 . 1
= Re j otherwise
41 . 0
983 . 0
= Re j
4 Calculate the heat transfer coefficient:
3
2
Pr
=
g g pg
v C j HTC
If the calculated value falls below 1E-10, it is reset to a value of 1.
Form of Heat Transfer Coefficient (gas): User Procedure
With this option, the user procedure pUser_g_HTC relates the local heat
transfer coefficient to the state of the bed at a particular point in the bed. This
means you can interface your own Fortran code to calculate the coefficients.
Note that the heat transfer coefficient becomes a distributed variable when
you select this option. The values are held in the variables HTC(1),
HTC(2)HTC(n).
In general terms:
) , , , (
gj j j gj j
v c P T f HTC =
Form of Heat Transfer Coefficient (gas): User Submodel
Here, the local heat transfer coefficient is defined through the user submodel
gUserHTC, using the same dependencies as in the User Procedure option.

Energy Balance Tab (gas): Form of Gas
Thermal Conductivity
If you selected non-isothermal with gas and/or solid conduction, you need to
choose the form of gas thermal conductivity.
In the Form of Gas Thermal Conductivity box, choose from:
Constant
Based on Axial Dispersion
User Procedure
User Submodel
Form of Gas Thermal Conductivity (gas): Constant
The thermal conductivity
g
k has a constant value, which you set in the layer
Specify form.
Form of Gas Thermal Conductivity (gas): Based on Axial
Dispersion
This option assumes that the analogy between heat transfer and mass
transfer is valid. The effective thermal conductivity coefficient is calculated as
the product of the heat capacity of the gas, the axial dispersion coefficient,
and the density of the gas:
gz
k = (Heat capacity) x (Averaged Axial dispersion coefficient) x
(Molar density)
( )
g
k
k zk pg gz
y E C k
=
Form of Gas Thermal Conductivity (gas): User Procedure
The thermal conductivity varies axially along the bed. If you supply the
necessary physical properties directly, Aspen Adsim interfaces a Fortran
subroutine through the procedure pUser_g_Kg. If the physical properties
come from a package such as PROPERTIES PLUS, Aspen Adsim handles the
required calls automatically.
Form of Gas Thermal Conductivity (gas): User Submodel
The thermal conductivity varies axially along the bed and is defined in the
user submodel gUserKg.

Energy Balance Tab (gas): Heat
Transfer to Environment
In the Heat Transfer to Environment box, choose from:
Adiabatic
Thin Wall
Rigorous Model
Heat Transfer to Environment (gas): Adiabatic
No heat transfer occurs between the bed and the wall.
Heat Transfer to Environment (gas): Thin Wall
With this option, the heat exchange between the gas in the bed and the
environment is included in the gas phase energy balance as:
) (
4
amb g
B
w
T T
D
H

The conductivity along the wall and the heat accumulation in the wall are
neglected.
w
H combines the heat transfer resistances of:
Boundary layer between gas and wall, on the inside of the column.
Material of the column wall, including insulation material.
Boundary layer between the outer column wall and the surroundings.
The following equation (Bird et al., 1960) calculates
w
H for the column cross
section shown in the Heat Transfer to Environment figure (on the next page).
1
2
1
1
1
1
2
1
ln ln
2
1
2
+
|
.
|
\
|
+
|
.
|
\
|
+ |
.
|
\
|
=
wo
o
o
i
wi
i
i
w
H
D
k
D
D
k
D
D
H
D
D
H
T
g
T
amb
H
wi
H
wo
k
1
k
2
D
i
D
1
D
o

Heat Transfer to Environment (gas): Rigorous Model
This option includes a wall energy balance equation that contains the
following terms:
Heat transfer from the gas in the bed to the inner wall.
Heat transfer from the outer wall to the environment (including the
influence of any insulating material).
Axial thermal conduction along the wall.
Heat accumulation within the wall material.
The wall is assumed to be thin and conductive enough for the inner and outer
wall temperatures to be equal. The adiabatic option, that is, ignoring the wall
energy balance, is valid only when the wall is extremely thin and non-
conductive.
Energy Balance Tab (gas): Form of
Gas-Wall Heat Transfer Coefficient
There are two options available for the definition of the gas-wall heat transfer
coefficient
w
H :
Constant
Estimated
Form of Gas-Wall Heat Transfer Coefficient (gas): Constant
In the Specify table for the layer, set the heat transfer coefficient
w
H to be a
fixed variable.
Form of Gas-Wall Heat Transfer Coefficient (gas): Estimated
With this option, the gas-wall heat transfer coefficient is calculated from the
local conditions inside the adsorbent layer. The correlation uses results from a
graphical representation given by Kast, 1988:
( ) 11 . 22 0477 . 0 10 2 1
2 6
+ + =
|
|
.
|
\
|
+
H H
H B
B sphere
w
Pe Pe
Pe D
H C
Nu
where:
sphere
C = 12 for a packed bed of spheres
g
char w
w
k
x H
Nu = = Nusselt number for gas-wall heat transfer
g
pg g g char
H
k
MC v x
Pe
= = Gas wall heat transfer Peclet number

char
x = 1.15(2
p
r ) = Characteristic length for a sphere
Reaction Tab (gas)
Use the Reaction tab to generate a layer model that combines adsorption with
reaction (heterogeneous and/or homogeneous).
The mass and energy balances must include the reaction terms as well as the
mass and heat transfer rates caused by adsorption. Furthermore, the
formation of additional solid phases, such as coke, must be accounted for.
About Gas Adsorption with Reaction
Processes
Adsorptive reactors combine, into a single process unit, the unit operations of
heterogeneous and/or homogeneous chemical reaction and adsorption. Such
a hybrid process gives benefits over conventional catalytic reactors:
Higher conversions, for example, when the product in an equilibrium
reaction is removed by adsorption from the gas phase. An example of
higher conversion is the catalytic dehydrogenation of methyl-cyclohexane
to produce toluene. Adsorption of toluene greatly enhances the
conversion.
Higher selectivity, when the desired product of an equilibrium reaction
scheme is adsorbed.
Adsorptive reactors are also used in a number of gas purification processes:
Removing sulfur compounds from gases by first contacting them with or
-ferric oxide monohydrates (Iron Sponge) to adsorb sulfur in the form of
ferric sulfide, then periodically reoxidizing the surface to form elemental
sulfur and to refresh the ferric oxides.
Removing mercury from natural gas streams by treatment in an ex-situ
TSA regenerative process. The process uses an activated carbon
adsorbent that contains sulfur, and which allows the formation of mercuric
sulfide.
Adsorptive reactors are also useful in air purification processes. Careful
selection of the adsorbent may allow one impurity to be adsorbed onto the
adsorbent surface, while another impurity reacts on it. For example, modified
activated carbon is used as an adsorbent for sulfur dioxide and a catalyst for
NOx reduction.
An important application of adsorptive reactors is the separation of
radioactive wastes. Such applications usually require extremely high degrees
of purification because of the high toxicity of many radioactive elements.
Nuclear power plants generate radioactive xenon and krypton as products of
the fission reactions, and these can leak out in small quantities into the
coolant, to be released to the atmosphere with other gases. To prevent such
release, off gases are treated in charcoal delay systems, which prevent the
release of xenon and krypton until sufficient time has elapsed for the short-
lived radioactivity to decay. Similarly, radioactive iodine from nuclear fuel
reprocessing may be captured by chemisorption on molecular sieve zeolites
containing silver.
Reaction Tab (gas): Reactions Present
In the Reactions Present box, choose a reaction type from:
None
Homogeneous
Heterogeneous
Homogeneous and Heterogeneous
Reactions Present (gas): None
No reactions are present in the gas or solid phases.
Reactions Present (gas): Homogeneous
Reactions are present in the gas phase only.
Reactions Present (gas): Heterogeneous
Reactions are heterogeneously catalyzed by a solid. The catalyst and
adsorbent are assumed to be different, giving rise to two distinct solid
phases. Solid reaction participants can be considered.
Reactions Present (gas): Homogeneous and Heterogeneous
Reactions are present in both the gas phase and the solid phase.
Reaction Tab (gas): Homogeneous
Rate Dependency
In the Homogeneous Rate Dependency box, select the type of expression for
homogeneous reaction rate. Choose from these options:
Homogenous Rate Dependency: Partial Pressure
Homogenous Rate Dependency: Concentration
Homogeneous Rate Dependency (gas): Partial Pressure
The reaction rate for components in the gas phase is related to the partial
pressure of the component and gas phase temperature through the procedure
pUser_g_Gas_Rx_Rate_Pp, which requires the user to supply the appropriate
Fortran subroutine.
Homogeneous Rate Dependency (gas): Concentration
The reaction rate for components in the gas phase is related to the
concentration of the component and gas phase temperature through the
procedure pUser_g_Gas_Rx_Rate_C, which requires the user to supply the
appropriate Fortran subroutine.
Reaction Tab (gas): Number of
Homogeneous Reactions
In the Number of Homogeneous Reactions box, select the number of
reactions that occur in the gas phase.
Reaction Tab (gas): Heterogeneous
Rate Dependency
In the Heterogeneous Rate Dependency box, select the type of expression for
heterogeneous reaction rate. Choose from:
Partial Pressure
Concentration
Heterogeneous Rate Dependency (gas): Partial Pressure
With this option, the reaction rate for components on the surface of the
catalytic adsorbent is related to the gas phase partial pressure of the
component and gas phase temperature, through one of these procedures:
pUser_g_Cat_Rx_Rate_Pp
pUser_g_Cat_Rx_Rate_Pp_Sol (for when solid reactants are present)
Both procedures require you to supply the appropriate Fortran subroutine.
Heterogeneous Rate Dependency (gas): Concentration
With this option, the reaction rate for components on the surface of the
catalytic adsorbent is related to the concentration of the component and gas
phase temperature through one of these procedures:
pUser_g_Cat_Rx_Rate_C
pUser_g_Cat_Rx_Rate_C_Sol (for when solid reactants are present)
Both procedures require you to supply the appropriate Fortran subroutine.
Reaction Tab (gas): Number of
Heterogeneous Reactions
In the Number of Heterogeneous Reactions box, select the number of
reactions that occur on the surface of the catalytic adsorbent.
Reaction Tab (gas): Are Solid
Reactants Present
This option is active only if heterogeneous reactions are present. Choose
from:
Yes. Here, solid reaction participants are present. The solids are formed
either by the reaction (for example carbon in reaction networks that suffer
from coking), or they represent catalytically active sites being deactivated or
reactivated. You define, through Fortran subroutines, the way solid
components interact with the gas phase. Aspen Adsim interfaces these
subroutines through one of these two procedures:
pUser_g_Cat_Rx_Rate_Pp
- or -
pUser_g_Cat_Rx_Rate_Pp_Sol
No. Here, no solid reactants are present.
Reaction Tab (gas): Solid Reactant List
In the Solid Reactant List box, choose a default list or a user-defined list of
solid reactants.
Procedures Tab (gas)
Use the Procedures tab to view a list of the user procedures in use within the
current adsorption layer model.
Gas Adsorption: Summary of
Mass and Energy Balance
Equations
This section summarizes the equations for mass and energy balances used for
gas adsorption processes in Aspen Adsim.
Gas Adsorption: Mass Balance for Gas
Phase
The overall mass balance for a multi-component gas phase accounts for the
convection of material and mass transfer, from the gas to the solid phase.
Aspen Adsim uses this equation only for constant pressure systems, and it is
suitable only for simulating breakthrough curves at constant pressure and
temperature.
The governing partial differential equation is:
( )
0 = +
t
w
z
v
k
k
s
g g

For an explanation of the symbols used, see Explanation of Equation Symbols,
later.
Each component in the gas phase is governed by a similar equation, with
extra terms for accumulation, and for axial and radial dispersion terms (if
required):
( )
0 +
1
2
2
= + + |
.
|
\
|

k
k
B
k g
k
rk i
k
zk i
J
t
c
z
c v
r
c
r
r r
E
z
c
E

In general, axial and radial dispersion needs to be considered, but the
dispersion coefficient can be difficult to measure. Aspen Adsim sets the
dispersion coefficient either to a constant value, or calculates it as a function
of local conditions (that is, a distributed parameter).
Gas Adsorption: Mass Balance for
Additional Solid Phase
The concentration of each solid component i is calculated from its formation
rate:
0
,
,
=
i sol
i sol
R
t
c

Gas Adsorption: Gas Phase Energy
Balance
The gas phase energy balance includes terms for:
Thermal conduction
Convection of energy, accumulation of heat
Compression
Heat transfer from gas to solid
Heat transfer from gas to the internal wall
Heat of reaction.
( ) ( ) 0
4

+
, ,
2
2
= + + + + +
+ +
Hx Hx
g
cat p cat s r o g
B
w
s g p
g g
g vg B
g
g g vg
g
i ga
Q a
t
T
C H T T
D
H
T T HTCa
z
v
P
t
T
C
z
T
v C
z
T
k

The above equation is in its most complete form, including axial thermal
conduction, heat transfer to the environment, and the effect of heterogeneous
and homogenous chemical reactions. The only term missing is the radial
thermal conduction term, which is included for 2-dimensional, vertical beds.
However, in this geometry, heat transfer to the environment is a boundary
condition so is not part of the energy balance (it is in the 1-dimensional case).
Gas Adsorption: Solid Phase Energy
Balance
The solid phase energy balance includes terms for:
Thermal conduction
Accumulation of heat
Accumulation of enthalpy in the adsorbed phase
Heat of adsorption
Gas-solid heat transfer from gas to solid (expressed in terms of a film
resistance, where the heat transfer area is proportional to the area of the
adsorbent particles)
The solid phase energy balance is:
( )
=
=
=
|
.
|
\
|
+
+ +
|
.
|
\
|

n
i
s g p
i
i s
s
n
i
i pai s
s
ps s
s
sr
s
sa
T T HTCa
t
w
H
t
T
w C
t
T
C
r
T
r r r
k
z
T
k
1
1
2
2
0
) (
1 1

Gas Adsorption: Wall Energy Balance
The wall energy balance includes terms for:
Axial thermal conduction along the wall
Heat accumulation within the wall material
Heat transfer from the bed to the inner wall
Heat transfer from the outer wall to the environment
The governing equation is:
( )
( )
( )
( )
( ) 0
4 4
2 2
2
2 2 2
2
=
+
+
+
+
+
amb w
B T B
T B
amb w g
B T B
B
w
w
pw w
w
w
T T
D W D
W D
H T T
D W D
D
H
t
T
c
z
T
k

For a 2-dimensional bed model, Aspen Adsim replaces the third term with the
sum of the conductive energy fluxes in the radial direction, which come from
the solid phase energy balances. These fluxes are the boundary conditions for
2-dimensional bed models.
Gas Adsorption: Summary of Factors
that affect the Mass Balance Equations
This section lists the factors that affect the mass balance in the solid and gas
phases.
Gas Adsorption: Axial Dispersion Term
The axial dispersion term is:
2
2
z
c
E
k
zk i

Gas Adsorption: Radial Dispersion Term
This term is only active if you chose vertical bed and two-dimensional spatial
discretization:
|
.
|
\
|
r
c
r
r r
E
k
rk i
1

Gas Adsorption: Convection Term
The convection term is:
( )
z
c v
k g

Gas Adsorption: Gas Phase Accumulation Term
The accumulation term is:
t
c
k
B

Gas Adsorption: Rate of Flux to Solid Surface
The rate of flux to the solid surface is given by:
J
w
t
S
=

Gas Adsorption: Rate of Adsorption
The rate of adsorption is represented as an accumulation term in the gas
phase mass balance. The linear driving force solid-film model is:
( )
s
k ads
k k k
k
J
w w MTCs
t
w

, *
= =
There are analogous expressions for gas films and quadratic driving forces. If
a particle material balance was considered,
t
w
k
is taken to be the integral

uptake of the particle as determined by the flux through the boundary layer.
(See Also Particle MB.)

Note: Procedure-defined expressions need adjusting accordingly.
Gas Adsorption: Reaction Term
The reaction term accounts for the removal or formation of components in the
gas phase, due to reaction on the solid catalyst's surface. It is represented
as:
k reac gas i k reac cat
J J
, , , ,
+
Where:
k reac cat
J
, ,
= rate of consumption or production of k by
heterogeneous (catalytic) reactions
k reac gas
J
, ,
= rate of consumption or production of k by homogeneous
(gas phase) reactions.
j gas k j gas
reacgas n
j
k reac gas
R J
, , ,
1
, ,
=
=
j cat k j cat
reaccat n
j
cat s k reac cat
R J
, , ,
1
, , ,

=
=
You must define the rates of reaction in a user procedure, as a function of
temperature, and one of partial pressure or component concentration. The
total rate of flux to the surface per unit volume is then:
k reac gas i k reac cat k ads k
J J J J
, , , , ,
+ + =
k reac gas i k reac cat
k
s k
J J
t
w
J
, , , ,
+ + =
Gas Adsorption: Defining the Mass
Balance for Additional Solid Phases
During the catalytic reaction, solid phases such as coke deposit sometimes
form, or a metal oxide catalyst is oxidized and/or reduced. The concentration
of each solid component i is calculated from its rate of formation:
0
,
,
=
i sol
i sol
R
t
c

You must define the reaction rate of the solid components in a Fortran
subroutine, as a function of temperature, pressure, and solid component
concentrations. Aspen Adsim interfaces this subroutine through the procedure
pUser_g_Cat_RX_Rate_Pp_Sol.
Gas Adsorption: Summary of Factors
that affect the Energy Balance
This section lists the factors that affect the energy balance equations in the:
Gas phase energy balance.
Solid phase energy balance.
Wall energy balance.
Gas Adsorption: Defining the Energy
Balance in the Gas Phase
This section lists the factors that affect the energy balance equations in the
gas phase.
Gas Adsorption: Effect of Compression
The reversible rate of internal energy increase per unit volume by
compression is:
z
v
P
g

Gas Adsorption: Convective Term
The gas convective term is always included in the gas phase energy balance:
z
T
v C
g
g g vg

Gas Adsorption: Accumulation in Gas Phase
The enthalpy accumulation in the gas phase is represented as:
t
T
C
g
g vg i

Gas Adsorption: Axial Thermal Conduction in Gas Phase
The axial gas thermal conduction (axial thermal dispersion) term is given by:
2
2
z
T
k
g
gz i

Where
gz
k is evaluated based on your choices in:
Energy Balance tab for 1-dimesional models.
Material/Momentum Balance tab for two dimensional models.
Gas Adsorption: Radial Thermal Conduction in Gas Phase
The radial gas thermal conduction term (radial thermal dispersion) is
represented as:
|
|
.
|
\
|
r
T
r
r r
k
g
gr i
1

Where
gr
k is evaluated according to the options selected in the material and
momentum balance tab for two-dimensional models.
Gas Adsorption: Gas-Solid Heat Transfer
Aspen Adsim uses a film resistance model to represent heat transfer between
gases and solids:
Rate of heat transferred per unit volume = ) ( s g
p
T T HTCa
with:
( )
p
i p
r
a
3
1 =
This is for adsorption only. You set
p
a for adsorption and reaction.
Gas Adsorption: Heat Exchange between Gas and Internal Wall
For one-dimensional vertical and horizontal bed models:
) ( 4 o g
B
w
T T
D
H

Where:
amb o
T T = for adiabatic/thin walls and
w o
T T = for thick walls
For other geometries, this term is missing because:
Radial bed models are always considered to be adiabatic.
For two dimensional vertical bed models, the heat transfer to the column
wall is one of the thermal boundary conditions for the radial direction.
Gas Adsorption: Rate of Heat Generation by Reaction
The rate of heat generation by reaction is the sum of the contributions from
individual reactions:

= =
+ =
cat nreac
l
l cat l Rcat cat s
gas nreac
k
k gas k Rgas i R
R H R H H
,
1
, , ,
,
1
, ,

Where:
k = index for the set of homogenous reactions
l = index for the set of heterogeneous reactions
l Rcat k Rgas
H H
, ,
, = molar heats of reactions k and l, typically in MJ/kmol
k gas
R
,
= rate of homogenous reaction k, typically in kmol/(m
3
s)
l cat
R
,
= rate of heterogeneous reaction l, typically in kmol/(kg s)
cat s,
= catalyst bulk density
You must define the rates of reaction in a user procedure, as a function of
temperature, and one of partial pressure or concentration. The heat of
reaction must also be defined as a function of temperature and mole fraction.
See the following procedures, described in the Adsim Library Reference guide:
pUser_g_Cat_RX_Rate_Pp_Sol
pUser_g_Cat_RX_Rate_C_Sol
pUser_g_Cat_RX_Rate_Pp
pUser_g_Cat_RX_Rate_C
pUser_g_Gas_RX_Rate_Pp
pUser_g_Gas_RX_Rate_C
pUser_g_Cat_RX_Heat
pUser_g_Gas_RX_Heat
Gas Adsorption: Heat Exchange between Gas and Internal Heat
Exchanger
The heat exchange between the gas phase and a heat exchanger (either as
jacket around the packed bed or via tubes surrounded by adsorbents) is given
by:
Hx Hx
Q a
Where
Hx
a is the specific heat exchange area per unit bed volume and
Hx
Q
the energy flux exchanged, given by:
( )
Hx g Hx Hx
T T U Q =
for single phase exchange media, and
( ) ( )
St g St Hx Cw g Cw Hx Hx
T T U T T U Q + =
, ,

for two phase exchange media.
See also Configure Form (gas) earlier in this chapter.
Gas Adsorption: Defining the Energy
Balance for the Solid Phase
This section lists the factors that affect the energy balance equations in the
solid phase.
Gas Adsorption: Accumulation in Solid Phase
The solid phase enthalpy accumulation is always included in the solid phase
energy balance:
t
T
C
s
ps s

Gas Adsorption: Axial Thermal Conductivity in Solid Phase
The solid thermal conduction term is:
2
2
z
T
k
s
sz

Gas Adsorption: Radial Thermal Conductivity in Solid Phase
This term is active only for vertical beds and two-dimensional spatial
discretization:
|
.
|
\
|
r
T
r
r r
k
s
sr
1

Gas Adsorption: Heat of Adsorption
The rate of heat generation by adsorption of each component i, per unit mass
of solid, is a function of the local rate of mass transfer:
t
w
H HT
i
i i
=
These rates are held in vectors
i
HT and summed for all components to give
the total rate of heat generation by adsorption per unit volume of solid:
( )
i
i s
HT
Gas Adsorption: Heat of Adsorbed Phase
The term for each component is a function of the loading and the temperature
in the solid phase:
t
T
w C H
s
i pai s i
=
The total contribution comes from the sum for all components: ( )
i
i
H
You supply
pai
C (heat capacity of adsorbed component i) as either a fixed
value for each component, or through a user procedure or submodel. Try
these guidelines when deciding what specific heat capacity to use (Tien,
1994):
For
c
T T << use
pai
C for liquid
For T just below
c
T use system knowledge to specify
pai
C
For
c
T T > use
pai
C for compressed gas
Gas Adsorption: Gas-Solid Heat Transfer
The gas-solid heat transfer term is the same as for the gas phase, but with
the sign reversed:
) ( s g
p
T T a HTC
Gas Adsorption: Defining Energy
Balance for the Wall
This is applicable only if you selected a rigorous model for the heat transfer to
the environment.
The following effects are considered:
Heat exchange between gas and wall.
Between wall and environment.
Axial thermal conductivity along wall.
Heat content of wall.
Gas Adsorption: Heat Exchange between Gas and Wall
When the rigorous wall energy balance is selected, Aspen Adsim includes, in
the wall energy balance, the heat exchange between the gas in the bed and
the inner surface of the wall.
The term is represented as:
( )
( )
w g
B T B
B
w
T T
D W D
D
H
+
2 2
4

Where
B
D = Internal diameter of layer
T
W = Width of column wall
The supply of
w
H is defined by the Form of Gas-Wall Heat Transfer
Coefficient option. It is either constant or estimated from a correlation. The
heat exchange between gas and wall is also included in the gas phase energy
balance. Note that the equation has a slightly different form, since the basis
of the equation is per unit volume of gas phase:
( )
w g
B
w
T T
D
H
4
Gas Adsorption: Heat Exchange between Wall and Environment
When you include a rigorous wall energy balance, the corresponding term in
the wall energy balance gives the heat transfer between the outer wall and
the environment:
( )
( )
) (
D
D 4

2 2
B
B
amb w
B T
T
amb
T T
D W
W H
+
+

Gas Adsorption: Axial Thermal Conductivity along Wall
The axial thermal conduction along the wall is always part of the wall energy
balance. The term is represented as:
2
2
z
T
k
w
w

You must specify the value of the wall thermal conductivity
w
k in the Specify
table for the layer.
Gas Adsorption: Heat Content of Wall
The Heat Content of Wall term is always included in the wall energy balance:
t
T
C
w
pw w

You must specify the value of the wall density
w
and the specific heat
capacity of the wall
pw
C in the Specify table for the layer.
Gas Adsorption: Explanation of
Equation Symbols
Symbol Explanation Aspen Adsim base units
a Specific particle surface. m
2
/m
3

Hx
a
Specific heat exchanger surface. m
2
(HX area)/m
3
(Bed)
P
a
Specific particle surface per unit volume
bed.
m
2
(Particle area)/m
3
(Bed)
A Area. m
2

AA Placeholder variable used for Dubinin-
Astakhov isotherm evaluation.

b Kinetic Langmuir factor. 1/bar
bk
c
Bulk gas phase concentration. kmol/m
3

k
c
Molar concentration of component k. kmol/m
3

msk
c
Macropore gas phase concentration. kmol/m
3

sol
c
Concentration of solid phase reactant. kmol/kg
pai
c
Specific heat capacity of adsorbed phase. MJ/kmol/K
cat p
c
,

Specific heat capacity of catalyst. MJ/kg/K
pg
c
Specific gas phase heat capacity at
constant pressure.
MJ/kmol/K
ps
c
Specific heat capacity of adsorbent. MJ/kmol/K
pW
c
Specific heat capacity of column wall. MJ/kg/K
vg
c
Specific gas phase heat capacity at
constant volume.
MJ/kmol/K
B
D
Bed diameter. m
efc
D
Effective micropore diffusion coefficient. m
2
/s
efP
D
Effective macropore diffusion coefficient. m
2
/s
ek
D
Effective adsorbed phase diffusivity of
component k.
m
2
/s
ki
D
Knudsen diffusion coefficient of component
i.
m
2
/s
mk
D
Mean molecular diffusion coefficient of
component k.
m
2
/s
k act
E
,

Activation energy for Arrhenius
relationship.
MJ/kmol
ik
E
Radial dispersion coefficient of component
k.
m
2
/s
zk
E
Axial dispersion coefficient of component k. m
2
/s
f
Function. -
eq
f
Equilibrium (isotherm) relationship. -
amb
H
Wall-ambient heat transfer coefficient. MW/m
2
/K
B
H
Height of adsorbent layer. m
i
H
Rate of change of heat of adsorbed phase. MJ/m
3
/s
R
H
Combined heats of homogenous and
heterogeneous reactions.
MJ/m
3
(Bed)/s
Rcat
H
Heat of catalytic reaction. MJ/kmol
Rgas
H
Gas phase heat of reaction. MJ/kmol
Ti
H
Heat of adsorption contribution to solid
phase energy balance.
MJ/m
3
/s
w
H
Gas-wall heat transfer coefficient. MJ/m
2
/s
i
H
Heat of adsorption of component i. MJ/kmol
HTC Gas-solid heat transfer coefficient. MJ/m
2
/s
IP Isotherm parameter, units depend on
isotherm.

j Colburn j-factor for heat or mass transfer. -
k ads
J
,

Mass transfer rate of component k owing to
adsorption.
kmol/m
3
(Bed)/s
k reac cat
J
, ,

heterogeneous catalytic reactions.
kmol/m
3
(Bed)/s
reac gas
J
,

homogenous, gas phase reactions.
kmol/m
3
(Void)/s
k
J
Mass transfer rate of component k to/from
adsorbent.
kmol/m
3
(Bed)/s
k
k
0

Pre-exponential factor for Arrhenius
relationship.
m/s
Pk
k
0

Pre-exponential factor for pressure
dependent Arrhenius relationship.
m/s
fk
k
Film mass transfer coefficient of component
k.
m/s
g
k
Gas phase thermal conductivity. MW/m/K
gr
k
Effective radial gas phase thermal
conductivity.
MW/m/K
dyn
gr
k

Dynamic contribution to
gr
k .
MW/m/K
stat
gr
k

Static contribution to
sr
k .
MW/m/K
i
k
Effective, lumped mass transfer coefficient
of component i.
1/s
s
k
Solid thermal conductivity. MW/m/K
gz
k
Effective axial gas phase thermal
conductivity.
MW/m/K
sr
k
Effective radial solid phase thermal
conductivity.
MW/m/K
stat
sr
k

Static contribution to
gr
k .
MW/m/K
sz
k
Effective axial solid phase thermal
conductivity.
MW/m/K
W
k
Thermal conductivity of column wall. MW/m/K
Ki
K
Isotherm slope of component i (Henrys
coefficient).
m
3
/kg
Ki
K
Dimensionless isotherm slope of
component i (Henrys coefficient).
-
mac
K
Macropore mass transfer coefficient. 1/s
mic
K
Micropore mass transfer coefficient. 1/s
p
K
Darcys constant. bar s/m
2

Pi
K
Macropore diffusion coefficient. m
2
/s
L Length of horizontal bed. m
M Molecular weight. kg/kmol
g
MTC
Gas film mass transfer coefficient. 1/s
s
MTC
Solid film mass transfer coefficient. 1/s
p Emissivity in calculation of effective
thermal conductivities.

P Pressure. bar
0
i
P
IAS vapor pressure. bar
sat
P
Saturation pressure. bar
Hx
Q
Heat transfer rate to internal heat
exchanger.
MJ/m
2
/s
r Radial co-ordinate (in packed bed or
particle).
m
c
r
Microparticle (crystal) radius. m
p
r
Particle radius. m
R Universal gas constant. bar m
3
/kmol/K
cat
R
Catalytic reaction rate. kmol/kg/s
gas
R
Gas phase reaction rate. kmol/m
3
/s
sol
R
Solid phase reaction rate. kmol/kg/s
t Time. s
cycle
t
Adsorption cycle time. s
T Temperature. K
0
T Equal to
amb
T or
W
T , depending on
context used.
K
amb
T
Ambient temperature. K
c
T
Critical temperature. K
CW
T
Cooling water temperature. K
s
T
Solid phase temperature. K
g
T
Gas phase temperature. K
Hx
T
Heat exchange medium temperature. K
St
T
Steam temperature. K
W
T
Wall temperature. K
Tort Adsorbent tortuosity. -
Hx
U
Overall heat transfer coefficient: gas to
heat exchange medium.
MW/m
2
/K
cw Hx
U
,

cooling water.
MW/m
2
/K
St Hx
U
,

steam.
MW/m
2
/K
g
v
Gas phase superficial velocity. m/s
k
w
Loading. kmol/kg
0
k
w
Pure component loading of component k. kmol/kg
W Width of horizontal bed. m
T
W
Width of column wall. m
char
x
Characteristic length. m
k
x
Mole fraction of component k in the
adsorbed phase.
-
k
y
Mole fraction of component k in the gas
phase.
-
z Axial co-ordinate. m
Z Gas compressibility factor. -

rg

Radiation contribution to
stat
gr
k
.

rs

Radiation contribution to
stat
sr
k
.

Factor used in
stat
gr
k
calculation.

r Radial discretization distance. m
B

Total bed voidage. m
3
(Void+Pore)/m
3
(Bed)
i

Interparticle voidage. m
3
(Void)/m
3
(Bed)
P

Intraparticle voidage. m
3
(Pore)/m
3
(Particle)

Function of packing density, used in
stat
sr
k

calculation.

Relative pressure:
k sat k
P P
,
/ .
-

Factor used in
stat
sr
k
calculation.

i

Activity coefficient of component i. -
u Dynamic viscosity. N s/m
2

i ads,
u
Chemical potential of component i in the
adsorbed phase.
MJ/kmol
i gas,
u
Chemical potential of component i in the
gas phase.
MJ/kmol
jk

Stoichiometric coefficient of component k
in reaction j.
-
0
i

Spreading pressure of component i. bar m
Time constant for adsorption cycle. -
g

Gas phase molar density. kmol/m
3

s

Adsorbent bulk density. kg/m
3

cat s,

Catalyst bulk density. kg/m
3

W

Wall density. kg/m
3

Parameter in Glueckauf expression. -
Particle shape factor. -

Dimensionless number Defining expression Description
W
Nu
g
char w
k
x H

Nusselt number for gas wall heat transfer.
H
Pe
g
pg g g char
k
MC v x

Gas-wall heat transfer Peclet number.
K
Pe
z
b
g
E
H v

Component Peclet number for mass
transfer.
Pr
M k
C
g
pg
u

Prandl number.
k
Sc
M D
g mi
u

Component Schmidt number.
k
Sh
mi
p fi
D
r k 2

Component Sherwood number.
Re
u
g g p
v M r 2

Particle Reynolds number.
2 Gas Cyclic Steady State Modeling 99
2 Gas Cyclic Steady State
Modeling
Introduction
Aspen Adsim 2004.1 presents an innovative new modeling approach to
maximize profitability in the design, simulation, and optimization of periodic
adsorption processes for gas separation, processes, such as Pressure Swing
Adsorption (PSA), Thermal Swing Adsorption (TSA), Vacuum Swing
Adsorption (VSA), etc.
Direct determination of the cyclic steady state, without carrying out a
dynamic simulation over a large number of cycles, is now available using
Aspen Adsim 2004.1.
This powerful tool - Cyclic Steady State (CSS) modeling (the result of
complete discretization of both time and space) presents a periodic adsorption
process as a steady state problem.
The Aspen Adsim 2004.1 CSS models offer an extremely efficient design tool
that can be more readily used as an optimization package to determine
optimal design and operating conditions for an adsorption process.
The following sections outline CSS modeling tasks and include instructions on
using CSS models for your engineering business:
What is CSS Modeling?
Discretization Techniques for Time and Space
Connectivity Between CSS Models
Bed Model Details
Material Balance
Momentum Balance
Kinetic Model
Energy Balance
Adsorption Equilibrium Models
User Guidelines
How to Create a CSS Simulation Flowsheet
How to Create a Dynamic Simulation Flowsheet using CSS Models
How to Convert a CSS Flowsheet to a Dynamic Flowsheet
How to a Convert Dynamic Flowsheet to a CSS Flowsheet
Developers Tips to Get Better Convergence Property in CSS Simulation
What is CSS Modeling?
A periodic adsorption process operates on sequential steps (for example,
continuously repeated steps of Feed, Purge, Pressure equalization, Blow
down, Production, etc.) with multiple adsorbers packed with single or multiple
adsorbent layers. Although the operation of each bed is batchwise, the whole
system is continuous because of the use of multi-beds that are ultimately
operated in a cyclic steady state within a confined cycle time. Cyclic Steady
State (CSS), which is the nature of periodic adsorption processes, implies a
steady state in which the conditions at the end of each cycle are identical to
those at the beginning.
The traditional approach for CSS determination is to carry out a dynamic
simulation of the system, beginning with a specified set of initial condition,
over a large number of cycles until a CSS is eventually confirmed from a
defined criteria, e.g., the cycle initial state at t
0
must be identical to the cycle
end state at t
N
, as illustrated in Figure 1.
Spatial
Domain
Time
Domain
Cycle end state(tN)
S
t
e
p
1
S
t
e
p
2
S
t
e
p
N
t1
t2
tN
tN-1
t0
dynamic simulation
C
y
c
l
e

i
n
i
t
i
a
l

s
t
a
t
e
(
t
0
)

Figure 1 Illustration for traditional dynamic simulation of a periodic
adsorption process
t0 tN
t1
t2
tN-1
Periodic Boundary
State(tN) = State(t0)
i.e. Cyclic Steady State
Time domain (t)
S
p
a
t
i
a
l

d
o
m
a
i
n

(
x
)

Figure 2 Illustration for the concept of CSS modeling system in Aspen
Adsim
From a mathematical point of view, the criterion for CSS is considered a
unique characteristic of a periodic adsorption process, and has brought ideas
to explore a better numerical method toward CSS in terms of cost-effective
process simulation. The existence of periodic time boundary inspires to
replace the initial condition by a periodicity condition requiring that the
system state at the end of each cycle is identical to that at its beginning.
As illustrated in Figure 2, the forced reformulation also constrains the system
within a specified time domain length, from the starting point (t
0
) to the
ending point (t
N
). This suggests a steady state simulation is feasible by
complete discretization of space and time within a confined time length (i.e.,
cycle time).
Based on the above concept, the CSS models in Aspen Adsim 2004.1 have
been developed to determine CSS from purely steady state simulation. Direct
determination of CSS will effectively save the costs for the optimization of
periodic adsorption process since the technique could offer an extremely
efficient design tool that can be more readily used as an optimization package
to determine optimal design and operating conditions.
Further benefits come from the fact that the graphic user interface of the
freshly released CSS models from Aspen Adsim 2004.1 is the same as those
of existing Aspen Adsim dynamic models. Therefore, existing Adsim users
should find it easy to use this new feature.
The high-level functionalities of CSS bed model (gCSS_Adsorber) in Aspen
Adsim 2004.1 are listed in Table 1, compared with the original Aspen Adsim
dynamic bed model (gas_bed).
Table 1. Functional comparison of CSS and dynamic bed models in
Aspen Adsim 2004.1

Discretization Techniques for
Time and Space
Spatial derivatives of CSS bed model (gCSS_Adsorber) are discretized by one
of the following numerical methods:
CFD4 4
th
Order Central Finite Difference, equivalent to CDS2 in gas_bed
OCFE2 2
nd
Order Orthogonal Collocation on Finite Elements
OCFE4 4
th
Order Orthogonal Collocation on Finite Elements
Time derivatives of CSS models are explained using 1
st
Order Backward Finite
Difference approximation:
( )
t
x t u x t u
t
x t u
j n j n j n
) , ( ) , ( ,
1

Connectivity between CSS
Models
CSS models contain at least an input and an output port (gCSS_Port). Each
port has associated variables that correspond to the material connection
stream (gCSS_Material_Connection) that allows reversible flow.
These are the available connections for CSS models:

Bed Model Details
Material Balance
The CSS bed model (gCSS_Adsorber) uses the following material balance for
the bulk gas adsorption:
( )
0
2
2
=
t
Q
t
C
x
C v
x
C
D
i
b
i
t
i g
i
b Li

The physical meanings of each term are:
2
2
x
C
D
i
b Li
Axial dispersion contribution

1

( )
x
C v
i g
Convection
t
C
i
t
Gas phase accumulation

2

t
Q
i
b
Adsorbed phase accumulation

3

The following continuity equation is required to complete the material balance
around the system,:
g
i
i
C =

Notation
i
C Gas phase concentration for component i, kmol/m
3

Li
D Axial dispersion coefficient for component i, m
2
/s
t Time, s
i
Q Amount adsorbed for component i, kmol/kg-adsorbent
g
v Superficial gas velocity, m/s
x Axial distance coordinate, m
b
Bed (interparticle) voidage
p
Intraparticle voidage
t
Total voidage
g
Gas density, kmol/m
3
b
Bed packing density, kg/m
3
p
Particle density (solid density, true density), kg/m
3
References
1 If a concentration gradient exists in a packed bed, a diffusive mass flux
will occur. In addition, eddy (turbulent) diffusion due to the flow also
contributes to the mass flux. The resultant flux is referred to as mass
dispersion, which may be expressed mathematically in terms of Ficks law,
where the proportionality constant is called dispersion coefficient.
Dispersion occurs in both radial and axial directions in the bed. The axial
dispersed mixing often occurs when a fluid flows through a packed bed
and may cause unfavorable separation efficiency as the separation factor
is becoming smaller. In general, flow through a packed bed may be
adequately represented with inclusion of the axial dispersed plug flow
consideration.
2 Here,
t
is the total bed voidage, which is the combined interparticle and
intraparticle voidages calculated from
( )
b p b t
+ = 1 .
3 Here,
b
is the bed (packing) density calculated from ( )
b p b
= 1 .
Momentum Balance
Gas flow through a packed bed can be described by a relevant pressure drop
correlation. Within the CSS adsorber model (gCSS_Adsorber), one of the
following pressure drop correlations may be chosen as the one. Note that
there is no other option to assume an ideal flow regime, such as Constant
Pressure and Velocity and Constant Pressure with Variable Velocity since the
CSS models has been developed fundamentally for cyclic process for gas
separation.
(1) Darcys Law:
g p
v K
x
P
=

(2) Blake-Kozeny:
( )
( )
g
b p
b g
v
r x
P
3 2
2 5
2
1 10 150

u
=

(3) Burke-Plummer:
( )
( )
2
3
5
2
1 10 75 . 1
g
b p
b g w
v
r
M
x
P

=

(4) Ergun Equation:
( )
( )
( )
( )
|
|
.
|
\
|

+

=

2
3
5
3 2
2 5
2
1 10 75 . 1
2
1 10 150
g
b p
b g w
g
b p
b g
v
r
M
v
r x
P

u

Notation
p
K Darcy Coefficient, bar.s/m
2

w
M Molecular weight of gaseous mixture, kg/kmol
P Gas pressure, bar
p
r Particle radius, m
g
b
Bed voidage (void fraction)
g
u Gas mixture viscosity, cP
g
Gas density, kmol/m
3
Particle shape factor
Kinetic Model
Rigorous simulation of an adsorption process requires a reliable
representation of the adsorption kinetics for the adsorbent used. In
adsorption, the mass transfer mechanism consists of four steps:
Fluid film transfer
Pore diffusion
Adhesion on surface
Surface diffusion
Because the surface adhesion rate approximates the order of the collision
frequency of the gas molecule on the solid surface, (which is much greater
than for the transport processes) the equilibrium is assumed instantaneously
at the interfaces.
Adsorptives initially transfer from the bulk gas phase through an external film
to the external surface of the particles. The molecules are diffused into the
pores of the particle, adsorbed on the active sites and then diffused along the
surface. While fluid film transfer and pore diffusion are treated as sequential
steps, pore diffusion and surface diffusion generally occur in parallel. Any
combination of the three steps can constitute the rate-controlling mechanism.
This mechanism definitely depends on the adsorption system and can vary
with the operating conditions of the process. Typically, a film adjacent to the
surface confines the mass transfer rate between solid and fluid phases and
this external film mass transfer resistance may be determined by the
hydrodynamic condition. It is in fact more convenient to depict film transfer
rate in terms of an effective transfer coefficient or a lumped resistance
coefficient rather than to use a diffusion equation to represent adsorption
kinetics in a rigorous manner.
The CSS adsorber model (gCSS_Adsorber) within Aspen Adsim 2004.1 limits
two types of lumped kinetic models for application. They are: Linear Driving
Force Approximation and Quadratic Driving Force Approximation. Both
approximations have a lumped resistance coefficient that may be determined
at either fluid or solid film where the mass transfer occurs:
(1) Linear Driving Force Approximation (LDFA):
( )
*
i i F
i
b
C C k
t
Q
i
=
at fluid film
( )
i i Si
i
Q Q k
t
Q
=
*
at solid film

(2) Quadratic Driving Force Approximation (QDFA):
( ) ( )
i
i i
Fi
i
b
C
C C
k
t
Q
2
2
* 2
at fluid film
( ) ( )
i
i i
Si
i
Q
Q Q
k
t
Q
2
2
2
*
at solid film
The lumped mass transfer coefficient,
Fi
k or
Si
k , can be determined by a
constant or by a certain relationship according to the dynamic conditions of
adsorption system. The CSS adsorber model (gCSS_Adsorber) provides the
following choices in determining the lumped mass transfer coefficient from
the empirical assessment by Aspen Adsim users:
Constant
LDFi i
k k =
Arrhenius
|
|
.
|
\
|
=
s
i
i i
RT
E
k k exp
0

Effective Diffusivity
2
15
p
ei
i
r
D
k = Linear Driving Force Approximation
2
2
p
ei
i
r
D
k
= Quadratic Driving Force Approximation

Pressure Dependent
P
k
k
Pi
i
=
Pressure Dependent Arrhenius
|
|
.
|
\
|
=
s
i Pi
i
RT
E
P
k
k exp
0

Notation
i
C Gas phase concentration for component i, kmol/m
3
*
i
C Equilibrium gas phase concentration for component i, kmol/m
3

ei
D Effective diffusivity for component i, m
2
/s
i
E Activation energy for component i, MJ/kmol
i
k Mass transfer coefficient (fluid or solid) for
component i, 1/s
i
LDF
k Mass transfer coefficient as a constant for
component i, 1/s
Pi
k Pressure dependent mass transfer coefficient
for component i, bar/s
i
k
0
Pre-exponent for component i, 1/s
Pi
k
0
Pre-exponent for component i, bar/s
Fi
k Fluid film mass transfer coefficient for component i, 1/s
Si
k Solid film mass transfer coefficient for component i, 1/s
P Gas pressure, bar
i
*
i
Q Equilibrium amount adsorbed for component i,
kmol/kg-adsorbent
p
r Particle radius, m
t Time, s
s
T Solid temperature, K
R Gas constant (8.31451e-3), MJ/kmol/K
b
3
Energy Balance
The CSS adsorber model (gCSS_Adsorber) uses the following energy balances
to represent the heat transportations of non-isothermal system with
compressible flow:
(1) In Fluid Phase:
( ) ( ) 0
2
2
= + +
w g
Hi
Hi
w s g p s
g
t g Vg
g g
g g Vg
g
b g
T T
V
A
H T T a H
t
T
C
x
v
P
x
T
v C
x
T
k

2
2
x
T
k
g
b g
Axial thermal conduction

x
T
v C
g
g g Vg
Convection
x
v
P
g
P-V work compression

t
T
C
g
t g Vg
Thermal accumulation in gas phase

( )
s g p s
T T a H Heat transfer between gas and solid

(adsorbent particle)
( )
w g
Hi
Hi
w
T T
V
A
H Heat transfer between gas and the
internal wall of adsorber

(2) In Solid Phase:
( ) 0
2
2
= |
.
|
\
|
s g p s
i
i
i p
s
b Ps
s
s
T T a H
t
Q
H
t
T
C
x
T
k
2
2
x
T
k
s
s
Axial thermal conduction

t
T
C
s
b Ps
Thermal accumulation in solid phase
|
.
|
\
|
i
i
i p
t
Q
H Thermal accumulation by the enthalpy of
adsorption
( )
s g p s
T T a H Heat transfer between gas and solid

(3) In Wall phase:
( ) ( ) 0
2
2
= +
amb w
Ho
Ho
amb w g
Ho
Hi
w
w
w Pw
w
w
T T
V
A
H T T
V
A
H
t
T
C
x
T
k
2
2
x
T
k
w
w
Axial thermal conduction along the wall

t
T
C
w
w Pw
Thermal accumulation in the wall

material
( )
w g
Ho
Hi
w
T T
V
A
H Heat transfer between gas and wall
( )
amb w
Ho
Ho
amb
T T
V
A
H Heat transfer between wall and
environment

Notation
p
a Particle external surface area to particle volume ratio (=3/rp), m
Hi
A Internal wall heat transfer area, m
Ho
A External wall heat transfer area, m
Vg
C Gas mixture heat capacity, MJ/kmol/K
Ps
C Solid (=adsorbent particle) heat capacity, MJ/kg/K
Pw
C Adsorber material (e.g., stainless steel) specific heat
capacity, MJ/kg/K
s
H Fluid/solid heat transfer coefficient, MW/m
2
/K
w
H Fluid/wall heat transfer coefficient, MW/m
2
/K
amb
H Wall/environment heat transfer coefficient, MW/m
2
/K
g
k Gas mixture thermal conductivity, MW/m/K
s
k Solid phase thermal conductivity, MW/m/K
w
k Wall phase thermal conductivity, MW/m/K
P Gas pressure, bar
i
t Time, s
g
T Gas temperature, K
s
T Solid temperature, K
w
T Wall temperature, K
g
Hi
V Internal wall element volume for heat transfer, m
2
Ho
V External wall element volume for heat transfer, m
2

i
H Enthalpy of adsorption for component i
(i.e., heat of adsorption), MJ/kmol
b
Bed voidage (void fraction)
t
Total voidage
g
Gas density, kmol/m
3
b
3
w
Wall material density, kg/m
3
Adsorption Equilibrium Models
Introduction
Adsorption equilibrium established after the adsorptive has been in with the
adsorbed surface for a long time, and can be represented in general form:
0 ) , , ( = T Q f
i i
(Eqn 1)
In this equation, Q
i
is the concentration for component i on adsorbed phase,
i.e., amount adsorbed,
is the density for component i in fluid phase, and T

is the temperature. For an isothermal condition, the Eqn1 can be represented
by the adsorption isotherm:
T i i
f Q ) ( = and
T i i
Q f ) ( = (Eqn 2)
Eqn 2, which is commonly referred to as adsorption equilibrium isotherm, is
most frequently used in researches including adsorption process simulation.
For pure component adsorption, an equilibrium relationship could simply be
represented by mathematical equation such as the Langmuir, the Freundlich,
the Sips, the Toth, and so on. Eqn 1 can also take the following form and is
called the adsorption isostere

(see Ref. 1):
i
Q i
T f ) ( = (Eqn 3)
However, the adsorption isostere cannot be measured directly because it is
impractical to hold
i
Q constant.
For multi-component system, the explanation of adsorption equilibrium
relationship often causes considerable attention due to a unique and complex
mixing rule that governing an adsorption system of interest. For many
decades, numerous researchers have considered multi-component adsorption
equilibria from thermodynamic perspective and developed a number of
theories or models based on various assumptions concerning the nature of
adsorbed phase.
The CSS model in Aspen Adsim offers the following types of adsorption
equilibrium models for multi-component system. Please note all equilibrium
models only require pure equilibrium information in order to predict mixture
equilibrium:
References
1 D. M. Young and A. D. Crowell, Physical Adsorption of Gases,
Butterworths, London (1962).
Mathematical Equation Form for
Extended Langmuir 1
{ }
+
=
k
k k
i i i
i
Py IP
Py IP IP
Q
2
2 1
1

(Pressure dependent equilibrium)

{ }
+
=
k
k k
i i i
i
C IP
C IP IP
Q
2
2 1
1

(Concentration dependent equilibrium)

i i
IP IP
2 1
, Isotherm parameters for component i
P Total gas pressure
i
y Gas phase mole fraction for component i
i
C Fluid phase concentration for component i
i
Q Adsorbed phase concentration (i.e., amount
adsorbed) for component I
Extended Langmuir 2
| | ( )
| | ( ) { }
+
=
k
k s k k
i s i i i
i
Py T IP IP
Py T IP IP IP
Q
3 2
3 2 1
exp 1
exp


| | ( )
| | ( ) { }
+
=
k
k s k k
i s i i i
i
C T IP IP
C T IP IP IP
Q
3 2
3 2 1
exp 1
exp

i i i
IP IP IP
3 2 1
, , Isotherm parameters for component i
s
T Adsorbent particle temperature in Kelvin
i
i
i
Extended Langmuir 3
( ) | | ( )
| | ( ) { }
+
+
=
k
k s k k
i s i i s i i
i
Py T IP IP
Py T IP IP T IP IP
Q
4 3
4 3 2 1
exp 1
exp


( ) | | ( )
| | ( ) { }
+
+
=
k
k s k k
i s i i s i i
i
C T IP IP
C T IP IP T IP IP
Q
4 3
4 3 2 1
exp 1
exp


i i i i
IP IP IP IP
4 3 2 1
, , , Isotherm parameters for component i
s
i
i
C Fluid phase concentration for
component i
i
Q Adsorbed phase concentration (i.e.,
amount adsorbed) for component I
Extended Langmuir 4
( ) | | ( )
| | ( ) { }
+
=
k
k s k k
i s i i
IP
s i
i
Py T IP IP
Py T IP IP T IP
Q
i
4 3
4 3 1
exp 1
exp
2


( ) | | ( )
| | ( ) { }
+
=
k
k s k k
i s i i
IP
s i
i
C T IP IP
C T IP IP T IP
Q
i
4 3
4 3 1
exp 1
exp
2


i i i i
IP IP IP IP
4 3 2 1
s
i
i
component i
i
Q Adsorbed phase concentration
(i.e., amount adsorbed) for component I
Extended Langmuir 5
| | ( ) | | ( )
| | ( ) { }
+
=
k
k s k k
i s i i s i i
i
Py T IP IP
Py T IP IP T IP IP
Q
4 3
4 3 2 1
exp 1
exp exp


| | ( ) | | ( )
| | ( ) { }
+
=
k
k s k k
i s i i s i i
i
C T IP IP
C T IP IP T IP IP
Q
4 3
4 3 2 1
exp 1
exp exp


i i i i
IP IP IP IP
4 3 2 1
s
i
i
component i
i
Q Adsorbed phase concentration (i.e.,
amount adsorbed) for component I
Loading Ratio Correlation 1
( )
( ) { }
+
=
k
IP
k k
IP
i i i
i
k
i
Py IP
Py IP IP
Q
3
3
2
2 1
1

{ }
+
=
k
IP
k k
IP
i i i
i
k
i
C IP
C IP IP
Q
3
3
2
2 1
1


i
IP
?
Isotherm parameters for component i
i
i
i
| | ( )( )
| | ( )( ) { }
+
+
+
=
k
T IP IP
k s k k
T IP IP
i s i i i
i
s k k
s i i
Py T IP IP
Py T IP IP IP
Q
5 4
5 4
3 2
3 2 1
exp 1
exp


| | ( )
| | ( ) { }
+
+
+
=
k
T IP IP
k s k k
T IP IP
i s i i i
i
s k k
s i i
C T IP IP
C T IP IP IP
Q
5 4
5 4
3 2
3 2 1
exp 1
exp


i
IP
?
s
i
i
i
( ) | | ( )( )
| | ( )( ) { }
+
+
+
+
=
k
T IP IP
k s k k
T IP IP
i s i i s i i
i
s k k
s i i
Py T IP IP
Py T IP IP T IP IP
Q
6 5
6 5
4 3
4 3 2 1
exp 1
exp


( ) | | ( )
| | ( ) { }
+
+
+
+
=
k
T IP IP
i s k k
T IP IP
i s i i s i i
i
s k k
s i i
C T IP IP
C T IP IP T IP IP
Q
6 5
6 5
4 3
4 3 2 1
exp 1
exp


i
IP
?
s
i
i
i
( ) | | ( )( )
| | ( )( ) { }
+
+
+
=
k
T IP IP
k s k k
T IP IP
i s i i
IP
s i
i
s k k
s i i i
Py T IP IP
Py T IP IP T IP
Q
6 5
6 5 2
4 3
4 3 1
exp 1
exp

( ) | | ( )
| | ( ) { }
+
+
+
=
k
T IP IP
i s k k
T IP IP
i s i i
IP
s i
i
s k k
s i i i
C T IP IP
C T IP IP T IP
Q
6 5
6 5 2
4 3
4 3 1
exp 1
exp


i
IP
?
s
i
i
i
| | ( ) | | ( )( )
| | ( )( ) { }
+
+
+
=
k
T IP IP
k s k k
T IP IP
i s i i s i i
i
s k k
s i i
Py T IP IP
Py T IP IP T IP IP
Q
6 5
6 5
4 3
4 3 2 1
exp 1
exp exp

| | ( ) | | ( )
| | ( ) { }
+
+
+
=
k
T IP IP
i s k k
T IP IP
i s i i s i i
i
s k k
s i i
C T IP IP
C T IP IP T IP IP
Q
6 5
6 5
4 3
4 3 2 1
exp 1
exp exp


i
IP
?
s
i
i
i
Extended Dual-Site Langmuir 1
{ } { }

+
+
+
=
k
k k
i i i
k
k k
i i i
i
Py IP
Py IP IP
Py IP
Py IP IP
Q
4
4 3
2
2 1
1 1


{ } { }

+
+
+
=
k
k k
i i i
k
k k
i i i
i
C IP
C IP IP
C IP
C IP IP
Q
4
4 3
2
2 1
1 1


i
IP
?
i
i
i
Extended Dual-Site Langmuir 2
| | ( )
| | ( ) { }
| | ( )
| | ( ) { }

+
+
+
=
k
k s k k
i s i i i
k
k s k k
i s i i i
i
Py T IP IP
Py T IP IP IP
Py T IP IP
Py T IP IP IP
Q
6 5
6 5 4
3 2
3 2 1
exp 1
exp
exp 1
exp


| | ( )
| | ( ) { }
| | ( )
| | ( ) { }

+
+
+
=
k
k s k k
i s i i i
k
k s k k
i s i i i
i
C T IP IP
C T IP IP IP
C T IP IP
C T IP IP IP
Q
6 5
6 5 4
3 2
3 2 1
exp 1
exp
exp 1
exp


i
IP
?
s
i
i
i
I.A.S.T. (Ideal Adsorbed Solution
Theory)
The IAST
1
is a widely used engineering thermodynamic method, analogues to
Raoults law in vapor-liquid equilibrium. The inputs to the IAST calculation are
the pure-component adsorption isotherms at the temperature of interest, and
the output is a prediction of mixture equilibrium.
It has been known that the deviations from IAST might result from the
chemical dissimilarity of the adsorptive species (as for deviations from
Raoults law in vapor-liquid equilibrium) or from the heterogeneity of the
adsorbent. Adsorbent heterogeneity might be present in one of following
forms
2
: chemical or structural heterogeneity of the adsorbent surface
3
,
variation of pore size and shape (either along the axis of individual pores or
among the pores), or due to connectivity effects
4,5
.

Nonideal adsorption can be accommodated in the general framework of
adsorbed solution theory by real adsorbed solution theory (RAST
1
)

, in which
nonideal interactions between the adsorbates on the adsorbent surface are
accounted for by activity coefficients, and by heterogeneous ideal adsorbed
solution theory (HIAST
6
), in which the energetic heterogeneity of the
adsorbent is taken into account.
Subject to the assumption of an ideal adsorbed phase, equality of chemical
potential in the bulk gas and adsorbed phases implies:
0
i i i
f x f = (Eqn 1)
where
i
f is the fugacity of component i in the bulk gas phase and
i
x is the
mole fraction of component i in the adsorbed phase;
0
i
f is the standard-
state fugacity, that is, the fugacity of pure component i at the mixture
spreading pressure, ,when the adsorbed and bulk gas phases are in
equilibrium. Please note, Eqn 1 describes the ideal adsorbed phase contacting
with real (i.e., nonideal) gas phase, which is accounted by introducing gas
fugacity instead of gas pressure. When an assumption of ideal gas phase is
invoked, then the basic equation of IAST can be written by:
0
i i i
P x P y = (Eqn 1)
where P is total gas pressure,
i
y is the gas mole fraction for component i
and
i
x is the mole fraction of component i in the adsorbed phase;
0
i
P is the
standard-state pressure, that is, the pressure of pure component i at the
mixture spreading pressure, ,when the adsorbed and bulk gas phases are in
equilibrium.
The spreading pressure is obtained from the experimental adsorption
isotherm, i.e., ( )
i i
P Q or ( )
i i
C Q , via the Gibbs adsorption isotherm:
=
0
0
ln
i
f
i i
f d Q
RT
A
(nonideal gas phase assumption) (Eqn 3)
=
0
0
ln
i
P
i i
P d Q
RT
A
(ideal gas phase assumption) (Eqn 4)
where A is the surface area of the adsorbent (which is not required in
practice, as the product A need not be separated in the calculation), R is
the gas constant, T is the temperature,
i
f and
i
P are the fugacity and the
pressure for pure component i .
The complete description of the IAST as a predictive tool for multicomponent
adsorption equilibria requires an expression for total amount adsorbed,
T
Q :
=
i
i
i
T
Q
x
Q
0
1
(Eqn 5)
and the stoichiometric constraint:
1 =
i
i
x (Eqn 6)
In Eqn 5,
0
i
Q is the amount component i adsorbed at the standard-state
pressure.
The CSS model in Aspen Adsim supports a comprehensive tool in applying the
IAST. The main benefits from the IAST application within the CSS model are:
Capability to account gas phase nonideality by considering the gas
fugacity that may be evaluated by either Aspen Properties or User
Procedure.
No restriction for the type of pure component isotherm in the IAST
calculation (namely, isotherm type free IAST). For example, it is now
available to assign the best-fit isotherm equation to each component
(e.g., the Langmuir isotherm for 1
st
component, the Freundlich isotherm
for 2
nd
component, the Sips isotherm for 3
rd
component, so on.), instead
of using a specific type isotherm for all adsorbates. The available pure
isotherm equations for the IAST within CSS model may be found at:
List of Pure Isotherms Available in IAST Calculation of CSS model
References
1 Myers, A. L.; Prausnitz, J. M. AIChE J. 1965, 11, 121.
2 Yun, J.-H.; Dren, T.; Keil, F. J.; Seaton, N. A. Langmuir 2002, 18, in
print.
3 Rudzinski, W.; Everett, D. M. Adsorption of Gases on Heterogeneous
Surfaces; Academic Press: New York, 1992.
4 Lpez-Ramon, M. V.; Jagiello, J.; Bandosz, T. J.; Seaton, N. A. Langmuir
1997, 13, 4435.
5 Davies, G. M.; Seaton, N. A. Langmuir 1999, 15, 6263.
6 Valenzuela, D.; Myers, A. L.; Talu, O.; Zwiebel, I. AIChE J. 1988, 34,
397.
Pure Isotherm List for the IAST
Calculation of CSS
The following are the pure isotherm equations available in the IAST
calculation by CSS bed model (gCSS_Adsorber) from Aspen Adsim 2004.1. In
the application, any combination of the pure isotherm equations will be
acceptable in representing mixture adsorption equilibria by means of IAST, as
predictive equilibrium theory.
Langmuir 1 - 2 parameters / isothermal assumption
Langmuir 2 - 3 parameters / temperature correlation
Dual Site
Langmuir 1 - 4 parameters / isothermal assumption
Dual Site
Sips (Langmuir-Freundlich) 1 - 3 parameters / isothermal assumption
Sips (Langmuir-Freundlich) 2 - 5 parameters / temperature correlation
Henry 1 - 1 parameters / isothermal assumption
Henry 2 - 2 parameters / temperature correlation
Freundlich 1 - 2 parameters / isothermal assumption
Toth 1 - 3 parameters / isothermal assumption
BET 1 - 1 parameters /
Langmuir 1
Pressure dependent
i i
i i i
i
P IP
P IP IP
Q
2
2 1
1+
=
i
IP
1
Isotherm parameter of comp
i
[kmol/kg-adsorbent]
i
IP
2
i
[bar]
i
Q
Equilibrium loading of comp
i
[kmol/kg-adsorbent]
i
P
Equilibrium pressure of comp
i
[bar]

Concentration dependent
i i
i i i
i
C IP
C IP IP
Q
2
2 1
1+
=
i
IP
1
i
[kmol/kg-adsorbent]
i
IP
2
i
[kmol/m3]
i
Q
i
[kmol/kg-adsorbent]
i
C
Equilibrium concentration of comp
i
[kmol/m3]
Langmuir 2
Pressure dependent
| | ( )
| | ( )
i i i
i i i i
i
P T IP IP
P T IP IP IP
Q
3 2
3 2 1
exp 1
exp
+
=
i
IP
1
Isotherm parameter of comp i [kmol/kg-adsorbent]
i
IP
2
Isotherm parameter of comp i [bar]
i
IP
3
Isotherm parameter of comp i [K]
i
Q Equilibrium loading of comp i [kmol/kg-adsorbent]
i
P Equilibrium pressure of comp i [bar]
T Temperature [K]

| | ( )
| | ( )
i i i
i i i i
i
C T IP IP
C T IP IP IP
Q
3 2
3 2 1
exp 1
exp
+
=
i
IP
1
i
IP
2
Isotherm parameter of comp i [kmol/m
3
]
i
IP
3
i
i
C Equilibrium concentration of comp i [kmol/m
3
]
T Temperature [K]
Langmuir 3
Pressure dependent
( ) | | ( )
| | ( )
i i i
i i i i i
i
P T IP IP
P T IP IP T IP IP
Q
4 3
4 3 2 1
exp 1
exp
+
+
=
i
IP
1
i
IP
2
Isotherm parameter of comp i [kmol/kg/ K]
i
IP
3
i
IP
4
i
i
T Temperature [K]

( ) | | ( )
| | ( )
i i i
i i i i i
i
C T IP IP
C T IP IP T IP IP
Q
4 3
4 3 2 1
exp 1
exp
+
+
=
i
IP
1
i
IP
2
Isotherm parameter of comp i [kmol/kg/K]
i
IP
3
3
]
i
IP
4
i
i
3
]
T Temperature [K]
Langmuir 4
Pressure dependent
( ) | | ( )
| | ( )
i i i
i i i
IP
i
i
P T IP IP
P T IP IP T IP
Q
i
4 3
4 3 1
exp 1
exp
2
+
=
i
IP
1
Isotherm parameter of comp i [kmol.K/kg-
adsorbent]
i
IP
2
Isotherm parameter of comp i [-]
i
IP
3
i
IP
4
i
Q Equilibrium loading of comp i [kmol/kg-
adsorbent]
i
T Temperature [K]

( ) | | ( )
| | ( )
i i i
i i i
IP
i
i
C T IP IP
C T IP IP T IP
Q
i
4 3
4 3 1
exp 1
exp
2
+
=
i
IP
1
Isotherm parameter of comp i [kmol.K/kg-adsorbent]
i
IP
2
i
IP
3
3
]
i
IP
4
i
Q Equilibrium loading of comp i [kmol/kg-
adsorbent]
i
3
]
T Temperature [K]
Langmuir 5
Pressure dependent
| | ( ) | | ( )
| | ( )
i i i
i i i i i
i
P T IP IP
P T IP IP T IP IP
Q
4 3
4 3 2 1
exp 1
exp exp
+
=
i
IP
1
i
[kmol/kg-adsorbent]
i
IP
2
i
[K]
i
IP
3
i
[bar]
i
IP
4
i
[K]
i
Q
i
[kmol/kg-adsorbent]
i
P
i
[bar]
T
Temperature [K]

| | ( ) | | ( )
| | ( )
i i i
i i i i i
i
C T IP IP
C T IP IP T IP IP
Q
4 3
4 3 2 1
exp 1
exp exp
+
=
i
IP
1
i
[kmol/kg-adsorbent]
i
IP
2
i
[K]
i
IP
3
i
[kmol/m3]
i
IP
4
i
[K]
i
Q
i
[kmol/kg-adsorbent]
i
C
i
[kmol/m3]
T
Temperature [K]
Dual-Site Langmuir 1
Pressure dependent
i i
i i i
i i
i i i
i
P IP
P IP IP
P IP
P IP IP
Q
4
4 3
2
2 1
1 1 +
+
+
=
i
IP
1
i
[kmol/kg-adsorbent]
i
IP
2
i
[bar]
i
IP
3
i
[kmol/kg-adsorbent]
i
IP
4
i
[bar]
i
Q
i
[kmol/kg-adsorbent]
i
P
i
[bar]

i i
i i i
i i
i i i
i
C IP
C IP IP
C IP
C IP IP
Q
4
4 3
2
2 1
1 1 +
+
+
=
i
IP
1
i
[kmol/kg-adsorbent]
i
IP
2
i
[kmol/m3]
i
IP
3
i
[kmol/kg-adsorbent]
i
IP
4
i
[kmol/m3]
i
Q
i
[kmol/kg-adsorbent]
i
C
i
[kmol/m3]
Pressure dependent
| | ( )
| | ( )
| | ( )
| | ( )
i i i
i i i i
i i i
i i i i
i
P T IP IP
P T IP IP IP
P T IP IP
P T IP IP IP
Q
6 5
6 5 4
3 2
3 2 1
exp 1
exp
exp 1
exp
+
+
+
=
i
IP
1
i
[kmol/kg-adsorbent]
i
IP
2
i
[bar]
i
IP
3
i
[K]
i
IP
4
i
[kmol/kg-adsorbent]
i
IP
5
i
[bar]
i
IP
6
i
[K]
i
Q
i
[kmol/kg-adsorbent]
i
P
i
[bar]
T
Temperature [K]

| | ( )
| | ( )
| | ( )
| | ( )
i i i
i i i i
i i i
i i i i
i
C T IP IP
C T IP IP IP
C T IP IP
C T IP IP IP
Q
6 5
6 5 4
3 2
3 2 1
exp 1
exp
exp 1
exp
+
+
+
=
i
IP
1
i
[kmol/kg-adsorbent]
i
IP
2
i
[kmol/m3]
i
IP
3
i
[K]
i
IP
4
i
[kmol/kg-adsorbent]
i
IP
5
i
[kmol/m3]
i
IP
6
i
[K]
i
Q
i
[kmol/kg-adsorbent]
i
C
i
[kmol/m3]
T
Temperature [K]
Sips (Langmuir-Freundlich) 1
Pressure dependent
i
i
IP
i i
IP
i i i
i
P IP
P IP IP
Q
3
3
2
2 1
1+
=
i
IP
1
i
[kmol/kg-adsorbent]
i
IP
2
i
[bar]
i
IP
3
i
[-]
i
Q
i
[kmol/kg-adsorbent]
i
P
i
[bar]

i
i
IP
i i
IP
i i i
i
C IP
C IP IP
Q
3
3
2
2 1
1+
=
i
IP
1
i
[kmol/kg-adsorbent]
i
IP
2
i
[kmol/m3]
i
IP
3
i
[-]
i
Q
i
[kmol/kg-adsorbent]
i
C
i
[kmol/m3]
Pressure dependent
| | ( )
| | ( )
T IP IP
i i i
T IP IP
i i i i
i
i i
i i
P T IP IP
P T IP IP IP
Q
5 4
5 4
3 2
3 2 1
exp 1
exp
+
+
+
=
i
IP
1
i
[kmol/kg-adsorbent]
i
IP
2
i
[bar]
i
IP
3
i
[K]
i
IP
4
i
[-]
i
IP
5
i
[K]
i
Q
i
[kmol/kg-adsorbent]
i
P
i
[bar]
T
Temperature [K]

| | ( )
| | ( )
T IP IP
i i i
T IP IP
i i i i
i
i i
i i
C T IP IP
C T IP IP IP
Q
5 4
5 4
3 2
3 2 1
exp 1
exp
+
+
+
=
i
IP
1
i
[kmol/kg-adsorbent]
i
IP
2
i
[kmol/m3]
i
IP
3
i
[K]
i
IP
4
i
[-]
i
IP
5
i
[K]
i
Q
i
[kmol/kg-adsorbent]
i
C
i
[kmol/m3]
T
Temperature [K]
Pressure dependent
( ) | | ( )
| | ( )
T IP IP
i i i
T IP IP
i i i i i
i
i i
i i
P T IP IP
P T IP IP T IP IP
Q
6 5
6 5
4 3
4 3 2 1
exp 1
exp
+
+
+
+
=
i
IP
1
i
[kmol/kg-adsorbent]
i
IP
2
i
[kmol/kg/K]
i
IP
3
i
[bar]
i
IP
4
i
[K]
i
IP
5
i
[-]
i
IP
6
i
[K]
i
Q
i
[kmol/kg-adsorbent]
i
P
i
[bar]
T
Temperature [K]

( ) | | ( )
| | ( )
T IP IP
i i i
T IP IP
i i i i i
i
i i
i i
C T IP IP
C T IP IP T IP IP
Q
6 5
6 5
4 3
4 3 2 1
exp 1
exp
+
+
+
+
=
i
IP
1
i
[kmol/kg-adsorbent]
i
IP
2
i
[kmol/kg/K]
i
IP
3
i
[kmol/m3]
i
IP
4
i
[K]
i
IP
5
i
[-]
i
IP
6
i
[K]
i
Q
i
[kmol/kg-adsorbent]
i
C
i
[kmol/m3]
T
Temperature [K]
Pressure dependent
( ) | | ( )
| | ( )
T IP IP
i i i
T IP IP
i i i
IP
i
i
i i
i i i
P T IP IP
P T IP IP T IP
Q
6 5
6 5 2
4 3
4 3 1
exp 1
exp
+
+
+
=
i
IP
1
Isotherm parameter of comp i [kmol.K/kg-adsorbent]
i
IP
2
i
IP
3
i
IP
4
i
IP
5
i
IP
6
i
i
T Temperature [K]

( ) | | ( )
| | ( )
T IP IP
i i i
T IP IP
i i i
IP
i
i
i i
i i i
C T IP IP
C T IP IP T IP
Q
6 5
6 5 2
4 3
4 3 1
exp 1
exp
+
+
+
=
i
IP
1
i
[kmol.K/kg-adsorbent]
i
IP
2
i
[-]
i
IP
3
i
[kmol/m3]
i
IP
4
i
[K]
i
IP
5
i
[-]
i
IP
6
i
[K]
i
Q
i
[kmol/kg-adsorbent]
i
C
i
[kmol/m3]
T Temperature [K]
Pressure dependent
| | ( ) | | ( )
| | ( )
T IP IP
i i i
T IP IP
i i i i i
i
i i
i i
P T IP IP
P T IP IP T IP IP
Q
6 5
6 5
4 3
4 3 2 1
exp 1
exp exp
+
+
+
=
i
IP
1
i
[kmol/kg-adsorbent]
i
IP
2
i
[K]
i
IP
3
i
[bar]
i
IP
4
i
[K]
i
IP
5
i
[-]
i
IP
6
i
[K]
i
Q
i
[kmol/kg-adsorbent]
i
P
i
[bar]
T
Temperature [K]

| | ( ) | | ( )
| | ( )
T IP IP
i i i
T IP IP
i i i i i
i
i i
i i
C T IP IP
C T IP IP T IP IP
Q
6 5
6 5
4 3
4 3 2 1
exp 1
exp exp
+
+
+
=
i
IP
1
i
[kmol/kg-adsorbent]
i
IP
2
i
[K]
i
IP
3
i
[kmol/m3]
i
IP
4
i
[K]
i
IP
5
i
[-]
i
IP
6
i
[K]
i
Q
i
[kmol/kg-adsorbent]
i
C
i
[kmol/m3]
T
Temperature [K]
Henry 1
Pressure dependent
i i i
P IP Q
1
=
i
IP
1
i
[kmol/bar/kg-adsorbent]
i
Q
i
[kmol/kg-adsorbent]
i
P
i
[bar]

i i i
C IP Q
1
=
i
IP
1
i
[m3/kg-adsorbent]
i
Q
i
[kmol/kg-adsorbent]
i
C
i
[kmol/m3]
Henry 2
Pressure dependent
( )
i i i i
P T IP IP Q
2 1
+ =
i
IP
1
i
i
IP
2
i
[kmol/bar/K/kg-adsorbent]
i
Q
i
[kmol/kg-adsorbent]
i
P
i
[bar]
T
Temperature [K]

( )
i i i i
C T IP IP Q
2 1
+ =
i
IP
1
i
[m3/kg-adsorbent]
i
IP
2
i
[m3/K/kg-adsorbent]
i
Q
i
[kmol/kg-adsorbent]
i
C
i
[kmol/m3]
T
Temperature [K]
Henry 3
Pressure dependent
( )
i
IP
i i
P T IP Q
i 2
1
=
i
IP
1
i
[kmol.K/bar/kg-adsorbent]
i
IP
2
i
[-]
i
Q
i
[kmol/kg-adsorbent]
i
P
i
[bar]
T
Temperature [K]

( )
i
IP
i i
C T IP Q
i 2
1
=
i
IP
1
i
[K.m3/kg-adsorbent]
i
IP
2
i
[-]
i
Q
i
[kmol/kg-adsorbent]
i
C
i
[kmol/m3]
T
Temperature [K]
Henry 4
Pressure dependent
| | ( )
i i i i
P T IP IP Q
2 1
exp =
i
IP
1
i
i
IP
2
i
[K]
i
Q
i
[kmol/kg-adsorbent]
i
P
i
[bar]
T
Temperature [K]

| | ( )
i i i i
C T IP IP Q
2 1
exp =
i
IP
1
i
[m3/kg-adsorbent]
i
IP
2
i
[K]
i
Q
i
[kmol/kg-adsorbent]
i
C
i
[kmol/m3]
T
Temperature [K]
Freundlich 1
Pressure dependent
i
IP
i i i
P IP Q
2
1
=
i
IP
1
i
i
IP
2
i
[-]
i
Q
i
[kmol/kg-adsorbent]
i
P
i
[bar]

i
IP
i i i
C IP Q
2
1
=
i
IP
1
i
[m3/kg-adsorbent]
i
IP
2
i
[-]
i
Q
i
[kmol/kg-adsorbent]
i
C
i
[kmol/m3]
Toth 1
Pressure dependent
( ) i
i
IP
IP
i i
i i
i
P IP
P IP
Q
3
3
1
2
1
+
=
i
IP
1
i
[kmol/kg-adsorbent]
i
IP
2
i
[bar]
i
IP
3
i
[-]
i
Q
i
[kmol/kg-adsorbent]
i
P
i
[bar]

( ) i
i
IP
IP
i i
i i
i
C IP
C IP
Q
3
3
1
2
1
+
=
i
IP
1
i
[kmol/kg-adsorbent]
i
IP
2
i
[kmol/m3]
i
IP
3
i
[-]
i
Q
i
[kmol/kg-adsorbent]
i
C
i
[kmol/m3]
BET 1
Pressure dependent
|
|
.
|
\
|
+
|
|
.
|
\
|
=
s
i
i
i
s
i
i
s
i
i
s
i
i
i i
i
P
P
IP
P
P
P
P
P
P
IP IP
Q
2
2 1
1 1

i
IP
1
i
[kmol/kg-adsorbent]
i
IP
2
i
[-]
i
Q
i
[kmol/kg-adsorbent]
i
P
i
[bar]
s
i
P
Saturated vapour pressure of comp
i
[bar]

|
|
.
|
\
|
+
|
|
.
|
\
|
=
RT P
C
IP
RT P
C
RT P
C
RT P
C
IP IP
Q
s
i
i
i
s
i
i
s
i
i
s
i
i
i i
i
2
2 1
1 1

i
IP
1
i
[kmol/kg-adsorbent]
i
IP
2
i
[-]
i
Q
i
[kmol/kg-adsorbent]
i
C
i
[kmol/m3]
s
i
P
Saturated vapour pressure of comp
i
[bar]
R
Gas constant, 8.31433e-2 [bar.m3/kmol/K]
T
Temperature [K]
User Guidelines
How to Create a CSS Simulation
Flowsheet
Preconditions: The user must hold the licenses for Aspen Adsim 2004.1 and
Aspen Properties 2004.1 (or Aspen Plus 2004.1). The property file, named
air.appdf, is used for component properties definition.
1 Start Aspen Adsim 2004.1.
2 Initialize component properties by loading a property definition.


3 Choose target components from the component list.
(Example. A user chooses N2 and O2 as the components for a simulation.)

4 Select CSS_Info from Structure Types folder by either pressing [Ctrl + I]
or clicking the right mouse button and choosing Create Instance.

5 A dialog box is displayed for the name of the structure instance, and user
enters a name.
(Example. Enter CSSInfo as the name of the structure instance.)

6 Aspen Adsim shows the instance in a folder of the same name below
Flowsheet\Structures folder.

7 Select the global non-isothermal/isothermal option by choosing TRUE or
FALSE the logical parameter, NonIsothermal, from the Specify Table of
the instanced structure.
(Example. Switch the global NonIsothermal parameter to TRUE from the
Specify Table of the instance structure CSSInfo.)

8 Construct a simulation flowsheet using models from the CSS folder of
Aspen Adsim Gas Library.
(Example. Re-construct N2PSACSS - supplied as one of Aspen Adsim
2004.1 demonstrations.)

9 The connect models using the stream, gCSS_Material_Connection,
from the Stream Types folder of Aspen Adsim Library and rename each
model, as shown in the picture.

10 Specify models by putting assumptions and parameter values that are
required for process simulation.
The following are typical items for the N2PSACSS example.
i Bed1 (gCSS_Adsorber): Click the right mouse button and select Specify
table from the Forms menu and specify the CSS bed model B1. Leave all
items as default, except the following:
Layer(1).xNodes 10
Layer(1).NonAdiabatic True
Layer(1).RigorousWallBalance True
ii Bed1 (gCSS_Adsorber): Use right mouse button and select Specify_ table
from Forms and specify the CSS bed model B1. Leave all items as default,
except the following:
Layer(1).Hs 1e-007
Layer(1).Ta 298.15
Layer(1).IP("N2",1) 0.00267288
Layer(1).IP("N2",2) 0.136
Layer(1).IP("O2",1) 0.00267287
Layer(1).IP("O2",2) 0.1413
Layer(1).ksLDF("N2") 0.00760501
Layer(1).ksLDF("O2") 0.04476
Table - Specify

Table - Specify_

iii TD1 and TD2 (gCSS_TankVoid): these two tank/void models have the
same specification.
The following items should be changed:
Ta 298.15
NonAdiabaticTankVoid True
Hamb 1.e-005
Hw 6.e-005
TD1

TD2

iv. VP1 (gCSS_Valve): change CheckValve option to True
VP1

11 Select the Cycle Organizer from the Tools menu. Aspen Adsim displays
the icon, Cycle_Organizer, on the simulation flowsheet, with a dialog box
from Cycle Organizer.

12 Cyclic Steady State simulation mode can be chosen by selecting Cycle
Options from the Cycle menu. To define a CSS simulation flowsheet,
check the check box out, Cyclic Steady-State mode.

13 Define process cycle/step information within the Step menu. For this
example, N2PSACSS, we have four process steps, and the interaction and
control details are as follows:

STEP1

STEP2

STEP3

STEP4

14 Define the variable to be manipulated and the values within the Cycle
Organizer.
STEP1

STEP2

STEP3

STEP4

15 Generate a Cycle Task either by executing Generate Task from Cycle
menu or by clicking Generate Cycle from the status bar of Cycle
Organizer. Aspen Adsim displays a green check-shape icon on the status
bar, indicating a Cycle Task has been created correctly.
BEFORE

AFTER

16 Close the Cycle Organizer, then confirm Aspen Adsim shows a green
square on the simulation status bar and that the simulation mode is now
set Steady State. If so, the simulation is ready to be run in CSS mode.

How to Create a Dynamic Simulation
Flowsheet using CSS Models
Preconditions: The user must be a the licensed user of Aspen Adsim 2004.1
and Aspen Properties 2004.1 (or Aspen Plus 2004.1). The property file,
named air.appdf, is used for component properties definition.
1 Start Aspen Adsim 2004.1.
2 Initialize component properties by loading a property definition.

3 Choose target components from the component list.
(Example. Choose N2 and O2 as the components for a simulation.)

4 Select CSS_Info from the Structure Types folder by either pressing [Ctrl
+ I] or clicking right mouse button and choosing Create Instance.

5 A dialog box is displayed to enter the name of the structure instance, and
the user enters a name.
(Example. Enter CSSInfo as the name of the structure instance.)

6 Aspen Adsim displays the instance in a folder of the same name below the
Flowsheet\Structures folder.

7 Select the global non-isothermal/isothermal option by choosing TRUE or
FALSE the logical parameter, NonIsothermal, from the Specify Table of
the instanced structure.
(Example. Switch the global NonIsothermal parameter to TRUE from the
Specify Table of the instance structure CSSInfo.)

8 Construct a simulation flowsheet using models from the CSS folder of
Aspen Adsim Gas Library.

9 Next, connect models using the stream, gCSS_Material_Connection,
from the Stream Types folder of Aspen Adsim Library and rename each
model, as shown in the picture.

10 Specify models by putting assumptions and parameter values required for
the process simulation. the following are typical items for the N2PSACSS
example.
v. Bed1 (gCSS_Adsorber): Click the right mouse button and select Specify
table from Forms menu, then specify the CSS bed model B1. leave all
items as default, except the following:
Layer(1).xNodes 10
Layer(1).NonAdiabatic True
Layer(1).RigorousWallBalance True
vi. Bed1 (gCSS_Adsorber): Click the right mouse button and select Specify_
table from Forms and specify the CSS bed model B1 - leave all items as
default, except the following:
Layer(1).Hs 1e-007
Layer(1).Ta 298.15
Layer(1).IP("N2",1) 0.00267288
Layer(1).IP("N2",2) 0.136
Layer(1).IP("O2",1) . 00267287
Layer(1).IP("O2",2) 0.1413
Layer(1).ksLDF("N2") 0.00760501
Layer(1).ksLDF("O2") 0.04476
Table - Specify

Table - Specify_

vii. TD1 and TD2 (gCSS_TankVoid): these two tank/void models have the
same specification.
The following items should be changed:
Ta 298.15
NonAdiabaticTankVoid True
Hamb 1.e-005
Hw 6.e-005
TD1

TD2

viii. VP1 (gCSS_Valve): change CheckValve option to True.
VP1

11 Select Cycle Organizer from the Tools menu; Aspen Adsim displays the
icon Cycle_Organizer, on the simulation flowsheet and the Cycle Organizer
dialog box.

12 Non Cyclic Steady State simulation mode can be chosen from the Cycle
Options in the Cycle menu. To define a dynamic simulation flowsheet,
uncheck Cyclic Steady-State mode check box and enter the value of
Maximum cycle for dynamic simulation.
13 Define process cycle/step information within the Step menu. For this
example, N2PSACSS, we have four process steps, and the interaction and
control details are as follows:

STEP1

STEP2

STEP3

STEP4

14 Define the variable to be manipulated and the values within Cycle
Organizer.
STEP1

STEP2

STEP3

STEP4

15 Generate a Cycle Task either by executing Generate Task from Cycle
bar, indicating the Cycle Task has been created correctly.
BEFORE

AFTER

16 Close Cycle Organizer and confirm that Aspen Adsim displays a green
square on the simulation status bar and that simulation mode is now set
Dynamic. If so, the simulation is ready to be run in dynamic mode.

How to Convert a CSS Flowsheet to a
Dynamic Flowsheet
Preconditions: There is an existing Aspen Adsim 2004.1 data file defined in
CSS mode to convert the simulation mode from CSS to dynamic. If you are
not sure which Aspen Adsim data file is defined in CSS mode, please refer to
How to Create a CSS Simulation Flowsheet.
1 Open the existing Aspen Adsim flowsheet (defined in CSS simulation
mode).
2 Activate the Cycle Organizer by double-clicking the icon and locate the
Cyclic Steady-State mode check box on the Cyclic Options Tab.

3 Uncheck the check box to convert the flowsheet from CSS to dynamic. The
Cyclic Organizer displays a dialog box to ask the Maximum Variable Steps
option (recommended answer is Yes).

4 Enter the maximum cycles value (e.g., 20) in the Cycle Options Tab and
generate the Cycle Task either by executing Generate Task from Cycle
bar, indicating the Cycle Task has been created correctly.
BEFORE

AFTER

5 Close the Cycle Organizer and then confirm Aspen Adsim displays a green
square on the simulation status bar and if simulation mode is now set
Dynamic. If so, the simulation is ready to be run in dynamic mode.

How to Convert a Dynamic Flowsheet
into a CSS Flowsheet
Preconditions: There is an existing Aspen Adsim 2004.1 dynamic flowsheet
created using CSS models and the user wishes to convert the simulation
mode from dynamic to CSS. If you are not sure which Aspen Adsim data file
is defined in dynamic mode using CSS models, please refer to How to Create
a Dynamic Simulation Flowsheet using CSS Models.
1 Open an existing Aspen Adsim flowsheet (defined in dynamic simulation
mode).
2 Activate the Cycle Organizer by double-clicking the icon and locate the
Cyclic Steady-State mode check box on the Cyclic Options Tab. Check the
check box to re-define the simulation as CSS flowsheet.
BEFORE

AFTER

3 After confirming (from the status bar of Cycle Organizer) the Cycle Task is
active, close the Cycle Organizer. If the Task is not active, generate a
Cycle Task either by executing Generate Task from Cycle menu or by
clicking Generate Cycle from the status bar of Cycle Organizer.
4 Aspen Adsim displays a green square on the simulation status bar and the
simulation mode is now set to Steady State. If so, the simulation is ready
to be run in CSS mode.

Developers Tips to Get Better
Convergence Property in CSS
Simulation
1 Careful consideration in setting Solver Property options is required to
ensure convergence of CSS models. In the Non Linear Solver Tab, we
recommend selecting the Newton Method for CSS simulation whilst the
Fast Newton is normally recommendable in a dynamic simulation.
2 Convergence criterion is recommended to set Residual and Variable.
3 Max. step reductions value should be maximized as 20.
4 Recommended Max. iterations value is 5000.
5 The value of Maximum variable step is highly sensitive for the
convergence property. For CSS simulation, a recommended default value
is 200, and this may be adjusted (normally increase as problem is
complex) but should not exceed 500. Note that the value of the Maximum
variable step must be reduced if the flowsheet follows dynamic
(not exceed 50).
Recommended Non Linear Solver Property

6 A new check box, Use transpose, has been added to the Solver
Properties dialog Linear Solver Tab. The recommended selection for this
option is CSS simulation.

7 The following dialog shows the recommended tolerance table for CSS
simulation.

3 Ion-Exchange Processes 184
3 Ion-Exchange Processes
This chapter contains for information on:
About Ion-Exchange Processes
Bed Model Assumptions for Ion-Exchange Processes
Configure Form for Ion-Exchange Processes
Configure Layer Form for Ion-Exchange Processes
General Tab
About Axial Dispersion in Ion-Exchange Processes
Kinetic Model Tab
Isotherm Tab
Summary of Mass Balance Equations for Ion-Exchange Processes
About Ion-Exchange Processes
In ion-exchange processes, a fluid phase (such as an aqueous solution)
containing cations and anions, is contacted with an ion-exchange resin.
Typically, the ion-exchange resin is inside a packed bed adsorption column.
The resin contains bound groups carrying a positive or negative ionic charge,
which are accompanied by displaceable ions of opposite charge (counterions).
The displaceable ions have the same charge as the ions of interest in the fluid
phase: since the ions in the fluid phase have a greater affinity for the bound
groups than those originally present, the latter are displaced by the former.
Generally, the resin has a fixed total charge capacity, so one ionic solute is
exchanged for another while maintaining charge neutrality.
Ion-exchange processes have become an important separation technique for
aqueous electrolyte solutions and are used in these applications:
Water softening, where monovalent cations replace multivalent cations.
Water purification, where hydrogen or hydroxide ions replace cations
(usually monovalent).
Multi-component separation of ionic mixtures of different type and charge.
Ion-exchange may be written as a reversible reaction involving charge
equivalent quantities. For example, in a water-softening process, the cation-
exchange process is written as:
Ca NaR CaR Na
2+ +
+ + 2 2
2

where R is a stationary, univalent, anionic group in the poly-electrolyte
network of the exchange phase.
Bed Model Assumptions for Ion-
Exchange
The bed model assumptions for ion-exchange are:
Overall and component material balances apply for the liquid phase.
Isothermal conditions apply.
Plug flow or plug flow with axial dispersion applies.
The liquid stream pressure is constant (no frictional pressure drop).
The superficial velocity and thus volumetric flow rate remain constant.
(The ion components are dilute so the effect of adsorption on the overall
mass balance is negligible.)
Ideal mixing occurs in the aqueous phase. Since the ionic components are
very dilute, overall molar volume remains constant.
Changes in molar volume between distinct, sequentially fed fluids are
allowed.
The total exchange capacity of the bed Q is constant.
A lumped mass-transfer rate applies, with a liquid- or solid-film
resistance. This resistance is either linear, quadratic, or user-defined.
The mass-action equilibrium is one alternative model for ion-exchange
behavior. Others include the extended Langmuir and extended Langmuir-
Freundlich models.
Configure Form (ionx)
In the Configure Form of the Ion-exchange process bed model:
Enter the number of layers within the bed (1 or more).
Click in the Description box for each layer and type in a brief name or
description.
Click Configure to open the Configure Layer dialog box.
Click Specify to open the specify form for the layer model.
Configure Layer Form (ionx)
Use the options in the Configure Layer form to specify the set of equations
within each layer of the bed.
For more information on choosing the options for your ion-exchange process,
see these sections:
General tab
Material/Momentum Balance tab
Kinetic Model tab
Isotherm tab
General Tab (ionx)
Use the General tab to specify these options for your ion-exchange process:
Discretization method
Number of nodes
General Tab (ionx): Discretization
Method to be Used
These discretization methods are available for ion-exchange processes:
UDS1
UDS2
CDS1
LDS
QDS
MIXED
BUDS
General Tab (ionx): Number of Nodes
In the Number of Nodes box, choose an appropriate number of nodes for your
chosen discretization method.
(ionx)
Use the Material/Momentum Balance tab to specify the basic assumptions
about material dispersion in the liquid phase for ion-exchange processes.
(ionx): Material Balance Assumption
In the Material Balance Assumption box, choose from one of the following
options:
Convection Only
Material Balance Assumption (ionx): Convection Only
This option omits the dispersion term from the material balance, so the model
represents plug flow with a zero dispersion coefficient (infinite Peclet
number).
Because the dispersion term is omitted, you do not need to supply the
dispersion coefficient.
Material Balance Assumption (ionx): Convection with Constant
Dispersion
The Convection with Constant Dispersion option includes the dispersion term
in the material balance for the bed. You must then supply a fixed value for
the dispersion coefficient,
z
E .
With this option, the dispersion coefficient is constant for all components
throughout the bed.
Material Balance Assumption (ionx): Convection with Estimated
Dispersion
The Convection with Estimated dispersion option includes the dispersion term
in the material balance for the bed.
Here, the dispersion coefficient varies along the length of the bed. Aspen
Adsim estimates the components' dispersion coefficients in an ion-exchange
bed using this correlation (Slater, 1991):
48 . 0
011 . 0 2 . 0
|
|
.
|
\
|
+ =
i z
P l
Re
E
d v

where:
z
l
v = Liquid Velocity
i
p
d = Particle diameter
u
l P l l
v d M
Re = = Reynolds number
u = Liquid viscosity
l
= Liquid molar density
l
M = Liquid molecular weight
Material Balance Assumption (ionx): Convection with User
The Convection with User Procedure Dispersion option includes the dispersion
term in the material balance for the bed.
The dispersion coefficient varies with axial position according to a user-
supplied Fortran subroutine, which Aspen Adsim interfaces using the
procedure pUser_i_Dispersion.
Material Balance Assumption (ionx): Convection with User
Submodel Dispersion
The Convection with User Submodel Dispersion option includes the dispersion
The dispersion coefficient varies with axial position according to the user-
supplied submodel iUserDispersion.
About Axial Dispersion in Ion-
Exchange Processes
As a fluid flows through a packed column such as an ion-exchange bed, axial
dispersion (mixing) tends to occur, which reduces the efficiency of separation.
Axial dispersion should be minimized in bed design, but, if it occurs, then
Aspen Adsim must account for its effects.
There are several sources of axial dispersion in ion-exchange processes
(Ruthven, 1984):
Channeling caused by non-uniform packing, for example where different
sections of the packing have different voidages.
Dispersion from wall effects due to non-uniform packing at the wall. This
can be avoided by packing the bed well, and having a sufficiently large
ratio of bed-to-particle diameters.
Hold-up of liquid in the laminar boundary layer surrounding the particles
combined with small random fluctuations in the flow.
Splitting and recombining of the flow around the particles.
The molecular diffusivities of liquids are too small to contribute significantly to
axial dispersion. In general, the mixing effects are additive and can be
lumped together into a single effective dispersion coefficient,
z
E . The
dispersion term in the material balance is usually expressed as:
2
2
z
c
E
k
z i

The type of flow determines whether this term is omitted or included in the
material balance.
Deciding When to Use Axial Dispersion
in Ion-Exchange Processes
In deciding whether to include axial dispersion in the bed model, it is useful to
work out the Peclet number, given an effective dispersion coefficient (
z
E ), a
liquid superficial velocity (
l
v ), and a bed height (
b
H ):
z
b
E
H v
Pe
l
=
The Peclet number quantifies the degree of dispersion introduced into the
system. It is dimensionless so is more convenient than the dispersion
coefficient for this purpose.
The following table shows the effect of different values of Peclet number:

If the Peclet number
is
The effect of axial dispersion on bed
performance is
0 Infinite: the bulk liquid is perfectly mixed., so
the liquid composition is homogeneous
throughout the entire bed.
< 30 Significant.
> 100 Very slight: The bed operates under near plug
flow conditions.
Zero: The bed operates under plug flow
conditions.
Numerical methods used to discretize the spatial derivatives in the general
equations can also introduce an artificial form of dispersion.
Kinetic Model Tab (ionx)
The overall mass transfer of ionic components between the bulk liquid phase
and the adsorbed phase must overcome two resistances:
Mass transfer resistance located in the boundary layer surrounding the
particle.
Mass transfer resistance inside the resin particle.
Typically, the second resistance determines the overall mass transfer rate.
Aspen Adsim lumps the overall resistance to mass transfer into a single
overall factor. You select the type of resistance from:
Film Model Assumption
Kinetic Model Assumption
Form of Lumped Resistance
Form of Mass Transfer Coefficient
Kinetic Model Tab (ionx): Film Model
Assumption
Solid The mass transfer driving force is expressed as a function of the
solid phase loading (solid film).
Fluid The mass transfer driving force is expressed as a function of the
liquid phase concentration (liquid film).
Kinetic Model Tab (ionx): Kinetic
Model Assumption
In the Kinetic Model Assumption box, choose from:
Lumped Resistance
User Procedure
User Submodel
Kinetic Model Assumption (ionx): Lumped Resistance
Here, the mass transfer driving force for component k is expressed as a
function of the liquid phase concentration (liquid film), or solid phase loading
(solid film).
This function is either linear or quadratic. See Form of Lumped Resistance,
later.
Kinetic Model Assumption (ionx): User Procedure
With this option, the component rates of mass transfer are related to local
conditions in the bed through a relationship you supply in a Fortran
subroutine, which Aspen Adsim interfaces using the procedure
pUser_i_Kinetic.
Kinetic Model Assumption (ionx): User Submodel
With User Submodel selected, the component rates of mass transfer are
related to local conditions in the bed through the user submodel iUserKinetic.
Kinetic Model Tab (ionx): Form of
Lumped Resistance
This option is active only if you selected Lumped Resistance as your Kinetic
Model assumption.
The following options are available:
Linear
Quadratic
Form of Lumped Resistance (ionx): Linear
The mass transfer driving force for component k is expressed as a linear
function of the liquid phase concentration or solid phase loading.
) (
*
k k k
k
c c MTCl
t
w
=
(fluid film)
) (
*
k k k
k
w w MTCs
t
w
=
(solid film)
Form of Lumped Resistance (ionx): Quadratic
The mass transfer driving force is expressed as a quadratic function of the
liquid phase concentration (fluid film) or solid phase loading (solid film).
k
k k
k
k
c
c c
MTCl
t
w
2
) ) ( (
2 * 2
(fluid film)
k
k k
k
k
w
w w
MTCs
t
w
2
) ) ((
2 2 *
(solid film)
Kinetic Model Tab (ionx): Form of
Mass Transfer Coefficient
Use this option to specify how to define the mass transfer coefficients. Choose
from:
Constant
User Procedure
User Submodel
Form of Mass Transfer Coefficient (ionx): Constant
With this option, the mass transfer coefficient for each component is constant
throughout the bed. You must supply a constant value of mass transfer
coefficient for each component in the Specify table of the layer.
Form of Mass Transfer Coefficient (ionx): User Procedure
Here, the mass transfer coefficients are functions of local bed conditions. The
function is implemented in a Fortran subroutine, which Aspen Adsim
interfaces using the procedure pUser_i_MTC.
Form of Mass Transfer Coefficient (ionx): User Submodel
With User Submodel selected, the mass transfer coefficients are functions of
local bed conditions, and are returned through the user submodel iUserMTC.
Isotherm Tab (ionx)
Use the Isotherm tab to specify the adsorption isotherms for use in your ion-
exchange process.
About Adsorption Isotherms for Ion-
Exchange Processes
The driving force behind an ion-exchange separation process is the departure
from adsorption equilibrium between the aqueous and adsorbed phases.
Consequently, adsorption isotherms (also known as ion-exchange equilibria)
are important data in the design of ion-exchangers. Aspen Adsim has a list of
commonly used, standard multi-component adsorption isotherms.
Important: The equations presented are for equilibrium conditions.
Depending on the mass transfer rate model you choose, they are used to
compute either:
w*, the loading that would be at equilibrium with the actual liquid phase
composition
-or-
c*, the liquid phase composition that would be at equilibrium with the
actual loading.
This choice is automatically handled by Aspen Adsim depending on your
selection of kinetic model.
The equilibrium variable arrays (of size number of nodes number of
components) are named either Ws or Cs. In bed models, these variables are
distributed, so they have a qualifier 1, 2, n (=number of nodes), depending
on the bed location.
Isotherm Tab (ionx): Isotherm
Assumed for Layer
In the Isotherm Assumed for Layer box, choose from:
Mass Action Equilibrium
Extended Langmuir
Extended Langmuir-Freundlich
User Procedure
User Submodel
Isotherm Assumed for Layer (ionx): Mass Action Equilibrium
R R
B
+
B
+
A
+ +
R R
A
+ +
B B

The exchange reaction in the ion-exchange process is typically takes the
form:
mB AR mBR A m + +
where m is a stoichiometric coefficient.
m is an integer or a fraction. It is given by the valence ratio of A and B.
A refers to an ionic component in solution.
B refers to a counter-ion on the ion-exchanger surface.
R refers to a bound group (of opposite sign to B).
The associated equilibrium relationship can be written as:
1
0
1
|
|
.
|
\
|
|
|
.
|
\
|
|
|
.
|
\
|
=
m m
B
B
A
A
AB
c
Q
y
x
x
y
K

where:
AB
K = Equilibrium constant or selectivity coefficient.
x = Equivalent mole fraction in the adsorbed phase.
y = Equivalent mole fraction in the aqueous phase.
0
c = Total ionic concentration.
Q = Ion-exchange resin capacity.
In Aspen Adsim, the parameter
1
IP equals
AB
K , and the parameter m equals
2
IP . The equation now becomes:
0 . 1
1
0
1
2 2
=
|
|
.
|
\
|
|
|
.
|
\
|
|
|
.
|
\
|
A A
IP IP
B
B
A
A
A
c
Q
y
x
x
y
IP
Isotherm Assumed for Layer (ionx): Extended Langmuir
The extended Langmuir isotherm was found to represent some experimental
data satisfactorily:
( )
b b
k
k k
i i
i
c IP c IP
c IP
w
2 2
1
1 + +
=

where b refers to the (original) counter-ion.
Isotherm Assumed for Layer (ionx): Extended Langmuir-
Freundlich
This isotherm is based on the Langmuir isotherm and expressed as:
( )
b k
i
IP
b b
k
IP
k k
IP
i i
i
c IP c IP
c IP
w
4 4
2
3 3
1
1 + +
=

where b refers to the (original) counter-ion.
Isotherm Assumed for Layer (ionx): User Procedure
You can supply your own, proprietary isotherm relationships through a
Fortran subroutine, which Aspen Adsim interfaces using one of two
procedures:
pUser_i_Isotherm_C for solid film kinetic model
pUser_i_Isotherm_W for liquid film kinetic model
Isotherm Assumed for Layer (ionx): User Submodel
With User Submodel selected, you supply the isotherm relationship through
the user submodel iUserIsotherm.
Summary of Mass Balance Equations
for Ion-Exchange Processes
This section summarizes the mass balance equations used by Aspen Adsim to
simulate ion-exchange processes.
The overall material balance is expressed as:
0 = +
t z
v
l
i
l
l

This equation accounts for the fact that, during an ion-exchange cycle,
solvents of different densities are being used in the different production,
purge and regeneration stages. Density remains unchanged as a result of the
ion-exchange process itself.
Each ionic species in the liquid phase, fed into the ion-exchange column, is
governed by the following material balance equation:
0
2
2
= + + +
k
k
i
k
l
k
z i
J
t
c
z
c
v
z
c
E

The mass transfer rate
k
J between the bulk liquid and the resin is given by:
( )
t
w
J
k
i k
= 1
where the uptake rate
t
w
k
can, for example, be determined by a solid film

linear driving force relationship, such as:
( )
k k sk
k
w w MTC
t
w
=
*

The number of counter ions being released from the resin and entering the
liquid phase is determined from the number of ions exchanged from the liquid
phase the total charge of both liquid and resin must remain neutral:
=
=
nc
b k
k
k b
J J
1

Hence the behavior of the exchanged counter ion in the liquid phase can be
described by:
0
1
2
2
= + +
=
nc
b k
k
k
b
i
b
l
b
z i
J
t
c
z
c
v
z
c
E

Explanation of Equation Symbols for
Ion-Exchange Processes
The tables explain the equation symbols used in Aspen Adsim's ion-exchange
mass balance equations.

Symbol Explanation Aspen Adsim
base units
b
c
Counter ion concentration in liquid phase. eq/m
3

k
c
Ion concentration in liquid phase. eq/m
3

*
k
c
Liquid phase ion concentration in equilibrium
with resin phase.
eq/m
3

0
c
Total liquid phase ion concentration. eq/m
3

p
d
Resin particle diameter. m
z
E
Axial dispersion coefficient. m
2
/s
B
H
Bed height. m
IP Isotherm parameter.
b
J
Counter ion material transfer rate. eq/m
3
/s
k
J
Ion material transfer rate. eq/m
3
/s
AB
K
Mass action equilibrium constant.
m Stoichiometric coefficient used in mass action
equilibrium.

l
M
Solvent molecular weight. kg/kmol
l
MTC
Liquid film mass transfer coefficient. 1/s
s
MTC
Q Total resin ion capacity. eq/m
3

t Time. s
k
w
Ion loading on resin. eq/m
3

*
k
w

Ion loading in equilibrium with liquid phase
ion concentration.
eq/m
3

k
x
Ion mole fraction in adsorbed (resin) phase.
k
y
Ion mole fraction in liquid phase.
i

Bed voidage.
u Solvent viscosity. N/m
2
/s
i

Solvent molar density. kmol/m
3

Dimensionless
number
Defining expression Description
Pe
z
B l
E
H v

Peclet number
Re
u
l P l l
v d M

Reynolds number
4 Liquid Adsorption Processes 197
4 Liquid Adsorption
Processes
This chapter contains information on liquid adsorption processes and how
they are simulated in Aspen Adsim. For more information, see the following
topics:
About Liquid Adsorption Processes
Bed Model Assumptions for Liquid Adsorption
Configure Form
Configure Layer Form
General Tab
Kinetic Model Tab
About Adsorption Isotherms for Liquid Adsorption
Guidelines for Choosing Aspen Adsim Isotherm Models
Energy Balance Tab
Procedures Tab
Summary of Mass and Energy Balance
Explanation of Equation Symbols
About Liquid Adsorption Processes
Liquid phase adsorption has long been used to remove contaminants present
at low concentrations in process streams, such as organics from waste water.
When contaminants are not well defined, liquid phase adsorption can improve
feed quality, defined by color, taste, odor, and storage stability.
Unlike trace impurity removal, using liquid phase adsorption for bulk
separation on a commercial scale is a relatively recent development. The first
commercial operation was in the 1960s, in hydrocarbon processing. Since
then, bulk adsorptive separation of liquids has been used to solve a broad
range of problems, including individual isomer separations and class
separations. The commercial availability of synthetic molecular sieves and
ion-exchange resins, and the development of novel process concepts have
been the two significant factors in the success of these processes.
Bed Model Assumptions for Liquid
Adsorption
For liquid adsorption, the bed model assumes:
Plug flow, or plug flow with axial dispersion.
The liquid phase pressure is either constant or varies according to a
laminar-flow momentum balance (with the pressure drop assumed
proportional to the flow velocity).
The superficial velocity is constant, or varies due to adsorption and
according to total mass balance.
Molar concentrations are calculated from molar volumes. Ideal mixing is
assumed to occur in the liquid phase, so molar volume is a linear function
of composition.
A lumped mass-transfer rate applies, with a liquid or solid-film resistance.
This resistance is either linear, quadratic or user-defined.
Mass transfer coefficients are either constant or user defined.
The adsorption isotherm is chosen from Aspen Adsim defined isotherms,
or specified by you.
Isothermal or non-isothermal conditions apply. The energy balance
includes terms for:
Thermal conductivity of gas and solid.
Liquid-solid heat transfer.
Heat of adsorption.
Enthalpy of adsorbed phase.
Heat exchange with environment.
Wall energy terms.
Configure Form (liq)
This section contains information on the Configure form for a liquid process
bed model. The following options are available:
Enter the number of layers within the bed (one or more).
Type a brief name or description in the Description box.
Click the Configure button to open the Configure Layer dialog box.
Click the Specify button to open the Specify form for the layer model.
Configure Layer Form (liq)
Use the options in the Configure Layer form to define the set of equations for
each layer of the adsorption bed.
For information on choosing the options for your liquid adsorption process,
see the following sections:
General Tab
Kinetic Model Tab
Isotherm Tab
Energy Balance Tab
Procedures Tab
General Tab (liq)
Use the General tab to specify the numerical options for your liquid adsorption
process.
General Tab (liq): Discretization
Method to be Used
These discretization methods are available for liquid adsorption processes:
UDS1
UDS2
CDS1
LDS
QDS
MIXED
BUDS
General Tab (liq): Number of Nodes
In the Number of Nodes box, choose an appropriate number of nodes for your
discretization method.
Material/Momentum Balance (liq)
Use the Material/Momentum Balance tab to:
Make basic assumptions about axial dispersion in the liquid phase.
Determine how to treat the pressure drop in the adsorption bed model.
Specify whether the velocity is constant or varies along the column.
Material/Momentum Balance Tab (liq):
Material Balance Assumption
In the Material Balance Assumption box, choose the material balance option
for your liquid adsorption process. Choose from:
Convection Only
Material Balance Assumption (liq): Convection Only
The Convection Only option leaves out the dispersion term from the material
balance for the bed. The model now represents plug flow with a zero
dispersion coefficient (infinite Peclet number).
Because the dispersion term is omitted, you need not supply the dispersion
coefficient.
Material Balance Assumption (liq): Convection with Constant
Dispersion
The Convection with Constant Dispersion option includes the dispersion term
in the material balance for the bed. You need to supply a constant value for
the dispersion coefficient,
z
E .
With this option, the dispersion coefficient is constant for all components
throughout the bed.
Material Balance Assumption (liq): Convection with Estimated
Dispersion
The Convection with Estimated Dispersion option includes the dispersion term
in the material balance for the bed.
With this option, the dispersion coefficient varies along the length of the bed.
Aspen Adsim estimates the values during the simulation, for each component,
using this correlation (Slater, 1991):
48 . 0
011 . 0 2 . 0
|
|
.
|
\
|
+ =
i i i z i
Re
E
r v
P l

Where:
z
l
v = Liquid Velocity
i
p
r = Particle radius
Re = Reynolds number
Material Balance Assumption (liq): Convection with User
The Convection with User Procedure Dispersion option includes the dispersion
With this option, the dispersion coefficient varies according to a user supplied
Fortran subroutine, which Aspen Adsim interfaces through the procedure type
pUser_l_dispersion.
Material Balance Assumption (liq): Convection with User
Submodel Dispersion
The Convection with User Submodel Dispersion option includes the dispersion
With this option, the dispersion coefficient varies according to the submodel
lUserDispersion.
Pressure Drop Assumption
Use the Pressure Drop Assumption box to specify how Aspen Adsim treats the
pressure drop in the adsorption bed model. You should base your choice on
your knowledge of the actual operating conditions in the plant.
This option corresponds to how internal superficial velocities are related to
local pressure gradients. It applies to laminar flow. You must choose an
appropriate material balance model with a particular pressure-drop option.
In the Pressure Drop Assumption box, choose from these options:
None
Darcy's Law
Karman-Kozeny
Pressure Drop Assumption (liq): None
With None selected, there is no pressure drop across the bed.
Pressure Drop Assumption (liq): Darcy's Law
Select the Darcy's Law option to apply a linear relationship between the liquid
superficial velocity and the pressure gradient at a particular point in a bed.
Darcy's law states that the pressure drop is directly proportional to flow rate:
l P
v K
z
p
=

Where:
p
K = Proportionality constant
Pressure Drop Assumption (liq): Karman-Kozeny
Select the Karman-Kozeny option to relate velocity to pressure drop:
( )
( )
p
i
i l
i p
r v
r
z
p
2
1 10 5 . 1
1
2
3
3

=

Velocity Assumption
In the Velocity Assumption box, choose from:
Constant Velocity
Varying Velocity
Velocity Assumption (liq): Constant Velocity
With Constant Velocity selected, the liquid velocity is constant along the bed,
so adsorption from the liquid phase has a negligible effect on the material
balance. These assumptions are valid only when modeling the removal of
trace components from a bulk liquid.
Velocity Assumption (liq): Varying Velocity
With Varying Velocity selected, the superficial velocity varies along the bed
according to the rate at which the liquid components are adsorbed onto the
solid, or desorbed. The rate is determined from material balance.
This option is applicable to bulk separation applications.
If you select this option:
The velocity profile is determined through the total material balance, by
the effect of the rate of adsorption.
The velocity profile is stored in the discrete variables Vl_in(1)Vl_in(n),
where n is the number of nodes used in the numerical method.
Overall Material Balance Assumption
In the Overall Material Balance Assumption box, choose from:
Constant Density
Dynamic Density
Overall Material Balance Assumption (liq): Constant Density
With the Constant Density option, the mass density is constant along the bed.
The velocity alone changes, and that according to the overall mass balance.
Overall Material Balance Assumption (liq): Dynamic Density
With Dynamic Density selected, mass density varies according to the material
balance. Both mass density and velocity vary according to the overall mass
balance.
Kinetic Model Tab (liq)
When a species is adsorbed from the bulk liquid phase onto an active surface
site of the adsorbents, it typically experiences the following mass transfer
resistances:
The resistance between the bulk liquid and the external adsorbents
surface.
The resistance exerted by the adsorbents pore structure. For bi-disperse
adsorbents (such as zeolites), this resistance can be further divided into:
Macropore resistance.
Micropore resistance.
These resistances are typically lumped into a single, overall mass transfer
coefficient.
The following options are available from the Kinetic Model tab:
Film Model Assumption
Kinetic Model Assumption
Form of Mass Transfer Coefficient
Kinetic Model Tab (liq): Film Model
Assumption
Solid the mass transfer driving force is expressed as a function of the
solid phase loading.
Fluid the mass transfer driving force is expressed as a function of the
liquid phase concentration.
Kinetic Model Tab (liq): Kinetic Model
Assumption
In the Kinetic Model Assumption box, choose from:
Linear lumped resistance.
Quadratic lumped resistance.
Micro and macropore.
User procedure.
User submodel.
Kinetic Model Assumption (liq): Linear Lumped Resistance
With Linear Lumped Resistance selected, the mass transfer driving force for
component i is expressed as a linear function of the liquid phase
concentration or solid phase loading.
( )
*
i i li
i
S
c c MTC
t
w
=
(fluid)
( )
i i si
i
w w MTC
t
w
=
*
(solid)
Kinetic Model Assumption (liq): Quadratic Lumped Resistance
With Quadratic Lumped Resistance selected, the mass transfer driving force is
expressed as a quadratic function of the liquid phase concentration or solid
phase loading.
( ) ( )
i
i i li i
S
c
c c MTC
t
w
2
2
* 2
(fluid)
( ) ( )
i
i i
si
i
w
w w
MTC
t
w
2
2
2
*
(solid)
Kinetic Model Assumption (liq): Micro and Macropore Model
Two concentration gradients greatly affect the diffusion rate:
Within the pores of the solid.
Within the void spaces between the particles, that is, within the
crystallines.
Under practical conditions in gas separation, pore diffusion limits the overall
mass transfer rate between the bulk flow and the internal surface of a
particle, so it is an important factor in the dynamics of adsorbers.
For more information, see Micro and Macro Pore Effects in Chapter 1.
Kinetic Model Assumption (liq): User Procedure
The User Procedure option relates the component rates of mass transfer to
the local bed conditions through a user-supplied Fortran subroutine, which
Aspen Adsim interfaces through the procedure type pUser_l_Kinetic.
Kinetic Model Assumption (liq): User Submodel
With User Submodel selected, the bed model calls the submodel lUserKinetic.
This submodel needs the relationship between the component rates of mass
transfer and the local bed conditions.
Kinetic Model Tab (liq): Form of Mass
Transfer Coefficient
In the Form of Mass Transfer Coefficient box, you choose how mass transfer
coefficients are defined. Choose from:
Constant
User Procedure
User Submodel
Form of Mass Transfer Coefficient (liq): Constant
With Constant selected, the mass transfer coefficient for each component is
constant through the bed. You must supply a constant value of mass transfer
coefficient for each component.
Form of Mass Transfer Coefficient (liq): User Procedure
If you choose User Procedure, the mass transfer coefficients are returned by a
Fortran subroutine you supply, which Aspen Adsim interfaces through the
procedure pUser_l_MTC.
Form of Mass Transfer Coefficient (liq): User Submodel
With User Submodel selected, the mass transfer coefficients are defined in
the user submodel lUserMTC.
About Adsorption Isotherms for Liquid
Adsorption
The driving force behind all adsorptive liquid separation processes is the
departure from adsorption equilibrium, so adsorption isotherms are important
data in adsorber design.
If you know the adsorption isotherms for the components of the feed, you can
create a bed model to predict the performance of the adsorber bed for the
specified operating conditions.
Aspen Adsim has a comprehensive list of multicomponent adsorption
isotherms.
Guidelines for Choosing Aspen Adsim
Isotherm Models
Make sure you choose a model that is appropriate for the process you are
investigating. The equilibrium specified by the isotherm model affects the
driving force for mass transfer. Consequently, you can obtain significantly
different simulation results when using different models, even if the model
parameters come from the same set of data.
The expressions in this section are equilibrium equations. Depending on the
mass transfer rate model you choose (See also Kinetic Model Tab (liq) on
page 4-202), the expressions are used to compute either:
w* The loading that would be at equilibrium with the actual liquid phase
composition
-or-
c* The liquid phase composition that would be at equilibrium with the
actual loading.
This choice is automatically handled by Aspen Adsim.
The equilibrium variable arrays (of size n) are named either Ws or Cs. In bed
models, these variables are distributed, so they have a qualifier 1, 2, ... n, to
denote their location in the bed.
The Ideal Adsorbed Solution Theory
(IAS)
Recently, the Ideal Adsorbed Solution Theory (IAS) has become popular for
multicomponent mixtures. The method lets you predict adsorption equilibria
for components in a mixture. It needs data only for the pure-component
adsorption equilibria at the same temperature, and on the same adsorbent.
The model treats the mixed adsorbate phase as an ideal solution in
equilibrium with the liquid phase. The model follows the formal,
thermodynamic approach for vapor-liquid equilibria, in which the fundamental
equations of thermodynamic equilibrium are developed, and applies this to
the liquid-adsorbed phase equilibria.
At first sight, ideal behavior in the adsorbed phase seems improbable.
However, many systems have shown strong correlation between experimental
data and predictions by IAS theory, including binary and ternary mixtures on
activated carbons and zeolites.
IAS is available in Aspen Adsim. To use it, choose the appropriate isotherm on
the Isotherm tab of the Configure Layer form. For a full description of the IAS
approach, see Chapter 4 of Ruthven (1984) or Chapter 3 of Kast (1988)
(German language).
Isotherm Tab (liq): Isotherm Assumed
for Layer
Use the Isotherm tab to choose which adsorption isotherms are used in your
liquid adsorption process. Choose from:
Langmuir models (1,2)
Dual-Site Langmuir models (1,2
Extended Langmuir models (1,2)
Freundlich models (1,2)
Langmuir-Freundlich models (1,2)
Extended Langmuir-Freundlich models (1,2)
Stoichiometric Equilibrium models (1,2)
IAS Langmuir models (1,2)
IAS Freundlich models (1,2)
IAS Langmuir-Freundlich models (1,2)
User Multicomponent Procedure
User Multicomponent Submodel
User Multicomponent Procedure with IAS
User Multicomponent Submodel with IAS
Isotherm Assumed for Layer (liq): Langmuir Models (1,2)
There are two types of Langmuir model available in Aspen Adsim:
Langmuir 1, which is temperature independent.
Langmuir 2, which is temperature dependent.
Langmuir 1
This isotherm is expressed as:
i i
i i i
i
c IP
c IP IP
w
2
2 1
1+
=
Langmuir 2
i
s
i
i
i
s
i
i i
i
c
T
IP
IP
c
T
IP
IP IP
w
|
|
.
|
\
|
+
|
|
.
|
\
|
=
3
2
3
2 1
exp 1
exp

Isotherm Assumed for Layer (liq): Dual-Site Langmuir Models
(1,2)
There are two types of Dual-Site Langmuir model available in Aspen Adsim:
Dual-Site Langmuir 1, which is temperature independent.
Dual-Site Langmuir 2, which is temperature dependent.

= =
+
+
+
=
nc
k
k k
i i i
nc
k
k k
i i i
i
c IP
c IP IP
c IP
c IP IP
w
1
4
4 3
1
2
2 1
1 1


= =
|
|
.
|
\
|
+
|
|
.
|
\
|
+
|
|
.
|
\
|
+
|
|
.
|
\
|
=
nc
k
k
s
k
k
i
s
i
i i
nc
k
k
s
k
k
i
s
i
i i
i
c
T
IP
IP
c
T
IP
IP IP
c
T
IP
IP
c
T
IP
IP IP
w
1
6
5
6
5 4
1
3
2
3
2 1
exp 1
exp
exp 1
exp

Isotherm Assumed for Layer (liq): Extended Langmuir Models
(1,2)
Aspen Adsim has two types of Extended Langmuir model:
Extended Langmuir 1, which is temperature independent.
Extended Langmuir 2, which is temperature dependent.
Extended Langmuir 1
=
+
=
nc
k
k k
i i i
i
c IP
c IP IP
w
1
2
2 1
1

Extended Langmuir 2
=
|
|
.
|
\
|
+
|
|
.
|
\
|
=
nc
k
k
s
k
k
i
s
i
i i
i
c
T
IP
IP
c
T
IP
IP IP
w
1
3
2
3
2 1
exp 1
exp

Isotherm Assumed for Layer (liq): Freundlich Models (1,2)
There are two types of Freundlich model available in Aspen Adsim:
Freundlich 1, which is temperature independent.
Freundlich 2, which is temperature dependent.
Freundlich 1
i
IP
i i i
c IP w
2
1
=
Freundlich 2
|
|
.
|
\
|
=
s
i IP
i i i
T
IP
c IP w
i
3
1
exp
2

Isotherm Assumed for Layer (liq): Langmuir-Freundlich Models
(1,2)
There are two types of Langmuir-Freundlich model available in Aspen Adsim:
Langmuir-Freundlich 1, which is temperature independent.
Langmuir-Freundlich 2, which is temperature dependent.
Langmuir-Freundlich 1
i
i
IP
i i
IP
i i i
i
c IP
c IP IP
w
3
3
2
2 1
1+
=
Langmuir-Freundlich 2
|
|
.
|
\
|
+
|
|
.
|
\
|
=
s
i IP
i i
s
i IP
i i i
i
T
IP
c IP
T
IP
c IP IP
w
i
i
4
2
4
2 1
exp 1
exp
3
3

Isotherm Assumed for Layer (liq): Extended Langmuir-
Freundlich Models (1,2)
There are two types of Extended Langmuir-Freundlich model available in
Aspen Adsim:
Extended Langmuir-Freundlich 1, which is temperature independent.
Extended Langmuir-Freundlich 2, which is temperature dependent.
Extended Langmuir-Freundlich 1
( )
=
+
=
n
j
IP
j j
IP
i i i
i
j
i
c IP
c IP IP
w
1
2
2 1
3
3
1

Extended Langmuir-Freundlich 2
=
|
|
.
|
\
|
|
|
.
|
\
|
+
|
|
.
|
\
|
=
n
j s
j IP
j j
s
i
IP
i i i
i
T
IP
c IP
T
IP
c IP IP
w
j
i
1
4
2
4
2 1
exp 1
exp
3
3

Isotherm Assumed for Layer (liq): Stoichiometric Equilibrium
Models (1,2)
Aspen Adsim has two types of Stoichiometric Equilibrium model:
Stoichiometric Equilibrium 1, which is temperature independent.
Stoichiometric Equilibrium 2, which is temperature dependent.
Stoichiometric Equilibrium 1
=
=
nc
k
k k
i i i
i
c IP
c IP IP
w
1
2
2 1

Stoichiometric Equilibrium 2
=
|
|
.
|
\
|
|
|
.
|
\
|
=
nc
k
k
s
k
k
i
s
i
i i
i
c
T
IP
IP
c
T
IP
IP IP
w
1
3
2
3
2 1
exp
exp

Isotherm Assumed for Layer (liq): IAS Langmuir Models (1,2)
With IAS Langmuir Models selected, the multicomponent adsorption behavior
is expressed using Ideal Adsorbed Solution theory in combination with pure
component isotherms. Aspen Adsim has two versions of the pure component
Langmuir model:
IAS Langmuir 1, which is temperature independent.
IAS Langmuir 2, which is temperature dependent.
IAS Langmuir 1
i i
i i i
i
c IP
c IP IP
w
2
2 1
1+
=
IAS Langmuir 2
i
s
i
i
i
s
i
i i
i
c
T
IP
IP
c
T
IP
IP IP
w
|
|
.
|
\
|
+
|
|
.
|
\
|
=
3
2
3
2 1
exp 1
exp

Isotherm Assumed for Layer (liq): IAS Freundlich Models (1,2)
With IAS Freundlich Models selected, the multicomponent adsorption behavior
is expressed using the Ideal Adsorbed Solution Theory in combination with
pure component isotherms. Aspen Adsim has two versions of the pure
component Freundlich model:
IAS Freundlich 1, which is temperature independent.
IAS Freundlich 2, which is temperature dependent.
IAS Freundlich 1
i
IP
i i i
c IP w
2
1
=
IAS Freundlich 2
|
|
.
|
\
|
=
s
i IP
i i i
T
IP
c IP w
i
3
1
exp
2

Isotherm Assumed for Layer (liq): IAS Langmuir-Freundlich
Models (1,2)
With IAS Langmuir-Freundlich selected, the multicomponent adsorption
behavior is expressed using the Ideal Adsorbed Solution Theory in
combination with pure component isotherms. Aspen Adsim has two versions
of the pure component Langmuir-Freundlich model:
IAS Langmuir-Freundlich 1, which is temperature independent.
IAS Langmuir-Freundlich 2, which is temperature dependent.
IAS Langmuir-Freundlich 1
i
i
IP
i i
IP
i i i
i
c IP
c IP IP
w
3
3
2
2 1
1+
=
IAS Langmuir-Freundlich 2
|
|
.
|
\
|
+
|
|
.
|
\
|
=
s
i
IP
i i
s
i
IP
i i i
i
T
IP
c IP
T
IP
c IP IP
w
i
i
4
2
4
2 1
exp 1
exp
3
3

Isotherm Assumed for Layer (liq): User Multicomponent
Procedure
You can supply your own, proprietary isotherm relationships through a
Fortran subroutine, which Aspen Adsim interfaces using one of two
procedures:
pUser_l_Isotherm_C for solid film kinetic model
pUser_l_Isotherm_W for liquid film kinetic model
( ) IP c c T f w
nc eq i
, ... ,
1
=
Isotherm Assumed for Layer (liq): User Multicomponent
Submodel
You can supply your own, proprietary isotherm relationships using the
submodel lUserIsotherm.
( ) IP c c T f w
nc eq i
, ... ,
1
=
Isotherm Assumed for Layer (liq): User Purecomponent
Procedure with IAS
Select the User Purecomponent Procedure with IAS option to supply pure
component, user-specified isotherms, which may be used as multicomponent
isotherms. In this case, two Fortran subroutines are needed:
The first subroutine is interfaced by the procedure type pUser_l_Isotherm_W.
This relates the fictitious pure component concentration
0
i
c (resulting in the
same spread pressure as the mixture at total concentration
tot
c ), to the
loading
0
i
w , using the pure component isotherm:
( ) IP c T f w
i eq i
, ,
0 0
=
The second Fortran subroutine evaluates the integral of the Gibbs isotherm to
give the spread pressure. It is interfaced by the procedure type
pUser_l_Gibbs. The relationship to be evaluated is:
( )
( )
= =
0
0
0
0
, ,
, ,
i
c
eq
i
i
dc
c
IP c T f
g IP c T g
RT
A
with

Isotherm Assumed for Layer (liq): User Purecomponent
Submodel with IAS
Select this option to supply pure component, user-specified isotherms, which
may be used as multicomponent isotherms. In this case, you must supply two
submodels:
The first submodel is lUserIsotherm. This relates the fictitious pure
component concentration
0
i
c (resulting in the same spread pressure as the
mixture at total concentration
tot
c ), to the loading
0
i
w , using a pure
component isotherm:
( ) IP c T f w
i eq i
, ,
0 0
=
The second submodel, lUserGibbs, evaluates the integral of the Gibbs
isotherm to give the spread pressure. The relationship to be evaluated is:
( )
( )
= =
0
0
0
0
, ,
, ,
i
c
eq
i
i
dc
c
IP c T f
g IP c T g
RT
A
with

Energy Balance Tab (liq)
Use the Energy Balance tab to specify how the energy balance is incorporated
into the model.
Energy Balance Tab (liq): Energy
Balance Assumption
In the Energy Balance Assumption box, choose from the following options:
Isothermal
Non-Isothermal with no Conduction
Non-Isothermal with Fluid Conduction
Non-Isothermal with Solid Conduction
Non-Isothermal with Fluid and Solid Conduction
Energy Balance Assumption (liq): Isothermal
The Isothermal option ignores the energy balance. Fluid and solid
temperatures are set to the same, constant value.
Energy Balance Assumption (liq): Non-Isothermal with No
Conduction
The Non-Isothermal with No Conduction option ignores the axial thermal
conduction for the fluid and solid phases within the energy balance.
Energy Balance Assumption (liq): Non-Isothermal with Fluid
Conduction
The Non-Isothermal with Fluid Conduction option includes the thermal
conduction (axial thermal dispersion) term in the fluid energy balance.
This term is represented as:
2
2
z
T
k
l
l

The liquid phase thermal conductivity can be supplied in different ways as
specified in the section Form of Fluid Thermal Conductivity.
Energy Balance Assumption (liq): Non-Isothermal with Solid
Conduction
The Non-Isothermal with Solid Conduction option includes the thermal
conduction term in the solid energy balance. The solid thermal conduction
term is represented as:
2
2
z
T
k
S
S

You must supply a value for
s
k .
Energy Balance Assumption (liq): Non-Isothermal with Fluid
and Solid Conduction
The Non-Isothermal with Fluid and Solid Conduction option includes the
thermal conduction term for both fluid and solid phases.
The liquid phase thermal conductivity can be supplied in different ways, as
specified in the section Form of Fluid Thermal Conductivity field.
Energy Balance Tab (liq): Consider
Heat of Adsorbed Phase
Aspen Adsim models enable you to include the heat capacity of the adsorbed
phase in the solid-phase energy balance. The Heat of Adsorbed Phase term is
optional.
In the Consider Heat of Adsorbed Phase box, select from No or Yes:
No Choose this option to ignore the enthalpy of the adsorbed phase
term in the solid phase energy balance.
Yes Choose this option if the enthalpy content of the adsorbed phase is
significant for your process, and you want to include it in the overall
energy balance.
The term for each component is a function of the loading and the
temperature in the solid phase:
t
T
w C H
S
i Pi p i ads
=
,

The total contribution is the sum for all components:
=
nc
i
i ads
H
1
,

Energy Balance Tab (liq): Heat of
Adsorption Assumption
If the solid-phase energy balance is significant for the process, you must
include the heat of adsorption within the balance. The rate of heat generation
by adsorption of each component i, per unit mass of solid, is a function of the
local rate of mass transfer and the heat of adsorption:
i
i
i
H
t
w
HT
=
These rates are held in vectors and summed for all components to obtain the
total rate of heat generation, by adsorption, per unit volume of solid:
( )
=
nc
i
i p
HT
1

In the Heat of Adsorption Assumption box, choose from:
None
Constant
User Procedure
User Submodel
Heat of Adsorption Assumption (liq): None
The heat generation by adsorption term is omitted from the energy balance.
Heat of Adsorption Assumption (liq): Constant
The Constant option assumes the heat of adsorption is constant for each
component i. Choose this option to set the heat of adsorption to constant
values. These are held in a vector called DH. You must provide the values of
the elements of DH.
Heat of Adsorption Assumption (liq): User Procedure
With User Procedure selected, the heat of adsorption comes from a user-
supplied Fortran subroutine, which Aspen Adsim interfaces using the
procedure pUser_l_DH. You can vary the heat of adsorption and make it a
function of, for example, local loading, temperature, and pressure. In general
terms:
) , , ( w P T f H
s
=
Heat of Adsorption Assumption (liq): User Submodel
With User Submodel selected, the heat of adsorption comes from the user
submodel lUserDH. You can vary the heat of adsorption and make it a
function of, for example, local loading, temperature, and pressure. In general
terms:
) , , ( w P T f H
s
=
Energy Balance Tab (liq): Form of Heat
Transfer Coefficient
If you request a non-isothermal energy balance, Aspen Adsim generates the
solid and fluid phase energy balances, using a film resistance due to heat
transfer between the solid and the fluid. Heat transfer is assumed to occur
between the two phases according to:
Rate of heat transferred per unit volume of bed ( ) ( )
S l i P
T T HTC a = 1
If there is no heat transfer resistance between the solid and fluid, the
temperature of the fluid and solid are equal (lumped). To obtain this
condition, set the heat transfer coefficient to a very large value (such as
1MW/m
2
/K).
In the Form of Heat Transfer Coefficient box, choose from:
Constant
Estimated
User Procedure
User Submodel
Form of Heat Transfer Coefficient (liq): Constant
Choose Constant to ensure the heat transfer coefficient has a single value,
which is held in a variable called HTC.
Form of Heat Transfer Coefficient (liq): Estimated
The heat transfer coefficient is estimated as follows:
1 Calculate the Reynolds number:
u
l l p
v M r
Re
2
=
If the calculated value falls below 1E-10, reset it to this value.
2 Calculate the Prandl number:
M k
C
Pr
l
pl
u
=
If the calculated value falls below 1E-10, reset it to this value.
3 Calculate the j-factor:
If Re < 190 then
51 . 0
66 . 1
= Re j otherwise
41 . 0
983 . 0
= Re j
4 Calculate the heat transfer coefficient:
3
2
Pr
=
l l pl
v C j HTC
If the calculated value falls below 1E-10, reset it to a value of 1.
Form of Heat Transfer Coefficient (liq): User Procedure
With the User Procedure option, the user procedure pUser_l_HTC relates the
local heat transfer coefficient to the state of the bed at a particular point in
the bed. This means you can interface your own Fortran code to calculate the
coefficients.
In general terms:
( )
l l
v C P T f HTC , , , =
Form of Heat Transfer Coefficient (liq): User Submodel
With User Submodel selected, the local heat transfer coefficient is defined
through the user submodel lUserHTC.
Energy Balance Tab (liq): Form of
Fluid Thermal Conductivity
If you selected Non-isothermal with Fluid and/or Solid Conduction, you need
to choose the form of fluid thermal conductivity .
In the Form of Fluid Thermal Conductivity box, choose from:
Constant
Based on Axial Dispersion
User Procedure
User Submodel
Form of Fluid Thermal Conductivity (liq): Constant
The thermal conductivity has a constant value, which you set.
Form of Fluid Thermal Conductivity (liq): Based on Axial
Dispersion
With Based on Axial Dispersion selected, the thermal conductivity coefficient
is calculated as the product of the molar heat capacity of the fluid, the axial
dispersion coefficient and the molar density of the fluid:
l z Pl l
E C k =
This method applies the analogy between heat and mass transfer.
Form of Fluid Thermal Conductivity (liq): User Procedure
With User Procedure selected, thermal conductivity varies axially along the
bed and is defined in a user-defined Fortran subroutine, which Aspen Adsim
interfaces using the procedure pUser_l_Kl.
Form of Fluid Thermal Conductivity (liq): User Submodel
With User Submodel selected, thermal conductivity varies axially along the
bed and is defined in the user submodel lUserKl.
Energy Balance Tab (liq): Heat
Transfer to Environment
In the Heat Transfer to Environment box, choose from:
Adiabatic
Thin Wall
Rigorous Model
Heat Exchange between Fluid and Wall
Heat Exchange between Wall and Environment
Axial Conductivity along the Wall
Heat Content of Wall
Heat Transfer to Environment (liq): Adiabatic
With Adiabatic selected, there is no heat transfer between the bed and the
wall.
Heat Transfer to Environment (liq): Thin Wall
With the Thin Wall option, the fluid phase energy balance includes the heat
exchange between the fluid in the bed and the environment:
( )
amb l
B
w
T T
D
H
4

Heat Transfer to Environment (liq): Rigorous Model
With Rigorous Model selected, the bed model applies a wall energy balance
equation that contains the following terms:
Heat transfer from the fluid in the bed to the inner wall.
Heat transfer from the outer wall to the environment.
The wall is assumed to be thin and conductive enough for the inner and outer
wall temperatures to be equal. The adiabatic option (that is, ignoring the wall
energy balance) is valid only when the wall is non-conductive, or there is an
infinite heat transfer resistance between the liquid and the wall surface.
Heat Transfer to Environment (liq): Heat Exchange Between
Fluid and Wall
When the rigorous wall energy balance is selected, the heat exchange
between the fluid in the bed and the inner surface of the wall is included in
the wall energy balance.
The term is represented as:
( )
w l
wi wo
wi
w
T T
D D
D
H
2 2
4

You must define the value of the liquid-to-wall heat transfer coefficient,
w
H .
The heat exchange between fluid and wall is also included in the fluid phase
energy balance. Note that the equation has a slightly different form, owing to
the different cross-sectional areas of the balances:
( )
w l
wi
w
T T
D
H
4

Heat Transfer to Environment (liq): Heat Exchange Between
Wall and Environment
When a rigorous wall energy balance is included, the heat transfer between
the outer wall and the environment is expressed as:
( )
amb w
wi wo
wo
amb
T T
D D
D
H
2 2
4

You must define the value of the heat transfer coefficient to the environment
amb
H and the temperature of the environment,
amb
T . To ignore the effect of
heat exchange with the environment in the energy balance, set the value of
the heat transfer coefficient to zero.
Heat Transfer to Environment (liq): Axial Thermal Conductivity
Along Wall
The axial thermal conduction along the wall is always included in the wall
energy balance. The term is:
2
2
z
T
k
w
w

You must specify the thermal conductivity of the wall material,
w
k .
Heat Transfer to Environment (liq): Heat Content of Wall
The heat accumulation of the wall is always included in the wall energy
balance. The term is:
t
T
C
w
pw w

You must specify the value of the wall density,
w
, and the specific heat
capacity of the wall,
pw
C .
Procedures Tab (liq)
Use the Procedures tab to view a list of the user procedures being used within
the current adsorption layer model.
Liquid Adsorption: Summary of Mass
and Energy Balance
For information on the equations used in Aspen Adsim for mass and energy
balances in liquid adsorption processes, see:
Liquid Adsorption: Mass Balance
Liquid Adsorption: Solid Phase Energy Balance
Liquid Adsorption: Fluid Phase Energy Balance
Liquid Adsorption: Wall Energy Balance
Liquid Adsorption: Mass Balance
The overall mass balance for a multi-component liquid phase contains terms
for:
Convection of material.
Accumulation of material in the liquid phase.
Mass transfer from the liquid to the solid phase.
( ) 0
1
= |
.
|
\
|
=
nc
i
i
i s Ml l
Ml
i
t
w
M v
z t

Each component in the liquid phase is governed by a material balance:
( ) 0
2
2
=
t
w
t
c
c v
z z
c
E
i
s
i
i i l
i
z i

Liquid Adsorption: Solid Phase Energy
Balance
The solid phase energy balance includes terms for:
Thermal conduction.
Accumulation of heat.
Accumulation of heat in the adsorbed phase.
Heat of adsorption.
Gas-solid heat transfer (expressed in terms of a film resistance where the
heat transfer area is proportional to the area of the adsorbent particles).
The solid phase energy balance is given as:
( ) ( )

= =
= |
.
|
\
|
+ + +
nc
i
s l p
i
i p
nc
i
i pli
s
p
s
ps p
s
s
T T HTC a
t
w
H w C
t
T
t
T
C
z
T
k
1 1
2
2
0

Liquid Adsorption: Fluid Phase Energy
Balance
The fluid phase energy balance includes terms for:
Thermal conduction.
Convection of energy.
Accumulation of heat, heat transfer from fluid to solid.
Heat transfer from fluid to the internal wall.
( ) ( ) ( ) 0
4
1
2
2
= + +
w l
wi
w
s l i p
l
l pl i
l
l l pl
l
i l
T T
D
H
T T HTC a
t
T
C
z
T
v C
z
T
k

Liquid Adsorption: Wall Energy
Balance
The wall energy balance includes terms for:
Heat transfer from the bed to the inner wall.
Heat transfer from the outer wall to the environment.
( ) ( ) 0
4 4
2 2 2 2 2
2
=
amb w
wi wo
wo
amb w l
wi wo
wi
w
w
pw w
w
w
T T
D D
D
H T T
D D
D
H
t
T
C
z
T
k
Liquid Adsorption: Explanation of
Equation Symbols

p
a
Specific particle surface. m
2
/m
3

A Area. m
2

k
c
Molar concentration of component k. kmol/m
3

0
i
c
IAS pure component concentration. kmol/m
3

pl
C
Specific liquid phase heat capacity. MJ/kmol/K
ps
C
Specific heat capacity of adsorbent. MJ/kmol/K
pW
C
Specific heat capacity of column wall. MJ/kg/K
B
D
Bed diameter. m
wi
D
Inner bed diameter. m
wo
D
Outer bed diameter. m
z
E
Axial dispersion coefficient. m
2
/s
eq
f
Equilibrium (isotherm) relationship. -
g Function. -
i ads
H
,

Heat of component i in adsorbed phase. MJ/m
3
/s
amb
H
Wall-ambient heat transfer coefficient. MW/m
2
/K
B
H
Height of adsorbent layer. m
i
HT
Heat of adsorption contribution to solid phase
energy balance.
MJ/m
3
/s
w
H
Gas-wall heat transfer coefficient. MJ/m
2
/s
i
H
Heat of adsorption of component i. MJ/kmol
HTC Liquid-solid heat transfer coefficient. MJ/m
2
/s
IP Isotherm parameter, units depend on
isotherm.

j Colburn j-factor for heat or mass transfer. -
l
k
Liquid phase thermal conductivity. MW/m/K
s
k
Solid thermal conductivity. MW/m/K
P
K
Darcys constant. bar s/m
2

M Molecular weight. kg/kmol
l
MTC
Liquid film mass transfer coefficient. 1/s
s
MTC
p Pressure. bar
p
r
Particle radius. m
R Universal gas constant. bar m
3
/kmol/K
t Time. s
T Temperature. K
amb
T
Ambient temperature. K
s
T
Solid phase temperature. K
l
T
Liquid phase temperature. K
W
T
Wall temperature. K
l
v
Liquid phase superficial velocity. m/s
k
w
Loading. kmol/kg
0
k
w
Pure component loading of component k. kmol/kg
W Width of horizontal bed. m
T
W
Width of column wall. m

i
Interparticle voidage. m
3
(Void)/m
3
(Bed)
u Dynamic viscosity. N s/m
2

0
i

Spreading pressure of component i. bar m
I M,

Liquid phase mass density. kg/m
3

l

Liquid phase molar density. kmol/m
3

p

Adsorbent apparent density. kg/m
3

s

Adsorbent bulk density. kg/m
3

W

Wall density. kg/m
3

Particle shape factor. -

Dimensionless number Defining expression Description
Pe
z
b l
E
H v

Peclet number for mass
transfer.
Pr
M k
C
l
pl
u

Prandl number.
Re
u
l l M p
v r
,
2

Particle Reynolds number.
5 Numerical Methods 224
5 Numerical Methods
This chapter describes the numerical methods available in Aspen Adsim to
solve its partial differential equations.
See these topics for more information:
About Numerical Methods
Choosing the Discretization Method
About the Discretization Methods
About Numerical Methods
Aspen Adsim uses a set of partial differential equations (PDEs), ordinary
differential equations (ODEs) and algebraic equations, together with the
appropriate initial and boundary conditions, to fully describe the adsorption or
ion-exchange column.
Spatial derivatives are discretized using algebraic approximations, and a set
of ordinary differential equations and algebraic equations (DAEs) results.
The spatial derivative terms within the partial differential equations are first-
or second-order derivatives of some distributed variable, such as
concentration, temperature or molar flux.
The approximations are defined over a fixed, uniform grid of points (nodes);
the distributed variables are defined for each node by means of variable sets.
The resulting system of differential and algebraic equations must be solved
simultaneously since they are coupled. In a sense, the dependent variables at
each node march in time along parallel lines perpendicular to the spatial
axis, which explains the commonly-used name for this solution technique: the
numerical method of lines.
The first-order spatial derivatives present the greatest challenge in providing
numerically accurate and stable approximations, particularly when the system
of equations is highly nonlinear a common occurrence in adsorption
process simulation. A typical problem is the propagation of steep
discontinuities known as fronts or shocks. The failure of approximations to
adequately represent the first order derivatives is manifested by two
unwanted and spurious effects:
Numerical diffusion leading to excessive smearing of the solution.
Numerical oscillations, leading to non-physical solutions and the violation
of physical bounds.
This chapter describes the methods available in Aspen Adsim to approximate
first-order spatial derivatives, showing where the methods come from and
how they are evaluated.
Choosing the Discretization Method
Your choice of discretization method depends chiefly on the type of process
you are simulating, and the level of accuracy, stability and speed you are
looking for.
Each of the numerical methods differ in:
Method of approximation of spatial derivatives.
Number of points.
Accuracy (including any tendency towards oscillatory behavior).
Stability.
Simulation time required.
The three best standard methods, in terms of accuracy, stability, and
simulation time are:
Upwind Differencing Scheme 1.
Quadratic Upwind Differencing Scheme.
Mixed Differencing Scheme.
The Biased Upwind Differencing Scheme and the Flux Limiter are
recommended in cases where the system is highly nonlinear and
breakthrough curves are very steep features associated with highly
nonlinear adsorption isotherms and near-equilibrium behavior. The Flux
Limiter technique gives the accuracy of a higher order technique, but with no
oscillations at small node counts.
Note that all second-order derivatives are approximated by a second-order
accurate central difference scheme, which is known to be accurate, stable,
and fast for all cases of interest.
For details on the integration of the resulting system of differential equations
with time, see the Aspen Custom Modeler Solver Options help.
About the Discretization Methods
To specify a discretization method:
On the General tab, in the Discretization Method to Be Used box, select
the method you require.

Choose from these options:
Upwind Differencing Scheme 1 (UDS1, first order)
Upwind Differencing Scheme 2 (UDS2, second order)
Central Differencing Scheme 1 (CDS1, second order)
Central Differencing Scheme 2 (CDS2, fourth order)
Leonard Differencing Scheme (LDS, third order)
Quadratic Upwind Differencing Scheme (QDS, third order)
Mixed Differencing Scheme (MDS, ~third order)
Biased Upwind Differencing Scheme (BUDS, fourth order)
Fromms scheme (FROMM, third order)
Flux limited discretization scheme (Flux limiter)
If you choose the Flux limited discretization scheme, you need to select one
of these suboptions:
OSPRE
SMART
van Leer
With schemes of higher order than UDS1 (first order), the bounds for some
variable types need modifying. This is because higher order methods that are
not flux limited tend to oscillate, so may return negative values for variables
types with a lower bound of zero. The typical changes required are:

Variable type Action normally required
g_Conc_Mol
l_Conc_Mol
i_Conc_Eq
Set the lower bound to minus the upper bound.
g_Loading
l_Loading
Set the lower bound to minus the upper bound.
i_Loading_Eq
Molefraction Widen the upper bound to 2, and set the lower
bound to minus the new upper bound.
Fraction Widen the upper bound to 2, and set the lower
bound to minus the new upper bound.
Upwind Differencing Scheme 1
Upwind Differencing Scheme 1 (UDS1) is the preferred option because it is:
Good all-round performer.
Unconditionally non-oscillatory.
Unconditionally stable.
Cheapest user of simulation time.
Reasonably accurate.
You increase accuracy by increasing the number of nodes. If you need greater
accuracy with a minimal increase in simulation time, use the Quadratic
Upwind Differencing Scheme. For Upwind Differencing Scheme 1 to achieve
the same level of accuracy, the number of nodes has to be increased by a
factor of two through four, leading to a similar increase in simulation time.
In most cases, use Upwind Differencing Scheme 1 first.
Derivation of Upwind Differencing Scheme 1
Upwind Differencing Scheme 1 is a first-order upwind differencing scheme,
based on a first-order Taylor expansion.
First-order (convection) term:
z z
i i i
=
Second-order (dispersion) term is approximated with a second-order accurate
central differencing scheme:
2
1 1
2
2
2
z z
i i i i

+
+
=
Evaluation of Upwind Differencing Scheme 1
Upwind Differencing Scheme 1 has the following advantages (+) and
disadvantages ():
+ Unconditionally stable (that is, it does not produce oscillations in the
solution).
+ Least simulation time.
Only first-order accurate.
Gives a large amount of so-called false or numerical diffusion.
(However, this problem decreases as the number of nodes is
increased.)
Upwind Differencing Scheme 2
The Upwind Differencing Scheme 2 (UDS2) option predicts sharper fronts
than Upwind Differencing Scheme 1, but the solution tends to oscillate.
Derivation of Upwind Differencing Scheme 2
Upwind Differencing Scheme 2 is a second-order upwind differencing scheme.
The first-order (convection) term:
z z
i i i i

2
4 3
2 1
+
=
2
1 1
2
2
2
z z
i i i i

+
+
=
Evaluation of Upwind Differencing Scheme 2
Upwind Differencing Scheme 2 has the following advantages (+)and
disadvantages ():
+ Second-order accuracy (because it includes a higher order derivative
than first-order upwind schemes).
May produce some numerical oscillations.
Central Differencing Scheme 1
Central Differencing Schemes 1 and 2 (CDS1 and 2) may be used if you
choose to include axial dispersion in the problem. They give good accuracy
with a reasonable CPU time requirement.
In a series of test problems, Central Differencing Scheme 1 used less CPU
time than Central Differencing Scheme 2, but produced greater oscillations.
Derivation of Central Differencing Scheme 1
Central Differencing Scheme 1 is a second-order central differencing scheme
and takes the form:
First-order convective term:
z z
i i
=
1 1
2

2
1 1
2
2
2
z z
i i i i

+
+
=
Evaluation of Central Differencing Scheme 1
Central Differencing Scheme 1 has the following advantages (+) and
disadvantages ():
+ Second-order accurate.
Numerical instabilities.
To overcome these instabilities, include axial dispersion in the bed model.
This may cause errors in simulation if there is little axial dispersion in the
beds, but these errors are no more inconvenient than the false diffusion
associated with upwind differencing.
Using Central Differencing Scheme 1 with axial dispersion may reduce the
number of nodes in the grid, allowing smaller simulation times.

Central Differencing Scheme 2
Central Differencing Schemes 1 and 2 (CDS1 and 2) are useful if you choose
to include axial dispersion in the problem. They can give good accuracy with a
reasonable CPU time requirement.
In a series of test problems, Central Differencing Scheme 2 produced smaller
oscillations than Central Differencing Scheme 1, but used more CPU time.
Derivation of Central Differencing Scheme 2
Central Differencing Scheme 2 is a second-order central differencing scheme
and takes the form:
First-order derivative:
z z
i i i i i

12
8 8
1 1 1 2 + +
+ +
=
2
1 1
2
2
2
z z
i i i i

+
+
=
Evaluation of Central Differencing Scheme 2
Central Differencing Scheme 2 has the following advantages (+)and
disadvantages ():
+ Third-order accurate.
Requires increased CPU time.
Leonard Differencing Scheme
The Leonard Differencing Scheme (LDS) is comparable with the Quadratic
Upwind Differencing Scheme:
Gives the same instability problems.
Less accurate.
Requires less CPU time.
Derivation of Leonard Differencing Scheme
The Leonard Differencing Scheme is a linear combination of the Central
Differencing Scheme 1 scheme and a second-order, four point finite
differencing scheme. This combination yields:
z z
i i i i

6
6 3 2
2 1 1 +
+ +
=
2
1 1
2
2
2
z z
i i i i

+
+
=
Evaluation of Leonard Differencing Scheme
The Leonard Differencing Scheme has the following advantages (+) and
disadvantages ():
+ Accurate.
Known to produce oscillations under convective conditions.
Quadratic Upwind Differencing
Scheme
If you need greater accuracy than the Leonard Differencing Scheme, with a
minimal increase in simulation time, use the Quadratic Upwind Differencing
Scheme (QDS).
The Quadratic Upwind Differencing Scheme is the most accurate of all the
methods for the same number of points.
Derivation of Quadratic Upwind Differencing Scheme
The Quadratic Upwind Differencing Scheme is based on quadratic
interpolation, as opposed to the linear interpolation typical of many other
schemes.
z z
i i i i i

8
7 3 3
2 1 1 +
+ +
=
2
1 1
2
2
2
z z
i i i i

+
+
=
The scheme is also referred to as QUICK (Quadratic Upstream Interpolation
for Convective Kinematics).
Evaluation of Quadratic Upwind Differencing Scheme
The Quadratic Upwind Differencing Scheme has the following advantages (+)
and disadvantages ():
+ Very accurate.
+ Little numerical dispersion.
+ Well suited to explicit (time) integration.
Oscillates under highly convective conditions.
Advantages of Quadratic Differencing Scheme: Example
Both the Quadratic Upwind Differencing Scheme and the Mixed Differencing
Scheme are more accurate than Upwind Differencing Scheme 1. They both
use about the same simulation time, which is typically about 25% more than
Upwind Differencing Scheme 1.
For Upwind Differencing Scheme 1 to achieve the same level of accuracy, you
must increase the number of nodes for Upwind Differencing Scheme 1 by a
factor of two through four, leading to an equivalent increase in simulation
time.

Aspen Adsim Breakthrough Plot
In this breakthrough plot, both the Quadratic Upwind Differencing Scheme
and the Mixed Differencing Scheme have 20 nodes. Initially, Upwind
Differencing Scheme 1 also had 20 nodes, which caused high numerical
diffusion.
The number of nodes in Upwind Differencing Scheme 1 is increased first to 50
and then to 100, to reduce this diffusion. The cost of this is increased
simulation time for Upwind Differencing Scheme 1.
Mixed Differencing Scheme
The Mixed Differencing Scheme is more stable than the Quadratic Upwind
Differencing Scheme, so may be the answer if the Quadratic scheme is
unstable.
Derivation of Mixed Differencing Scheme
The Mixed Differencing Scheme is a combination of the Quadratic Upwind
Differencing Scheme and the Upwind Differencing Scheme 1.
z z
i i i i

12
11 7 3
2 1 1 +
+ +
=
2
1 1
2
2
2
z z
i i i i

+
+
=
Evaluation of Mixed Differencing Scheme
The Mixed Differencing Scheme has the following advantages (+)and
disadvantages ():
+ Accurate.
Advantages of Mixed Differencing Scheme: Example
The Mixed Differencing Scheme is a compromise between accuracy and
stability. It uses slightly less simulation time than the Quadratic Upwind
Differencing Scheme.

Axial Profile Plot
This graph shows that Upwind Differencing Scheme 1 and Mixed Differencing
Scheme are the most stable of all the methods, while Central Differencing
Scheme 1 is the least stable.
Note that, in cases with initially clean beds, problems can sometimes be more
difficult to initialize with Mixed Differencing Scheme than with Upwind
Differencing Scheme 1.

Biased Upwind Differencing Scheme
It is known that:
High-order central difference approximations tend to produce excessive
oscillations upwind from a discontinuity.
Upwind difference schemes tend to produce excessive oscillations
downwind of a discontinuity.
Carver and Schiesser (1980) suggest that a correct combination of the two
largely cancels out these upwind and downwind oscillations. From this, they
developed a five-point biased upwind differencing scheme consisting of one
point downwind and three grid points upwind. The approximation is a
combination of central and upwind difference approximations. Results suggest
that the biased scheme performs better than classical approximations.
Use Biased Upwind Differencing Scheme (BUDS) when the system is highly
nonlinear, and where the presence of sharp fronts requires accurate solution.
Because of its fourth-order accuracy, BUDS provides good accuracy for a
smaller number of nodes than other lower-order approximations, while the
extra CPU time is small.
A potential drawback with BUDS is that, under certain circumstances, it also
produces oscillatory behavior. If this happens, then all the other linear
differencing schemes are also likely to suffer this problem, with the exception
of UDS1.
Derivation of Biased Upwind Differencing Scheme
The fourth-order Biased Upwind Differencing Scheme is based on a fifth-order
Taylor expansion.
First order (convection) term:
z z
i i i i i i

1 1 2 3
3 10 18 6
+
+ + +
=
Second order (dispersion) term is based on a second-order accurate central
differencing scheme:
2
1 1
2
2
2
z z
i i i i

+
+
=
Evaluation of Biased Upwind Differencing Scheme
The Biased Upwind Differencing Scheme has the following advantages (+) and
disadvantages ():
+ Fourth-order accurate, so gives good accuracy for small node counts
(so is especially suited to sharp fronts).
+ Simulation time only slightly larger than third-order schemes.
+ Good stability, and less likely to produce oscillations than other higher-
order linear discretization techniques.
May produce oscillations under extreme conditions.
Fromms scheme
Fromms scheme is the sum of a first order and a second order scheme. It
may produce instabilities for large ratios of time to spatial discretization step.
Derivation of Fromms' Scheme
First order (convection) term:
( ) { } { } ( )
z z
i i i i i i i

2 1 1 1
25 . 0
+
+
=

2
1 1
2
2
2
z z
i i i i

+
+
=
Flux Limited Discretization Scheme
Flux limited schemes combine the accuracy of higher order finite differencing
schemes with the stability of the first order upwind differencing scheme
(UDS1).
Derivation of the Flux Limited Discretization Scheme
The flux limited differencing scheme is:
( ) ( )
z
r
z
r
z z
i i
i
i i
i
i i i

2 1
1
1 1
2
1
2
1

Here is the flux-limiter function and r the gradient ratio, calculated as:
1
1
=
i i
i i
i
r

There are three versions of the flux-limiter function to choose from:
van Leer
OSPRE
SMART
2
1 1
2
2
2
z z
i i i i

+
+
=
6 Estimation with Aspen Adsim 236
6 Estimation with Aspen
Adsim
The chapter contains the following information about the Estimation Module:
Two Estimation Tools in Aspen Adsim 2004.1
About the Estimation Module
Defining Estimated Variables in the Estimation Module
Steady State Estimation Using the Estimation Module
Dynamic Estimation Using the Estimation Module
Performing Estimation Using the Estimation Module
Converting Estimation Module Data
Recommendations when Using the Estimation Module
Two Estimation Tools in Aspen Adsim
2004.1
Aspen Adsim 2004.1 has two estimation tools; one internal, and one external:
Estimation Module, which is the existing, internal estimation tool that has
been available since Aspen Adsim 10.0
This chapter describes how to use the Estimation Module.
Estimation features built into Aspen Custom Modeler, which are now
accessible from Aspen Adsim 2004.1:
Simulation engine data tables.
Automation (via any COM-compliant application).
This new development links Aspen Adsim more tightly to the overall
system. For more information, consult the Aspen Custom Modeler help
files. To do this, first open the Aspen Adsim 2004.1 help file, navigate to
the topic 'Two Estimation Tools in Aspen Adsim 2004.1', then use the
available links.
About the Estimation Module
The Estimation Module has been in existence since Aspen Adsim 10.0, It
provides an alternate estimation method to automation. The interface
simplifies the entry of:
Estimated variables.
Measured data.
Estimation solver options.
The Estimation Module provides two main types of estimation:
Steady-state (fitting constant parameters to static data).
Dynamic (fitting constant parameters to time-dependent data).
To access the Estimation Module:
On the Tools menu, click Estimation Module.
This places an Estimation Module block on the flowsheet, provided one is not
already there. The block opens to display the Estimation Module form. An
indication is given if either previously defined data or results are available.

The Estimation Module form contains:
Buttons for commonly performed tasks (these are on the right-hand side).
Tabs for different data types.
This table lists the buttons on the Estimation Module form:

Button name Description
Store Store entered information in flowsheet block.
Clear Clear all current data in the Estimation Module.
Load Replace current data with data stored in flowsheet
block.
Open Open version 10.0 estimation files.
Run Execute estimation run.
Help Open help page.
Copy Table Copy currently visible table onto the clipboard.
This table lists the tabs on the Estimation Module form:

Tab name Description
Estimated Variables Currently selected Fixed variables to be
estimated and their results (if available).
Experimental Data Measured experimental data.
Estimation Solver Options Solver options associated with estimation.
Defining Estimated Variables in the
Estimation Module
Use the Estimated Variables tab to define the variables that need to be fitted
against experimental data. A list shows those variables that have a Fixed
specification (assumed constant during the simulation), to a maximum of
three levels of submodel hierarchy. The list shows only the valid variables
that were available on opening.

To select a variable for estimation, select the adjacent box. All selected
variables are added to the table. In the table, you can:
Modify the initial value (guess).
Change the units of measurement of the initial value.
View the result after a successful estimation run, along with other
statistical information.
Steady-State Estimation Using the
Estimation Module
Aspen Adsim typically uses steady-state estimation to fit isotherm parameters
to static experimental data. For this purpose, the static_isotherm model is
provided, which gives access to both the standard inbuilt isotherms and user
defined isotherms.
The standard flowsheet for static isotherm fitting contains only a
static_isotherm block.
You can add any number of experiments. Each experiment:
Can be included in the estimation run.
Has an individual experimental weighting (the default value being 1).
Dynamic experimental data cannot used or entered.
Manually Entering Steady-State
Experimental Data
To add steady-state experimental data:
1 In the Experimental Data tab, click the Add button. The New Experiment
dialog box appears, where you select Steady-State experiment type.

The dialog box looks different if experiments already exist in the
Estimation Module. These must be of one type: steady-state or dynamic.
So as an example, if you are adding to a set of steady-state experiments,
then the dialog box only has the steady-state option.
2 Click OK to return to the Experimental Data tab.

This now has a list of the data sets, as well as extra tabs for adding
experimental conditions and measurements. You can weight each
experiment individually, the default being 1.
3 Define the experimental conditions using the variables added to the Fixed
Variables list, for example the temperature, pressure and mixture
composition.
Only variables that are Fixed, and which are chosen for estimation, can be
selected. The value of the Fixed variables can be modified.
4 Add measured data to the Measured Variables list. The following tips are
useful:
You can add any Free, Initial or RateInitial variable to the list.
The units of measurement are those currently active.
Each experimental point can have an individual weighting applied, the
default weighting being 1.
When additional experiments are added, the same variables can be
copied from the currently active experiment.
Steady-State Experimental Data from
the Clipboard
To import steady-state experimental data, for example from Microsoft
Excel:
1 Create a new steady-state experiment, as described in Manually Entering
Steady-State Experimental Data on page 6-239. The experimental name
is used as the prefix for any copied experiment.
2 When creation is complete, you are prompted with a dialog box asking if
you want to copy data from Microsoft
Excel. Click the Yes button.

3 The Obtain Steady State Experiments From Clipboard dialog box appears,
which requires copied data to function. Leave this dialog box untouched
for now.

4 Open Microsoft
Excel and copy the data set to the clipboard.

The Estimation Module assumes that copied data takes this format:
Each row is a single experiment.
Columns represent experimental variables (normally, you list the
manipulated variables first, followed by the measured variables).

5 Return to the Obtain Steady State Experiments From Clipboard dialog box,
and click the Paste button. A populated table now appears in the dialog
box.

6 For each column of data, mark whether it is a varied (manipulated) or
measured variable. To do this, select the column and click either the
Varied or Measured buttons.
A list appears, from which you select the appropriate variable for the
column.

7 Transfer the pasted data to the Estimation Module, either by clicking the
Close button or the Process button.
The experiments created on processing the data are added to any
other existing experiments in the Estimation Module.
If any bounds are exceeded, a further dialog box opens in which you
can automatically readjust the bounds for all variables of a similar type
in the simulation.
Dynamic Estimation Using the
Estimation Module
Use dynamic estimation whenever the experimental data is time-dependent,
for example the measured outlet composition over time. Aspen Adsim does
not assume a specific flowsheet layout, or the use of specialized models. You
can use a standard process flowsheet that includes any operational task.
Manually Entering Dynamic
Experimental Data
To add dynamic experimental data:
1 In the Experimental Data tab, click the Add button. The New Experiment
dialog box appears, where you select the Dynamic experiment type.

The New Experiment dialog box looks different if experiments already
exist in the Estimation Module. These must be of one type: steady-state
or dynamic. So as an example, if you are adding to a set of dynamic
experiments, then the dialog box has only the dynamic option.
2 Click OK to return to the Experimental Data tab.

The Experimental Data tab now has a list of the data sets, as well as extra
tabs for adding experimental conditions and measurements. You can
weight each experiment individually, the default weighting being 1.
3 Define the experimental conditions using the variables added to the Fixed
Variables and Initial Variables list, for example the temperature, pressure
and mixture composition.
Only variables that are Fixed, and which are chosen for estimation, can be
selected. The value of the Fixed and Initial variables can be modified.
4 Add measured data to the Measured Variables list.
You can add any Free, Initial or RateInitial variable to the list.
A new tab is created for each measured variable, through which you
define the time dependency.
When new variables are added to an experiment, it is possible to copy
the same time points from the currently selected variable.
The units of measurement for any variable are those currently active.
Each experimental point can have an individual weighting applied (the
default value is 1).
Dynamic Experimental Data from the
Clipboard
To import dynamic experimental data, for example from Microsoft
Excel:
1 Create a new dynamic experiment. When this is completed, the Paste
Data button is enabled:

2 The Obtain Dynamic Measurements for Experiment DynExpt From
Clipboard dialog box appears, which needs copied data to function. Leave
this dialog box untouched for now.

3 Open Microsoft
Excel and copy the data set to the clipboard.

The Estimation Module assumes that copied data takes this format:
Each row represents a time point.
Columns represent experimental variables.

4 Return to the Obtain Dynamic Measurements for Experiment DynExpt
from Clipboard dialog box and click the Paste button. A populated table
now appears in the dialog box.

5 For each column of data, mark whether it is the time of measurement, or
the measured variable. To do this, select the column and click either the
Time or Measured buttons. For measured variables, a list appears, from
which you select the appropriate variable for the column.

6 Transfer the pasted data to the Estimation Module, either by closing the
dialog box, or by clicking the Process button.
The experiments created on processing the data are added to any
other existing experiments in the Estimation Module.
If any bounds are exceeded, a further dialog box opens in which you
can automatically readjust the bounds for all variables of a similar type
in the simulation.
Performing Estimation Using the
Estimation Module
To perform an estimation using the Estimation Module, click the Run button
and leave the module open during the run. You cannot interact with the
module during a run.
After a successful estimation run, the module retrieves the results and stores
them in the Estimation Module block on the flowsheet. The following results
are available:
Final estimated value
Standard deviations
Correlation matrix
Covariance matrix
Converting Estimation Module Data
To convert from using the (old) Estimation Module to the (new) estimation
tools available in Aspen Custom Modeler, use the script Convert_EstMod
located in the Aspen Adsim library Script folder.
To use the script:
1 Open the input file you want to convert.
2 Double-click the script in the library.
After the script has converted the data, the Estimation Module block
disappears from the flowsheet.
To view the experimental data, from the Tools menu click Estimation,
which accesses the new estimation system.
3 Save the input file.
Recommendations When Using the
Estimation Module
The following tips will help you get the best out of the Estimation Module:
To check that the initial values used for the variables to be estimated give
a converged solution, complete these two steps:
Execute a steady-state run for steady-state estimation.
Execute an initialization run for steady-state estimation.
These two steps are important as they ensure that the first iteration of the
estimation solver will succeed.
Use estimation solver tolerances that are greater than the general solver
options.
If simulation convergence gives rise to multiple solutions, try a different
initial guess.
Try to measure variables that are sensitive to the estimated variables.
Singular convergence normally indicates an insensitive measured variable.
Check the bounds of the estimated variables. For example, ensure the
lower bound of a strictly positive isotherm parameter is zero.
The fit is only as accurate as the range of data presented by the
experiments, so include more than one set of experimental data. For
example, with a single data set, the estimated value is useful only for the
operating range of the data.
7 Cyclic Operation 249
7 Cyclic Operation
Many adsorption processes operate in a cyclic manner. Each cycle is described
by a series of single or multiple sequential steps or discrete events. When
simulating a cyclic process, you must be able to specify when certain events
are going to occur.
Aspen Adsim contains a Cycle Organizer for you to define cyclic operations.
This chapter contains information on the following topics:
Cyclic Operations in Aspen Adsim 2004.1
About the Cycle Organizer
Opening the Cycle Organizer
Cycle Organizer Window
Step Control
Step Variables
Interaction Control
Additional Cycle Controls
Additional Step Controls
Generating Cyclic Tasks
Activating and Deactivating Tasks
Cyclic Reports
Cyclic Operations in Aspen Adsim
2004.1
In Aspen Adsim 2004.1, the Configure form has been extensively modified to
allow for many new features. Input files created in previous releases are still
compatible. When you open the Cycle Organizer, the old cycle definitions are
automatically converted to match the new system, and the old cyclic task is
automatically deleted. You then need to regenerate the cyclic task.
About the Cycle Organizer
The Cycle Organizer lets you rapidly create the steps that define a cyclic
process. Use it to:
Create any number of steps.
Define the step termination event.
Manipulate flowsheet variables for a given step.
Generate a cyclic task based on the Task Language.
Distribute cycle information to other flowsheet blocks through global
variables.
Store multiple cycle definitions.
Control variable recording and automated snapshots.
Execute V(isual)B(asic) scripts for additional calculations and control.
Here is some more information about the Cycle Organizer:
The main Configure form gives the status of the system and the active
state of the cyclic task.
All entered data is stored in the block on the flowsheet. This allows the
data to be saved with the flowsheet input file.
Only one Cycle Organizer block is allowed on the flowsheet.
When you configure the flowsheet for cyclic operation, it is advisable to
configure it as if it is about to execute the first step of the cycle.
On adding a new step, you are asked two questions:
Is the new step to be placed before or after the currently selected
step?
Is the information to be copied from the currently selected step into
the newly created one (to act as a template).
Opening the Cycle Organizer
To access the Cycle Organizer:
From the Tools menu, click Cycle Organizer.
If a Cycle Organizer block does not exist on the flowsheet, one is
automatically placed on the flowsheet and the Cycle Organizer window
appears. The block looks like this:

To open Cycle Organizer block present on the flowsheet, use either the Tools
menu or double-click the flowsheet block.
Cycle Organizer Window
The Cycle Organizer window looks like this:

The Cycle Organizer toolbar gives access to the various fields and controls
needed to define and generate a cyclic task.
The table lists the main buttons on the toolbar, their purpose, and the options
available on their drop-down menus. (The Print and Online button are not
described.)

Toolbar button Purpose Options
Cycle Cycle controls, such as
creating and activating
cycles.
Cycle Options
New Cycle
Generate Task
Activate Cycle
Delete Cycle
Step Step controls, such as
modifying and inserting
steps.
Control
Manipulated
Interactions
Other
Add/Insert Step
Delete Step
Variable
(available only if you
selected Manipulated from
the Step menu)
Adding or Deleting
variables.
Add Variable/s
Delete Variable/s
Step Control
There are three ways to define the termination of a given step:
Explicit time, where termination is linked to elapsed time.
Discrete event, where termination is linked to an event, such as when a
vessel has reached a given pressure.
Dependent on another step.
If the step is the second half of an interaction, the step is controlled by the
elapsed time for the interactions first half. This ensures step symmetry within
the cycle.
To access the step control panel:
In the Cycle Organizer window, click the Step toolbar button; or from the
neighboring drop-down menu, click Control.
Time Driven Step
Time Driven Step is the most common step control method. Here, the step
control is a fixed elapsed time; for example, the step is set to terminate after
60 seconds. The step time remains constant from cycle to cycle.
To select a time-driven step control:
Enable the Time Driven radio button and give the step time in the
specified units:

When the cyclic task is generated, the value is automatically converted to the
base time units assumed by the models. Likewise, should the time unit of
measurement change, any variable that is ramped in the current step, and
any dependent or interacting step, automatically have their times and time
units modified.
Discrete Event Driven Step
Event-driven step controls are implicit events, for which the time of
occurrence is unknown. For example, "the step will terminate when a vessel
has reached a given pressure". To define the event, enable one of these three
radio buttons:
Value a comparison between a Free variable and a value defines the
event.
Variable a comparison between a Free variable and another variable
defines the event.
Expression a complex expression defines the event.
Discrete Event Driven Step: Variable/ValueComparison
With Value as your choice of step control, a comparison between a Free
variable and a value defines the event.

To define the event:
1 Enable the Value radio button.
2 Specify the monitored variable, either by selecting it from a list of
variables, or by typing the exact name.
3 Select a comparison operator from:
== Equal to
<> Not equal to
<= Less than or equal to
>= Greater than or equal to
4 Give the value for comparison, in the unit of measurement of the
monitored variable.
The unit of measurement can be modified.

Discrete Event Driven Step: Variable/Variable Comparison
With Variable as your choice of step control, a comparison between two
variables defines the event.

The procedure for this is similar to the Value option, described in the previous
subsection, except that you must specify two variables:
Monitored variable.
Variable to make the comparison with.
Discrete Event Driven Step: Complex Expression
With Expression selected, a complex expression that is built up from logical
operators defines the event.
This is useful when the step termination depends on a true or false condition.

To define the expression:
1 Enable the Expression radio button.
2 Double-click in the Expression text box.
The Expression Builder dialog box appears, where you create expressions:

3 Insert typical operations for the comparisons, using the buttons provided.
A searchable list is provided to ensure that you insert only valid variables
into the expression.

Note: No error checking is provided for the expression entered,
so take care to enter values that are within the valid bounds and
in the compared variable's base unit of measurement.
Discrete Event Driven Step: Step Dependent
The final method of step control is to make the step dependent on a previous
step.

To use this option:
1 Enable the Step dependent radio button.
2 In the neighboring drop-down menu, specify the dependent step.
Only steps that occur before the current step can be selected. Likewise,
this option is not available for the first step in any given cycle.
If the step for which a dependency is being defined, is the start of a chain of
step interactions, all interacting steps assume the elapsed time and time unit
of measurement of the dependent step. Likewise, all ramp times will be
checked and converted to the new time unit of measurement.
Step Variables
Within each step of a cycle, different variables may be modified. These
variables may control, for example:
Feed condition
Valve opening
Heater duty
The variable change may be stepped or a gradual/ramped change.
To access the list of manipulated variables:
From the Step button's drop-down list, click Manipulated.
Adding Step Variables
To add a new manipulated step variable:
1 Click the Variable button on the toolbar; or from its drop-down list, click
Add Variable/s.
The Variable Selector dialog box appears, which lists the available fixed
and initial variables that have not already been selected in the current
step.

2 Select a variable using one of these actions:
Double-click on the variable in the list.
Type the name of the variable in the text box at the top of the dialog
box (a dynamic search takes place during typing).
Select multiple variables, using either the SHIFT or CTRL key.
Use wildcards in the text box to reduce the list size and then select.
Valid wildcards are:
* for any character combination.
? for a single character place holder.
Note the following points:
There is no limit to the number of variables that can be manipulated in a
given step.
You can access all variables in the flowsheet, except global variables.
Selected variables are listed alphabetically in the table.
Removing Step Variables
You remove step variables directly from the Cycle Organizer window.
To remove a single manipulated variable:
1 Select the row of the required variable.
2 From the Variable button's drop-down menu, click Delete Variable/s.
To remove a series of variables in contiguous rows, select the rows to be
deleted.
Changing Step Variable Values

For each defined manipulated variable, the following fields are given:

Field Description
Value Value of the variable for the current step. A check is made to
ensure the value is within the bounds for the variable in the
current unit of measurement. If a bound is violated, you can
automatically adjust bounds for all variables of the same type.
Units Unit of measurement. To modify this, double-click the field and
a drop-down menu appears. On changing the unit of
measurement, any values provided for the Value and Target
fields are automatically recalculated.
Spec Specification of the variable. This cannot be modified.
Ramped Variable to be ramped. Double-clicking this field displays a
drop-down menu, where you choose between no ramping,
linear ramping or S-shaped ramping.
Target Target value of the ramp. This is visible only for ramped
variables. For ramped variables, the number in the Value
column is used as the initial starting point of the ramp.
Time Elapsed time of a ramp. This is visible only for ramped
variables.
For time-driven steps, the value entered here cannot be
greater than the step time.
With discrete event-driven steps; if the event occurs before the
ramp has completed, the step terminates when the ramp has
completed.
There is no limit to the number of variables that can be ramped in a given
step.
Interaction Control
If the flowsheet contains interaction units (see Single Bed Approach in
Chapter 7), the Step toolbar's drop-down menu contains an Interactions
option:
This option accesses the Interaction Control table, which lists the interaction
units and the currently defined step interactions.
Defining a Step Interaction
To define a step interaction:
Double-click on the step containing the source material, and from the
drop-down list, select the step in which the material is returned.

Note the following points about step interactions:
Once you select an interacting step, the target cell updates automatically.
The last row also shows the root defining step for any interactions. This
step defines the elapsed time for all associated interacting steps.
Interaction numbers are:
Positive for forward interactions, where material is accepted early in
the cycle and returned later in the same cycle.
Negative for reverse interactions.
A single interaction unit is not restricted to a single set of interacting
steps; it can be reused for any number of interacting step sets. However,
only a single quantity of material can be accepted or returned for a given
step. For this reason, if you want to transfer multiple amounts of material
in a step, you must use more than one interaction.
Deleting Interaction Steps
To delete an interaction:
From the drop-down list, click None.
Adding Extra Interaction Steps
If you insert additional steps before or between existing interacting steps, the
interaction numbers are renumbered automatically. For example, if you insert
a step between the interacting steps 1 and 3 for unit D1, the new interacting
steps are now 1 and 4.
Interacting Steps and Time Controls
Once you have defined an interacting pair of steps, the second half of the pair
is forced to be time controlled. This ensures time symmetry and maintenance
of the material balance between interacting steps.

The time control is based on:
Fixed time for a time driven step.
Elapsed time for an event driven step.
The Cycle Organizer continually checks the root defining steps of all
interactions, to ensure time controls are in place.
Explanation of Why Time Controls Are Imposed
A single step cannot receive material from both a time driven step, and one
that is event driven; nor from two similarly controlled steps that use different
times or events. This is because the duration of an event driven step may
change from cycle to cycle, so the elapsed time can vary.
For example, in a five-step process using three interaction units, step 1 is
time driven, and step 2 event driven. Interaction unit D1 has interactions
13 and 54; interaction unit D2 has a single interaction 24; interaction
unit D3 has a single interaction, 35.

The table suggests that step 3 is time driven, and step 4 is time driven based
on the elapsed time of the event in step 2. In step 5, however, we have two
interactions: one with step 4 (assumed event driven) and the other with step
3 (assumed time driven). In this instance, the step that occurs first is
assumed as the root defining step. Thus steps 2 through 5 are all dependent
on the elapsed time of step 1.
Additional Cycle Controls
To access additional cycle controls:
Click the Cycle toolbar button, or from the buttons drop-down menu, click
Cycle Options.
The additional controls provided for the overall cycle include:
Number of cycles to execute.
Record frequency.
End of cycle snapshots.
Cycle steady-state testing.

Maximum Cycles Box
Use the Maximum Cycles box to specify the maximum number of cycles to
execute in a given run. It is coupled to the Record Initial and Record
Frequency options.
Assuming you have set the run options for indefinite running, the simulation
automatically pauses once the given number of cycles has been performed.
Click the Play button again to execute a further batch of cycles.

Record Initial and Record Frequency
Boxes
Use the Record Initial box to specify the number of cycles at the start of the
simulation for which the record attribute remains on. This applies only to
variables that have it set to true and time equals zero.
Use the Record Frequency box to specify the cycle at which the record
attributes are switched off and then back on for a single cycle.
If you set these two options to 1, the variables are recorded for all cycles.
If you set Record Initial to 5, Record Frequency to 10, and the Maximum
Cycles to 25, variables are recorded only for cycles 1, 2, 3, 4, 5, 15 and
25. This significantly reduces the size of the plot data file.
When using these options, the maximum number of cycles is always
automatically modified to ensure the last cycle executed is recorded.
Take Snapshot Box
To automatically take a snapshot at the end of every cycle (or cycles based
on the settings for Record Initial and Record Frequency):
Select the Take Snapshot at End of Cycle box.
Taking a snapshot at the end of each cycle is useful if you want a material
balance at points during the run. The simulator uses the snapshots to rewind
to a time point in history.
Cyclic Steady State Testing Box
Select the Cyclic Steady State Testing box to test when the dynamic cyclic
simulation has reached a periodic, cyclic, steady state. You need to set a
tolerance for this option to work.
During the simulation, the total loading and total solid temperature at the end
of a cycle are compared to the value of the previous cycle.

When their relative difference is below the test tolerance, the simulation
pauses.

If the Record Initial and Record Frequency are not equal to 1, the simulation
automatically pauses after the next recorded cycle.
Additional Step Controls
To access the additional step controls:
Click the Step toolbar button, or from the buttons drop-down menu, click
Other.
The additional controls provided for the overall cycle include:
Execution of a named script.
End of step snapshots.

Execute End of Step Script Box
Select this box to run a flowsheet level script at the end of a step, for every
cycle. This is useful for executing external calculations or runtime logging.
Specify the script in the Script Name box. If the script does not exist during
cyclic task generation, a template script with the name provided is
automatically created.

Take Snapshot at End of Step Box
To automatically take a snapshot at the end of step for every cycle (or cycles
based on your settings for Record Initial and Record Frequency settings):
Select the Take a Snapshot at End of Step box.
Taking a snapshot at the end of each cycle is useful if you want a material
balance at points during the run. The simulator uses the snapshots to rewind
back to a time point in history.
Generating Cyclic Tasks
Once a new cycle has been defined, or changes made to an existing
definition, the cyclic task needs generating before the simulation can be run.
This is indicated in the Cycle Organizer status bar, as follows:

To generate the cyclic task:
From the Cycle button's drop-down menu, click Generate Task.
View the Cycle Organizer status bar to see how the generation is progressing:
You see when the cyclic task has been successfully
generated (should there be any errors, these will be given in the
simulation messages window).
You see when there is another inactive cycle.
Note the following points:
If any variable in a step is ramped, additional tasks are generated. The
"callable" task contains a single ramp statement. The names of these
additional tasks are prefixed by the main task name, followed by an index
indicating the step and the manipulated variable.
Generated cyclic tasks are created using the Task Language. You can open
and edit tasks using this language, but any changes you make are lost if
you regenerate the task using the Cycle Organizer.
Only a single cycle definition can be active. If there is more than one cycle
description stored within the Cycle Organizer, whenever it is opened it will
always display the currently active cycle (or the first cycle definition
should no cycle be active).
Activating and Deactivating Cyclic
Tasks
Use the Cycle Organizer to activate and deactivate cyclic tasks.
If cyclic tasks have been generated for all cycle definitions stored within the
Cycle Organizer, you must not activate and deactivate the task by double-
clicking the task in the Flowsheet section of Simulation Explorer.
To activate a cycle:
With the cycle currently inactive , from the Cycle drop-
down menu, click Activate Cycle.
To deactivate a cycle:
With the cycle currently active , from the Cycle drop-
down menu click Deactivate Cycle.
This also deactivates any other currently active cycle definition.
Cyclic Reports
Cyclic reports are now available that provide information on the quantity and
quality of material passing along a stream during any step, and any cycle.
In overview, you are picking out information about particular steps and
cycles, from the larger Block and Stream reports. Cyclic reports therefore
require:
A Cycle Organizer on the flowsheet.
Block and Stream reporting enabled.
There are two types of Cyclic report:
Cyclic Stream reports
Cyclic Recovery reports
Preparing Aspen Adsim for Cyclic
Reporting
Before you start your simulation, you need to enable Block and Stream
reporting, and specify when to stop recording information for the Cyclic
report.
To prepare for cyclic reporting:
1 From the Tools menu, point to Report and then click Reporting.
The Flowsheet Reporting dialog box appears:

2 Select the Enable blocks/streams reports box, and underneath, state the
number of recorded cycle histories.
3 Click OK.
When you now run the simulation, step-by-step and cycle-by-cycle
information is recorded, until the number of cycle histories is reached (this is
11 cycles in our example).
Cyclic Stream Reports

The Cyclic Stream report gives the following information, based on either a
total cycle or on an individual step, for each direction of every Aspen Adsim
stream on the flowsheet:
Total material passed.
Cycle or step averaged flowrate.
Total of component passed.
Cycle or step averaged component composition.
Total energy passed.
Cycle or step averaged enthalpy.
It also gives the start time, end time and the elapsed time of the selected
cycle or step.
Creating Cyclic Stream Reports
You create Cyclic Stream reports for either a cycle or a step.
To create a Cyclic Stream report:
1 From the Aspen Adsim Tools menu, point to Report and click Stream
Report.
The Cyclic Report dialog box opens.

You now build the report to view it.
2 Enable either the Cycle radio button or Step radio button.
3 In the Cycle number list, select a cycle number.
For a step report, you also need to select a step.
4 Click the Build button, or from its drop-down menu click Stream Report.
This builds and then displays the Cyclic Stream report.
Cyclic Stream reports can be:
Copied to the clipboard, where additional information is added, such as
the date and time, and input file name.
Printed to the default printer, which prints only the currently visible
columns of the report. The report can be resized.
Cyclic Recovery Reports

The Cyclic Recovery Report gives the following recovery information for every
product stream with respect to every feed stream:
Total material
Individual component
Total energy
Creating Cyclic Recovery Reports
You create Cyclic Recovery reports for either a cycle or a step.
To create a Cyclic Recovery report:
1 From the Aspen Adsim Tools menu, point to Report and click Stream
Report.
The Cyclic Report dialog box opens.

You now build the report to view it.
2 Enable either the Cycle radio button or Step radio button.
3 In the Cycle number list, select a cycle number.
For a step report, you also need to select a step.
4 From the Build button's drop-down menu, click Recovery Report.
This builds and then displays the Cyclic Recovery report.
8 Flowsheeting 268
8 Flowsheeting
This chapter contains information on:
About model types
General model types
Reversibility
About flowsheets in Aspen Adsim
Types of Flowsheet in Aspen Adsim
Single bed approach
Pressure interaction diagram
Interactions
Specifications for flowsheets
Physical properties
Connecting to Aspen Dynamics flowsheets
About Model Types
For reversible flow within an Aspen Adsim flowsheet, you need to make some
modeling assumptions that define the type of flowsheet interactivity. These
assumptions are broadly similar between gas, ion-exchange and liquid
systems.
The models in the Aspen Adsim library support these flow regimes:

8 Flowsheeting 269
General Model Types
The general model types available in Aspen Adsim are:

Model type Used in Description Typical
models
Non-Reversible Gas
Ion-Exchange
Liquid
Assumes that there is no flow reversal in
the model. Material flow is from
Process_In to Process_Out.
All models
(except for
adsorbent/resin
beds) can be
configured in this
way.
Reversible Flow
Setter
Gas Relates pressure drop across the model to
the flowrate through the model.
Able to specify the flowrate directly.
The model does not contain any material
holdup, but may contain a momentum
balance.

Typical models:
gas_bed,
gas_valve,
gas_ramp.
Reversible Pressure
Setter
Gas Accumulates material and energy
(adsorbent beds are an exception).
The pressure at each port is equated
directly to the internal pressure.
Able to specify the pressure directly.
.
gas_tank_void,
gas_buffer_intera
ction, gas_feed,
gas_product.
Non-Reversible Delay Gas Used as part of an interaction train.
Stores stream information or passes
downstream/upstream pressure
information.
gas_valve,
gas_ramp,
gas_interaction.
Reversible Ion-Exchange
Liquid
Feed or product train to allow for
reversible flow.
Feeds, products,
valves, tanks,
distributors.
Reversibility
You get reversibility within the flowsheet by categorizing the models into
certain types.
Consider the gas phase system as a typical example:
The usual modeling approach is to equate the outlet condition to either the
internal condition (a tank for example) or inlet condition (a valve for
example).
8 Flowsheeting 270
Y
1
T
1
P
1
H
1
Y
2
T
2
P
2
H
2
F = (P
s1,out
,P
s2,in
)
Y
s1,out
= Y
s2,in
T
s1,out
= T
s2,in
H
s1,out
= H
s2,in
Y
s1,in
= Y
1
T
s1,in
= T
1
P
s1,in
= P
1
H
s1,in
= H
1
Tank1
Valve
Tank2 Y
s1,in
= Y
s1,out
T
s1,in
= T
s1,out
P
s1,in
= P
s1,out
H
s1,in
= H
s1,out
Y
s2,in
= Y
s2,out
T
s2,in
= T
s2,out
P
s2,in
= P
s2,out
H
s2,in
= H
s2,out
S1 S2

This approach works if the pressure in tank 1 is greater than, or equal to the
pressure in tank 2. To allow for a reversed pressure profile, the stream
condition must not be directly related to the tank condition, otherwise the
model becomes singular. This is where the model type is introduced.
To allow for reverse flow between tanks 1 and 2, the stream condition needs
to be determined not by the tanks, but by the unit in-between, the valve unit.
The valve uses the following information to ensure the appropriate flow
condition is selected:
Internal composition of the tanks, from the tank units.
Pressure difference across the valve itself.
We now introduce the concept of flow setter models and pressure setter
models:
As the valve model sets the stream conditions and determines the flow,
the underlying model is described as a flow setter.
The tanks accumulate only material and energy, and relate their pressure
to this accumulation, so the underlying model is described as a pressure
setter.
To finally accomplish this task, the streams must carry information, such as
the internal condition of the pressure setters (the tanks), as well as the actual
stream condition.
8 Flowsheeting 271
Y
1
T
1
P
1
H
1
Y
2
T
2
P
2
H
2
F = (P
s1,out
,P
s2,in
)
Y
s1,out
= Y
s2,in
T
s1,out
= T
s2,in
H
s1,out
= H
s2,in
If P
s1,out
>= P
s2,in
Then Y
s1,out
= Y
s1,out,r
Else Y
s2,in
= Y
s2,in,r
If P
s1,out
>= P
s2,in
Then T
s1,out
= T
s1,out,r
Else T
s2,in
= T
s2,in,r
If P
s1,out
>= P
s2,in
Then H
s1,out
= H
s1,out,r
Else H
s2,in
= H
s2,in,r
Y
s1,in,r
= Y
1
T
s1,in,r
= T
1
P
s1,in
= P
1
H
s1,in,r
= H
1
Tank1
Valve
Tank2
Y
s1,in
= Y
s1,out
Y
s1,in,r
= Y
s1,out,r
T
s1,in
= T
s1,out
T
s1,in,r
= T
s1,out,r
P
s1,in
= P
s1,out
H
s1,in
= H
s1,out
H
s1,in,r
= H
s1,out,r
S1 S2
Y
s2,in
= Y
s2,out
Y
s2,in,r
= Y
s2,out,r
T
s2,in
= T
s2,out
T
s2,in,r
= T
s2,out,r
P
s2,in
= P
s2,out
H
s2,in
= H
s2,out
H
s2,in,r
= H
s2,out,r
Y
s2,out,r
= Y
2
T
s2,out,r
= T
2
P
s2,out
= P
2
H
s2,out,r
= H
2

By using an alternating sequence of pressure and flow setters, you can model
process trains where reversibility may occur, without causing singularities.
For adsorbent and resin beds, it is important that the discretization scheme
used to solve the partial differential equations can cope with flow reversal at
either the inlet and outlet boundaries, or internally.
8 Flowsheeting 272
1 2 n-1 n
1 2 n-1 n
1 2 n-1 n
Forward Direction
Reverse Direction
Discretization
Nodes
Outlet
Boundaries
Inlet
Boundaries
Process Out
Process Out
Process In
Process In
1 2 n-1 n
Outlet
Boundaries
1 2 n-1 n
Inlet
Boundaries

The scheme used within the adsorbent and resin models assumes a constant
discretization mesh, with the boundaries evaluated at each local node with
respect to the flow and/or pressure gradient. This approach allows for the
chosen discretization method to automatically switch between forward and
backward differencing.
About Flowsheets in Aspen Adsim
You create Aspen Adsim flowsheets either interactively through the graphical
user interface, or from a prepared template. The available models are
classified into three main phases or types:
Gas
Ion-exchange
Liquid
You can mix these phase types on a flowsheet, subject to these restrictions:
Use a common global component list.
8 Flowsheeting 273
Interconnect model blocks using only the appropriate stream type for the
phase or model type. The only exception is a gas phase model block,
which can contain a liquid outlet to remove any condensed material.
The flowsheeting environment is very flexible, allowing you to create any
process flowsheet subject to these restrictions:
Overall model size versus simulation speed.
Available models/process operation descriptions.
Hardware limitations.
The flowsheet scope should ideally cover only the adsorbent columns and any
immediate equipment required to operate the process.
When creating new problems, it is good practice to start with a simple
flowsheet to ensure the column model assumptions are correct. Once
validated, you can then add further complexity, such as column deadspaces,
interaction units, other columns and cyclic behavior.
Connectivity on Flowsheets
You must use the correct material connection (stream) when connecting
model blocks on the flowsheet:

Model prefix Stream type
gas_ gas_Material_connection
ionx_ ionx_Material_Connection
liq_ liq_Material_Connection
Create the connections by dragging and dropping from the library to the
flowsheet. Connectivity is enforced by the port types used by each library
model and material connection:

Model prefix Port type
gas_ g_Material_Port
ionx_ i_Material_Port
liq_ liq_Material_Port
So, a model with the prefix 'gas_' accepts only connections made with a
gas_Material_Connection.
The ports and material connections pass the following information between
model blocks (depending on phase or type):
Molar/Volumetric flowrate
Molefraction composition/Component concentration
Molar density
Absolute temperature
Pressure
Specific enthalpy
8 Flowsheeting 274
Controllers are not connected using material connections; they use a special
stream type called ControlSignal instead. ControlSignal connects a single
exposed variable from one model block to another single exposed variable in
the same or another model block.
Templates
Predefined process templates are available through the Template Organizer.
To access this:
From the File menu, click Templates.
The Template Organizer appears:

The available templates feature:
Recommended solver options.
Runtime options set to the appropriate time units.
Default component list configured for use with Fortran-based physical
properties and populated with dummy components.
Flowsheet layouts based on standard descriptions.
Before copying a template to the current working directory, a name is
requested, which is then used for both the input file and the directory that
houses all the files for the new problem.
Demonstrations
All of the examples in the Aspen Adsim casebook come as part of the
standard installation. These casebook examples are a further source of
process templates.
8 Flowsheeting 275
To access the example files:
From the File menu, click Demonstration Organizer.
The Demonstration Organizer appears:

To open a casebook example:
Select the problem of interest and click Open.
You are told if a set of files will be copied, or if a copy of the example already
exists.
Types of Flowsheet in Aspen Adsim
There are three types of flowsheet in Aspen Adsim:
Simple flowsheet
Intermediate flowsheet
Full flowsheet
Types of Flowsheet: Simple Flowsheet
The simple flowsheet is the smallest workable flowsheet to operate an
adsorbent/resin bed. It is a recommended starting point for new simulations.
Use it to:
Ensure the absorbent/resin bed works effectively.
Simplify testing of key parameters and configuration assumptions.
The simple flowsheet typically includes the following unit operations for all
phases or types:
8 Flowsheeting 276
Feed boundary unit.
Adsorbent/resin bed (can contain any number of layers).
Product boundary unit.
Adsorbent or
Resin Bed
Product Boundary
Feed Boundary

Intermediate Flowsheet
The intermediate flowsheet is useful for simulating non-interacting adsorption
cycles. It builds upon the simple flowsheet by including (except for ion-
exchange):
Adsorbent bed deadspaces or voids.
Feed and product valves.
8 Flowsheeting 277
Adsorbent
Bed
Product Boundary
Feed Boundary
Top
Deadspace
(Tank)
Bottom
Deadspace
(Tank)
Product Valve
Feed Valve

Use the intermediate flowsheet to simulate:
Co-current or counter-current adsorption.
Repressurization and depressurization.
Purge using streams of different compositions.
Full Flowsheet
The full flowsheet is the final step in flowsheet complexity. It builds on either
the simple or intermediate flowsheet by including:
Interactions with other adsorbent/resin beds.
Additional feed or product trains.
Intermediate buffer tanks or pressure receivers.
Feed and product pumps.
To simulate interacting beds, there are two levels of overall model
complexity:
8 Flowsheeting 278
Single bed approach this uses a single bed to simulate processes
containing more than one bed.
Rigorous multi-bed this simulates all adsorbent/resin beds with
interconnecting units.
Single Bed Approach
An inherent problem when modeling an adsorption system is the number of
equations to be solved, the majority of which are discretizations of the partial
differential equations.
One way of modeling adsorption systems that comprise multiple
adsorbent/resin beds, is to use the single bed approach. For the method to be
valid:
Each adsorbent/resin bed (or series bed train) must be identical.
Each adsorbent/resin bed must undergo the same steps in a given cycle.
If these assumptions are met, then you can rigorously model a single real
adsorbent/resin bed and store any information (material) that would normally
be sent to an interacting bed. This stored information can then be replayed
back to the real bed later in the cycle.
The single bed approach retains the accuracy of the final results (see the
spreadsheet included within the installation):
Same average purity.
Same number of cycles to achieve cyclic steady-state.
Simulation speed is also improved:
Fewer equations (due to fewer beds).
Less data to be communicated between the client (GUI) and the server
(simulation engine).
Pressure Interaction Diagram
Before creating a flowsheet, it is important to sketch out the pressure
interaction diagram for your process. This diagram is a graph of pressure
versus time, with material interactions overlaid.
In the following example, a simple three step Oxygen VSA process is
examined. The process uses three identical adsorbent beds, each undergoing
the following steps in a cycle:
Production at high pressure with some product that counter-currently
repressurizes another bed.
Evacuate to low pressure. The material is sent to waste.
Repressurize using product material.
The Pressure-Interaction diagram for the process looks similar to this:
8 Flowsheeting 279
P
t
Bed 1
Bed 2
Bed 3
60 180 120

If the single bed approach is applied, using Bed 1 as the real bed, the
interactions would look like this:
8 Flowsheeting 280
P
t
Bed 1
Bed 2
Bed 3
60 180 120
Record
Replay
Flowsheet Scope

Material profile information from step 1 can be stored and then replayed back
to Bed 1 during step 3. The final pressure-interaction diagram for the new
single bed process looks like this:
8 Flowsheeting 281
P
t
Bed 1
60 180 120

Interactions
When material from a step is used by another step, this is called an
interaction. Aspen Adsim handles any number of interactions in an adsorption
process cycle.
Using the Oxygen VSA example, the pressure-interaction diagram was as
follows:
P
t
Bed 1
60 180 120

The three, 60 second duration steps were:
Step 1 0 through 60 seconds there was production with some
material used to repressurize another bed.
Step 2 60 through 120 seconds there was counter-current
evacuation to waste.
Step 3 120 through 180 seconds there was counter-current
repressurization with product material.
In this example there is only one interaction, a top-to-top interaction between
steps 1 and 3. To create this interaction when using the single bed approach,
you must use an interaction model to simulate the bed that the real modeled
bed is interacting with. In gas systems, for example, it is named
gas_interaction. The interaction model records one or more of the following
profiles (dependent on the phase of the system):
Flowrate
Composition or concentration
Density
8 Flowsheeting 282
Temperature
Pressure
Specific enthalpy
To use the gas_interaction model, for example:
The inlet stream must always be connected to a valve (configured as a
non-reversible delay) whose inlet is connected to point on the flowsheet
where material is withdrawn. The valve passes the interaction unit
information about the upstream (or relative bed) pressure. Typically, the
valve inlet is connected to a gas_tank_void model that is being used to
simulate an adsorbent bed deadspace or void.
The outlet stream defines where material is returned to the flowsheet. No
valve is required on the outlet stream.
Real Bed
Scope
Store Profile
Real Bed
Scope
Replay Profile
Valve Present
In Scope
Valve Not Present
In Scope
Store Replay

Use the withdrawal and return point for material, to define whether the
interaction is:
Top-to-top
Top-to-bottom
Bottom-to-bottom
Bottom-to-top
So, for the Oxygen VSA example, the following additions are needed to create
a top-to-top interaction off the real adsorbent beds top void.
8 Flowsheeting 283
Tank
Valve
Interaction
From bed
To product

Notes:
o The interaction units use the Delay function.
o The accuracy of the delay function is dependent on the
communication interval, not the integration step size. It is
recommended that you have at least four communication
points within the shortest step.
o If the simulation is closed or a snapshot re-used, the delay
buffer is emptied and all historical profile information is lost.
o The snapshot does not store delay information.
Specifications for Flowsheets
This section gives information on:
Solver Options
Run Time Options
Model Specification
Consistency and Model Definition Checks
Solver Options
If you create a flowsheet that is not based on a template, the following solver
options are recommended as good initial starting points:
General Tab: Solver Options
The recommended solver options are:
8 Flowsheeting 284

Option Value
Absolute Variable Tolerance 1e-5
Relative Variable Tolerance 1e-5
Absolute Equation Tolerance 1e-7
Variable Change Tolerance 1e-5
Numerical Derivative Absolute Tolerance 1e-6
Numerical Derivative Relative Tolerance 1e-6
Solver Scaling Disabled
Eliminate Equivalence Equations Enabled, Standard
Integrator Tab: Solver Options

Option Value
Integrator Variable Step Implicit Euler
Initial Integration Step 1
Minimum Integration Step 1
Maximum Integration Step 5
Step Reduction Factor 0.5
Maximum Step Increment Factor 1.5
Absolute Integration Error Tolerance 1e-5
Tear Integration Tolerance 1
Maximum Corrector Iterations 500
Show Highest Integration Errors 0
Use Interpolation Enabled
Reconverge Torn Variables Disbaled

Note: When running rapid cycles, the integration steps may need
reducing.
Linear Solver Tab: Solver Options

Option Value
Name MA48
Drop Tolerance 0
Pivot Tolerance 0
Re-analyse Threshold 2
8 Flowsheeting 285
Re-analyze FLOPS Window Size 0
Re-pivot every 0
Solver searches 3
Non-Linear Solver Tab: Solver Options

Options Value
Mode General
Method Fast Newton
Convergence Criterion Residual
Maximum Divergent Steps 20
Maximum Step Reductions 20
Maximum Iterations 500
Maximum Fast Newton Steps 8
Dogleg Method Disabled
Run Time Options
To set the runtime options for Aspen Adsim:
From the Run menu, click Run Options.
The following settings are recommended:

Options Value Comments
Solution Time Units Seconds Time unit assumed by library models.
Display Update 2 Interval when data is communicated between
client and server.
Communication Problem
dependent
Resolution at which plot data and delay
information is saved. Small values make the
plot data file grow more rapidly.
When using interactions, ensure this value is
set to provide at least five communication
points in the shortest interaction step.
When studying rapid transients, set this to a
small value.
Pause at Problem
dependent
Uncheck when using the Cycle Organizer (run
time controlled by maximum number of cycles).
Check and provide a desired end time for other
simulations. This value can also be modified
using the Run menu Pause At option.
Pause after Unchecked Number of communication intervals to execute.
Real time
synchronization
Unchecked Real time to simulation time factor. A value of
zero indicates run as fast as possible.
8 Flowsheeting 286
Model Specification
Aspen Adsim library models may require one or more of the following types of
specification:
Definition of model assumptions.
Specification of constant variables.
Initial and preset conditions.
The normal approach is to first configure the model, then specify the constant
variables exposed and finally, if required, specify the model initial condition.
Defining Model Configurations
The model configuration is the selectable assumptions a model may have. For
example, with an adsorbent layer, you have the option to:
Include a dispersive term in the component material balance.
Specify whether the layer is isothermal or non-isothermal.
You set these options in the model Configure form, which opens when you
double-click a flowsheet model block. This form displays selection boxes for
any available adjustable assumptions. On changing an assumption, the model
automatically reconfigures, so there may be slight pause depending on the
overall complexity of the change.
Specification of Constant Variables
All models in the Aspen Adsim library contain recommended fixed variables.
This ensures that the overall degrees of freedom of a complete problem are
always met. Therefore, there is no need to determine which values are
required to be specified. Each model in the Aspen Adsim model library
contains a Specify table. You access the Specify table in one of these three
ways:
Using the Configure form for the model.
From the Flowsheet menu, clicking Forms options.
Using the models context sensitive menu (selecting and right-clicking a
flowsheet model block).
The recommended columns made visible in the Specify table are:
Value
Units
Derivative
Specification
Description
Presets and Initialization
If a model contains state variables (variables that are differentiated with
respect to time), initial values are required. Adsorbent layer and tank models
typically fall into this category.
To define the preset and initial variables, click the button on the Configure
form to open the Initials table, which shows the recommended variables to
preset and initial.
8 Flowsheeting 287
For an adsorbent/resin bed:
Provide values for a single discretization node within a given layer. To
propagate this value through the rest of the layer, either click the Initialize
button on the models configure form, or select Check & Initial from the
Flowsheet menu.
To specify a layer that is at saturated equilibrium with a given bulk phase
composition, initialize the bulk phase values (molefraction or
concentration) and for the loading, set the derivatives to zero with a
specification of Rateinitial.
For a gas adsorbent layer that includes a pressure drop correlation
(momentum balance), the standard specification is to initialize the
superficial velocity and initial ncomps-1 bulk phase molefractions.
For a gas phase tank or void:
Preset (provide free specified values for) the internal composition.
Preset (provide a free specified value for) the internal pressure.
Provide an initial value of the temperature.
From the above and using the internal volume, the initialize method
calculates the material molar holdup.
A valid alternative specification is to initialize the temperature, pressure
and ncomps-1 internal molefractions, and to free the internal molar
holdup.
If you modify initial or preset values solely in the Initials table (and not
elsewhere), the Check & Initial option in the Flowsheet menu always ensures
that the problem contains the correct number of initial variables.
The recommended columns to made visible in the Initials table are:
Value
Units
Derivative
Specification
Description
Consistency and Problem Definition
Checks
When creating and specifying a flowsheet, it is recommended that you make
these checks:
For cyclic processes, configure the flowsheet with first step conditions.
Check the initial and preset pressure conditions throughout the flowsheet.
Ensure the pressure gradient is correct for the direction of material travel,
for example feed to product.
Allow cross-valve pressure drops of at least 1 mbar.
For gas adsorbent beds, for robust initialization assume a small initial
superficial velocity, for example 3.55e-4 m/s.
Pay particular attention to the deadspaces connected to a gas adsorbent.
Ensure the pressure profile between the two units are reasonable and in
the correct direction, and that the deadspaces have been correctly
8 Flowsheeting 288
initialized. Unreasonable initial conditions for deadspace are the principal
cause of full flowsheet convergence problems at the start of the
simulation.
Make use of the Flowsheet menu Check & Initial option. It indicates
unconnected and invalid streams, corrects interaction unit configurations,
runs any model-based initialization methods, and correctly configures
material stream source and destination unit types.
If the model has too many initial variables, use Variable Finder to find all
Initial and Rateinitial variables. Set the specification of any found variables
to Free and then use the Check & Initial option from the Flowsheet menu.
The default initial condition is reconstructed.
Make use of the recommended Fixed variables. If any are set to a
specification of Free, another variable needs to be Fixed and vice-versa.
For example, using a simple gas flowsheet, the default specification is for
it to be pressure driven. If forced feed is required, set the feed unit
flowrate specification to Fixed and the product unit specification to Free.
The library models contain default specifications. Should the problem
become over or underspecified, use either the specification analysis tool;
or using Variable Finder, find all variables and from the properties page,
set the specification to default values.
For flowsheets with interaction units, ensure the run time communication
interval allows at least five communication points within the shortest
interacting steps.
For processes that operate under rapid cyclic conditions, ensure the
integrator step sizes are suitable. For example, when using the Variable
Step Implicit Euler integrator, try setting the maximum integrator step to
half the shortest step time, and the initial and minimum steps sizes to 1/5
through 1/10 of the maximum integrator step.
The default solution bounds for variables defined in the library are suitable
for most problems. However, when operating with large pressure or
temperature swings, or very rapid cycles, the default bounds may need
readjusting. Use the Variable Finder for this.
If you receive messages stating that empty arrays are being passed to
procedures, this usually indicates that the current component list is not
defined. When flowsheeting, it is usual to first create the component list
and then start placing models on the flowsheet.
If a spanner/wrench appears in the specification window when
flowsheeting, ensure that a component list is defined and that all
connections are in place.
Physical Properties
Various physical properties are required by the Aspen Adsim models. Typical
properties required are:
Molecular weight
Viscosity
Density
Enthalpy
Aspen Adsim supports two ways of supplying this physical property data:
8 Flowsheeting 289
User Fortran subroutines.
External physical property application (Properties Plus, Aspen Properties).
The component list created for the problem governs the method in which
physical properties are called.
If you use a template, the default component list assumes that user
Fortran subroutines are being used.
When starting a new problem (without a template), the default component
list is configured for use with an external properties application. To modify
it for use with user-Fortran, you must first convert it to a component set
(to do this, right-click the list and select convert).
If a new component list is created, by default it is assumed an external
properties application will be used. If you want the user Fortran option,
select the Is ComponentSet box is on creation.
Use of User Fortran
Historically, Aspen Adsim assumed that any physical property calculations or
data were supplied through user Fortran subroutines.
The advantages of using user Fortran based calculations are:
Simulation speed.
When distributing a problem, only need to additionally supply the library.
Disadvantages of using the user Fortran method are:
Inflexibility when changing component names. Arrays indexed by
component name are passed to procedures in ASCII order, hence
subroutines may need modifying in response to changing component
order.
Addition and removal of components from the simulation. The user
subroutines either need reworking after each change or a collection of
different versions of subroutines (each assuming different numbers of
components) will be required.
When creating a component list:
The interface between the subroutine and model is defined by the Procedure
type. The procedure definition defines the calling arguments, subroutine
name and library name. The subroutines created then need to be compiled
into a library so that they link to the simulation during runtime.
It is important that the compiled library is placed in the simulator engines
working directory. The working directory has the same name as the current
simulation, and is one level down from the default working directory. For
example, if the name of the current problem is N2PSA.ada and the default
working folder has been defined as C:\MySims, the simulation engines
working folder for this problem is C:\MySims\N2PSA.
This applies to both local PC and remote server implementations.
8 Flowsheeting 290
Using a Physical Properties Application
The simplest way of incorporating physical property calculations and data, is
to use an external physical properties application such as Properties Plus or
Aspen Properties.
The advantages of using an external physical properties application are:
Ability to create a single definition file containing all the components and
physical property methods of interest, and only those required in the
current problem.
Large collection of rigorous physical property methods.
Extensive component database.
The disadvantages are:
Speed penalties.
Requires application on same machine.
When using Properties Plus or Aspen Properties, for example, the steps
required before using either application are:
1 Create an .appdf file.
2 In Aspen Adsim, within the Explorer window, right-click Component Lists
and select Properties. Define where the .appdf is located.
3 Create or convert a component list and select the components required.
Switching Between Methods
To switch between using user Fortran and an external properties application
for the supply of physical property calculations and data:
1 If converting from user Fortran to an external application, ensure the link
to an .appdf file is already defined. (To do this, right-click the
ComponentLists object in Explorer and browse for a previously created
.appdf file.)
2 Select the currently active component list.
3 Right-click the list and select Convert.
The component list switches to the other method its currently using.
When switching from Fortran to application based properties, if the
component names originally defined are present in the .appdf file, the
same components will be present, otherwise mismatches will be
discarded.
4 Open the Configure form for any library model of the flowsheet. The global
variable that switches the two methods is automatically updated.
8 Flowsheeting 291
Connecting to Aspen Dynamics
Flowsheets
You can now connect Aspen Adsim flowsheet sections to Aspen Dynamics
flowsheet sections (except for ion-exchange flowsheets). There are two new
utilities models for this purpose:
Dynamics_Inlet_Connect
Dynamics_Outlet_Connect
These models are in the Utilities folder of the Aspen Adsim library.
The model link must be done from within Aspen Adsim; the link cannot be set
up from Aspen Dynamics.

Tip: If you are creating an Aspen Adsim flowsheet for connection
with an Aspen Dynamics flowsheet, it is good practice to name
the active component list as 'Type 1'. This simplifies later
conversion.
Typical Workflows
When you want to connect Aspen Dynamics models to Aspen Adsim models,
there are two possible situations:
Attach individual Aspen Dynamics models to an existing Aspen Adsim
simulation.
Attach a complete Aspen Dynamics simulation to an existing Aspen Adsim
simulation.
Attaching Individual Aspen Dynamics Models
To attach an individual Aspen Dynamics model (for example, a rigorous
compressor model) to an existing Aspen Adsim simulation:
1 In Aspen Adsim, open the Aspen Adsim simulation.
2 Open the Aspen Dynamics library. To do this:
From the File menu, click Open Library and navigate to the Lib folder of
the AMSystem 2004.1 installation.
3 Place the required Aspen Dynamics model onto the Aspen Adsim
flowsheet.
4 Attach the new Aspen Dynamics flowsheet block to an existing Aspen
Adsim flowsheet block, as follows:
Attach an Aspen Adsim material stream to the Aspen Adsim flowsheet
block, and an Aspen Dynamics material stream to the newly placed Aspen
Dynamics flowsheet block. Now connect these two streamsusing either a
Dynamics_Inlet_Connect or Dynamics_Outlet_Connect model from the
Utility folder of the Aspen Adsim library. Your choice depends on whether
the Aspen Dynamics model is on the inlet or outlet side of the Aspen
Adsim mode.
5 Repeat steps 3 and 4 until the flowsheet is complete.
8 Flowsheeting 292
6 Check and modify the global variables relating to Aspen Dynamics flow
schemes. You do this in the Global variables table, or from the Configure
form of a Dynamics_Inlet_Connect or Dynamics_Outlet_Connect block:

Global
variable
Brief
description
Notes
GlobalPDriven Is the flowsheet
pressure driven?
For gas systems, set to True.
GlobalPropMode Property mode Default is Local. If property
convergence is difficult, set to
Rigorous. (Aspen Adsim uses
only rigorous property calls.)
GlobalRFlow Reverse flow? Set to True if the model is
expected to operate
reversibly.
7 Specify, and provide initial values for, the new Aspen Dynamics blocks.
Attaching Complete Aspen Dynamics Flowsheet
To attach a complete Aspen Dynamics simulation to an existing Aspen Adsim
simulation (for example, an Aspen Dynamics based cryogenic distillation train
to an Aspen Adsim TSA system for air dehumidification):
1 In Aspen Adsim, open the Aspen Adsim simulation.
2 Check the component lists being used:
Ensure matching component list names between the Aspen Adsim and
Aspen Dynamics simulations. Typically, the Aspen Dynamics version is
called Type1. If necessary, you must rename the Aspen Adsim
component list name to match. If the Aspen Adsim component list
name is Default, you cannot rename it through the GUI. Instead, open
the input file (.ada extension) within a text editor and search and
replace the original component name, to the new component name.
Ensure the same components are actively in use.
Ensure the same properties definition file, .appdf, is in use.
3 The type of Aspen Dynamics flowsheet that can be imported depends on
the type of Aspen Adsim flowsheet:
For gas-based Adsim flowsheets, imported Aspen Dynamics flowsheets
must be pressure driven. See Valid Flowsheet Combinations, later.
For liquid-based Aspen Adsim flowsheets, imported Aspen Dynamics
flowsheets may be either pressure driven or flow driven. See Valid
Flowsheet Combinations, later.
You must check the Globals table in Aspen Adsim and set the global
parameters GlobalPDriven and GlobalRFlow to match those in the
Aspen Dynamics flowsheet to be imported.
4 From the File menu, click Import Flowsheet. This imports the Aspen
Dynamics simulation into Aspen Adsim.
Note these points:
Aspen Adsim does not support flowsheet hierarchy, so all Aspen Adsim
based blocks and streams must exist on the main flowsheet.
8 Flowsheeting 293
Repeated blocks, streams, plots, tables and tasks names are flagged
during the flowsheet import. You can rename or delete these
repetitions, or import the flowsheet into a hierarchy block.
Aspen Adsim automatically opens the Aspen Dynamics model library
during the import.
The Aspen Adsim simulation flowsheet is updated with the imported
Aspen Dynamics simulation flowsheet.
For common global variables, Aspen Adsim retains the original settings
from before the flowsheet was imported.
5 Repeat steps 2 through 4 until all the required flowsheet sections are
present within Aspen Adsim.
6 Between each flowsheet section, connect the appropriate Aspen Adsim or
Aspen Dynamics feed and product streams:
For an existing Aspen Adsim feed or product stream, remove the
boundary termination block (unlike Aspen Dynamics, Aspen Adsim has
no concept of using open ended streams to indicate flowsheet
boundaries). Now connect these open-ended Aspen Adsim streams
with their Aspen Dynamics counterparts, using either a
Dynamics_Inlet_Connect or a Dynamics_Outlet_Connect from the
Utilities folder of the Aspen Adsim library. (Your choice depends on
whether the Aspen Dynamics model is on the inlet or outlet side of the
Aspen Adsim flowsheet.)
7 Repeat step 6 until the flowsheet is complete.
8 In the Cycle Organizer, modify the cycle description to account for any
cyclic operation of imported Aspen Dynamics blocks, then regenerate the
cyclic task.
Valid Flowsheet Combinations
The valid combinations of Aspen Adsim and Aspen Dynamics flowsheets are:
Connect gas-based Aspen Adsim flowsheets to pressure driven Aspen
Dynamics flowsheet sections.
Connect liquid-based Aspen Adsim flowsheets to flow driven Aspen
Dynamics flowsheet sections.
Further valid combinations are also possible, and these are listed in the
following table. Some combinations have constraints: in the table, bracketed
numbers mark where this happens and you should refer to the notes
underneath for more details.

Inlet side section
(Aspen Dynamics)
Outlet side section
(Aspen Dynamics)
Gas
(Aspen Adsim)
Liquid
(Aspen Adsim)
Pressure driven Pressure driven Supported (1) Not Supported
Pressure driven Not present Supported (2) Supported (3)
Not present Pressure driven Supported (4) Supported (5)
Flow driven Flow driven Partial support (6) Supported
Flow driven Not present Partial support (7) Supported
8 Flowsheeting 294
Not present Flow driven Partial support (8) Supported
Reversible
(pressure driven)
Reversible
(pressure driven)
Supported (9) Not supported
Reversible
(pressure driven)
Not present Supported (10) Supported
Not present Reversible
(pressure driven)
Supported (11) Supported
You cannot mix flow assumptions, for example a pressure driven inlet and a
flow driven outlet. This is because a single set of global variables is used to
control the Aspen Dynamics flowsheet assumption.
The following notes relate to the bracketed numbers (denoting constraints) in
the previous table:
1 Connect the Aspen Dynamics flowsheet sections on both the inlet and
outlet sides to a pressure node (a gas_tank_void for example).
2 Connect the Aspen Dynamics flowsheet section on the inlet side to a
pressure node (a gas_tank_void for example).
3 Fix a pressure at the Aspen Adsim flowsheet outlet.
4 Connect the Aspen Dynamics flowsheet sections on the outlet side to a
pressure node (a gas_tank_void, for example).
5 Fix a pressure at the Aspen Adsim flowsheet inlet.
6 Connect both Aspen Dynamics flowsheet sections only to a gas_bed
model.
7 Connect the Aspen Dynamics flowsheet only to an Aspen Adsim gas_bed
inlet.
8 Connect the Aspen Dynamics flowsheet only to an Aspen Adsim gas_bed
outlet.
9 Connect the Aspen Dynamics flowsheet sections on both the inlet and
outlet sides to a pressure node (a gas_tank_void for example). The single
bed approach is not recommended; use a full rigorous Aspen Adsim
flowsheet instead.
10 Connect the Aspen Dynamics flowsheet section on the inlet side to a
pressure node (a gas_tank_void for example). The single bed approach is
not recommended; use a full rigorous Aspen Adsim flowsheet instead.
11 Connect the Aspen Dynamics flowsheet section on the outlet side to a
pressure node (a gas_tank_void, for example). The single bed approach is
not recommended; use a full rigorous Aspen Adsim flowsheet instead.
Global Variables
A number of global variables control the operation of both Aspen Adsim and
Aspen Dynamics models. These variables can be found in the Globals table
within the Simulation object in the Simulation Explorer. You can also access
many of these global variables through the Configure form of the
Dynamics_Inlet_Connect and Dynamics_Outlet_Connect model blocks.
8 Flowsheeting 295
The global variables used are as follows:
Global variable Default
value
Description
GlobalPropMode Local The global property mode.
Aspen Dynamics models use GlobalPropMode to select
between local or rigorous physical properties
calculations:
The Local option uses simplified functions whose
parameters are updated from an external physical
property package. This improves the simulation time.
The rigorous option uses methods contained within the
external physical properties package.
Note: All Aspen Adsim models use rigorous property
calls.
GlobalPdriven False Is the simulation pressure driven?
Aspen Dynamics models use GlobalPdriven to switch the
overall flowsheet scheme between pressure-driven flow
and flow-driven flow. In general, for Aspen Dynamics
models used in conjunction with Aspen Adsim models:
When the system is gas, set to True.
When the system is liquid, set to False.
Note: If you anticipate flow reversibility within Aspen
Dynamics models, the flowsheet must be pressure
driven (so set the parameter to True).
GlobalRFlow False Does the simulation support reverse flow?
Aspen Dynamics uses GlabalRFlow to switch between
uni-directional and bi-directional flow. For bi-directional
flow, you must also set GlobalPdriven to True, otherwise
the Aspen Dynamics models will default to uni-
directional, flow-driven flow.
GlobalTimeScaler 1 Seconds per model time unit.
Aspen Dynamics models assume time units of hours,
whereas Aspen Adsim models assume seconds. When
models from both products exist on the same flowsheet,
a common time unit needs to be adopted to successfully
calculate time derivatives and delay times. Aspen
Dynamics uses GlobalTimeScaler to rescale time
derivatives and calculated delay times, from hours to
seconds.
IsSingleBed False Is the single bed approach being used?
IsSingleBed indicates to Aspen Adsims
Dynamics_Inlet_Connect and Dynamics_Outlet_Connect
models, whether the Aspen Adsim flowsheet is using the
Single-Bed approach to simulate a multi-bed flowsheet
using a single column.
When set to True, a set of equations is enabled that
generate pseudo continuous flow from an inherently
discontinuous flow.
8 Flowsheeting 296
Connecting to a Single Bed Approach
Flowsheet
The single bed approach to modeling a cyclic adsorption process is an
abstract representation of the real process, so it suffers from the inherent
behavior of discontinuous flow at the flowsheet boundaries. For example, a
product stream from an Aspen Adsim flowsheet may be active (producing
material) only during one step in the cycle.
time
Flowrate
Cycle

This behavior can disrupt Aspen Dynamics flowsheets that are connected to
this same outlet boundary, as they may be expecting to continuously receive
material. For example, a discontinuous supply of material may cause adverse
effects to downstream units such as distillation columns or compressors.
To counter this problem, the Dynamics_Inlet_Connect and
Dynamics_Outlet_Connect models have been developed, which contain a
series of expressions to generate a pseudo continuous flow of material. They
use a similar set of expressions to the gas_interaction model. The flow,
composition, temperature, pressure and enthalpy profiles are recorded during
the flow of actual material, whilst a delay function is used to reproduce the
same profile, periodically throughout the rest of the cycle.
time
Flowrate
Cycle
Delayed Profiles
DT
2 x DT
3 x DT
4 x DT

The two models use a variable that switches/toggles to indicate when flow of
real material occurs. When set to 1 (that is On, for real flow), the inlet and
outlet port variables are mapped together and the time at which the switch
8 Flowsheeting 297
was set to 1 is recorded. When no real flow is occurring, the variable switches
to 0 (that is Off, for pseudo flow); and the time at which the switch occurred
is recorded, and a delay time is calculated. The Aspen Dynamics port
variables are then mapped to the appropriate Aspen Adsim port variables, but
through the delay function. When the elapsed time from the switch off
exceeds the calculated delay time, the delay time is incremented by the
original delay time.
DelayTime
Time Seconds
0 10 20 30 40 50 60 70 80 90 100
B
1
.
T
o
g
g
l
e

B
1
.
D
e
l
a
y
T
i
m
e

1
2
3
4
5
6
7
8
9
1
0
-
5
0
5
1
0
1
5
2
0
2
5
3
0

The result of this procedure is a continuously variable delay time that
produces a profile with a repeating pattern.
Output_Values
Time Seconds
0 10 20 30 40 50 60 70 80 90 100
B
1
.
C
a
l
c
O
u
t
p
u
t

B
1
.
R
e
a
l
O
u
t
p
u
t

0
.
5
1
1
.
5
2
-
1
-
0
.
5
0
0
.
5
1

This method is applicable only if the assumption that the flow profile expected
at the inlet and/or outlet side of the Aspen Adsim flowsheet is consistent
within a given cycle.
The delay function is used to replicate flow profiles. This, coupled with the
fact that it uses interpolation of historical data, explains why you may see a
slight degradation in the overall material balance.
9 Reference List for Adsorption Processes 298
9 Reference List for
Bird, R.B., Stewart, W.E., Lightfoot, E.N., Transport Phenomena, John
Wiley and Sons, New York, 1960.
Carberry, J.J., Chemical and Catalytic Reaction Engineering, McGraw-Hill,
New York, 1976.
Carver, M.B., Scheisser, W.E., American Institute of Chemical Engineers,
Annual Meeting, November 16-18, 1980.
Costa, E., Sotelo, J.L., Calleja, G., Marron, C., Adsorption of Binary and
Ternary Hydrocarbon Gas Mixtures on Activated Carbon: Experimental
Determination and Theoretical Prediction of the Ternary Equilibrium Data,
AIChE Journal, Vol. 27, No. 1, 1981.
Froment, G.F. and Bischoff, K.B., Chemical Reactor Analysis and Design,
John Wiley and Sons, New York, 1990.
Kast, W., Adsorption aus der Gasphase, VCH, Weinheim, 1988.
Nakao, S.I., Suzuki, M.U., Mass Transfer Coefficient in Cyclic Adsorption
and Desorption, Journal of Chem. Eng. of Japan, Vol 16, No 2, 1983.
Reid, C.R., Prausnitz, J.M., Sherwood, T.K., The Properties of Gases and
Liquids, McGraw-Hill, New York, 1977.
Ruthven, D.M., Principles of Adsorption and Adsorptive Processes, John
Wiley and Sons, 1984.
Slater, M.J., The Principles of Ion Exchange Technology, Butterworth,
Heinemann, Boston, 1991.
Tien, Chi, Adsorption Calculations and Modeling, Butterworth-Heinemann,
1994.
Wakoo, N., Chem Eng Sci, 31, pp 11-15, 1976.
Yang, R.T., Gas Separation by Adsorption Processes, Butterworth, 1987.

Index 299
Index
A
Activating cyclic tasks 257
Adsorbed solution theory (gas) 64
Adsorption isotherms (gas)
about 51
choosing 52
list 55
multicomponent mixture isotherms 52
Aspen Custom Modeler 230
Aspen Properties 284
available 299
Axial dispersion (gas) 22
Axial dispersion (ionx) 182
Axial dispersion (use for differencing schemes)
223
B
B.E.T isotherm (gas) 58
B.E.T. Multilayer isotherm (gas) 58
Bed model assumptions (gas) 11, 13
Bed model assumptions (ionx) 179
Bed model assumptions (liq) 192
Bed model ports (gas) 14
Bed models (gas) 14
Biased Upwind Differencing Scheme 227
Brunaur, Emmet and Teller See B.E.T
Burke-Plummer equation (gas) 26
C
Central differencing schemes 222, 223
Complex expression step control 248
Compressiblity (gas) 21
Conduction (gas) 65
Conduction (liq) 207, 210
Configure form (gas)
about 15
bed types 16
internal heat exchanger 19
spatial dimensions of beds 18
Configure form (ionx) 179
Configure form (liq) 192
Configure form tabs (gas)
Energy Balance 64
General 20
Isotherm 51
Kinetic Model 31
Material/Momentum Balance 22
Procedures 76
Reaction 73
Configure form tabs (ionx)
General 180
Isotherm 185
Kinetic Model 183
Configure form tabs (liq)
Energy Balance 206
General 193
Isotherm 200
Kinetic Model 196
Procedures 213
Index 300
Configure Layer form (gas) 20
Configure Layer form (ionx) 179
Configure Layer form (liq) 192
Connecting controllers 268
Connectivity in flowsheets 267
Consistency checks for flowsheets 281
Constant variables (specifying) 280
Controllers 268
ControlSignal stream 268
Convection (gas) 23
Convection (ionx) 180
Convection (liq) 193
Convert_EstMod script 241
Cycle controls 254
Cycle Organizer
about 243
cycle controls 254
Cycle Organizer window 244
cyclic reports 258
cyclic tasks 257
interaction control 252
opening 244
step controls 246, 256
step variables 250
Cycle Organizer block 244
Cycle Organizer window 244
cycle controls 254
cyclic reports 258
cyclic tasks 257
interaction controls 252
step controls 256
step variables 250
Cycle snapshots 255
Cyclic corrections (gas) 49
Cyclic operations 243
Cyclic Recovery report 260
Cyclic reports 258
Cyclic Recovery reports 260
Cyclic Stream reports 259
preparing 258
Cyclic Stream report 259
Cyclic tasks 257
D
Darcy's Law (gas) 26
Darcy's law (liq) 195
Deactivating cyclic tasks 257
Demonstration Organizer 269
Demonstrations 268
Density (liq) 196
Discretization methods
about 218
choosing 219
list 219
recommended 219
Discretization methods (gas) 20
Discretization methods (ionx) 180
Discretization methods (liq) 193
Dispersion (gas) 23
Dispersion (ionx) 180, 182
Dispersion (liq) 193
Dispersion coefficient (ionx) 180
Dispersion coefficient (liq) 193
Dispersive properties (gas) 27
documentation 297
Dual Layer B.E.T isotherm (gas) 62
Dual-Site Langmuir isotherm (gas) 61
Dual-Site Langmuir isotherms (liq) 201
Dubinin-Astakov isotherm (gas) 59
Dynamic estimation
about 236
entering data manually 237
importing data from clipboard 238
E
Effective diffusivity (gas) 36, 39, 50
Energy balance assumption (gas) 64
Energy balance assumption (liq) 206
Index 301
Energy balance equations (gas)
factors affecting equations 81
gas phase 78, 81
solid phase 78, 84
wall 79, 86
Energy balance equations (liq) 213
Energy Balance tab (gas) 64
Energy Balance tab (liq) 206
Enthalpy (gas) 65
Enthalpy (liq) 208
Equation symbols (gas) 87
Equation symbols (ionx) 189
Ergun equation (gas) 27
Estimated mass transfer coefficient (gas) 50
Estimated Variables tab 232
Estimation
converting Estimation Module data 241
dynamic 236
estimated variables 232
Estimation Module 230
methods available 230
performing using Estimation Module 241
recommendations 241
steady-state 233
Estimation methods 241
Estimation Module
about 230
converting to Aspen Custom Modeler
methods 241
defining estimated variables 232
dynamic estimation 236
recommendations 241
steady-state estimation 233
using 241
Estimation Module block 231
Estimation Module form 231
Event-driven step controls 246
Experimental Data tab 233, 237
Expression Builder dialog box 249
Extended Langmuir isotherm (ionx) 187
Extended Langmuir isotherms (gas) 60
Extended Langmuir isotherms (liq) 201
Extended Langmuir-Freundlich isotherm (gas)
61
Extended Langmuir-Freundlich isotherm (ionx)
187
Extended Langmuir-Freundlich isotherms (liq)
203
F
Film model assumption (gas) 31
Film model assumption (ionx) 183
Film model assumption (liq) 197
Flow reversibility 263
Flowsheet specifications See Specifying
flowsheets
Flowsheet types 269
full 271
intermediate 270
simple 269
Flowsheets
about 266
Connectivity 267
Cycle Organizer block 244
demonstrations 268
interactions 275
model types 263
physical property calculations 282
Pressure Interaction diagram 272
reversibility of flow 263
single bed approach 272
specifications 277
templates 268
types 269
Fluid phase energy balance (liq) 214
Fluid thermal conductivity (liq) 210
Flux Limited Differencing Scheme 229
Flux Limiter method? (gas) 21
Freundlich isotherms (gas) 56
Index 302
Freundlich isotherms (liq) 202
Fromm's Scheme 228
Full flowsheet 271
G
g_Material_Port 267
Gas adsorption processes (overview) 11, 12
Gas model assumption (gas) 21
Gas thermal conductivity (gas) 69
gas_Material_connection 267
Gas-Wall heat transfer coefficient (gas) 72
General tab (gas) 20
General tab (ionx) 180
General tab (liq) 193
Generating cyclic tasks 257
Glueckauf approximation (gas) 49
gUserCompressibility submodel 22
gUserCpa submodel 66
gUserDH submodel 67
gUserDispersion submodel 24
gUserEffDiff submodel 37, 41, 50
gUserGibbs submodel 63
gUserHTC submodel 68
gUserIsothermC submodel 63
gUserIsothermPoi submodel 63
gUserIsothermPp submodel 63
gUserKg submodel 69
gUserKinetic submodel 35
gUserKineticModel submodel 43
gUserMTC submodel 49
H
Heat capacity (gas) 66
Heat capacity (liq) 208
Heat exchanger (gas) 19
Heat of adsorbed phase (gas) 65
Heat of adsorbed phase (liq) 208
Heat of adsorption (gas) 66
Heat of adsorption (liq) 208
Heat transfer coefficient (gas) 67
Heat transfer coefficient (liq) 209
Heat transfer to environment (gas) 70
Heat transfer to environment (liq) 211
Henry isotherms (gas) 57
Henry's coefficient (gas) 47
Heterogeneous rate dependency (gas) 75
Heterogeneous reactions (gas) 74
Homogeneous rate dependency (gas) 74
Homogeneous reactions (gas) 74
Horizontal beds (gas) 16
I
i_Material_Port 267
IAS (gas) 53, 64
IAS (liq)
about 200
IAS Freundlich isotherms 204
IAS Langmuir isotherms 204
IAS Langmuir-Freundlich isotherms 205
Purecomponent procedure with IAS isotherm
206
Purecomponent submodel with IAS isotherm
206
IAS Freundlich isotherms (liq) 204
IAS isotherm (gas) 63
IAS Langmuir isotherms (liq) 204
IAS Langmuir-Freundlich isotherms (liq) 205
Ideal Adsorbed Solution theory See IAS
Ideal gas (gas) 21
Importing data from Microsoft Excel
dynamic 239
steady-state 235
Initialization for models 280
Interaction control 252
Interactions 252
Interactions between steps 275
Interactions example 275
Intermediate flowsheet 270
Index 303
Internal heat exchanger (gas) 19
Ion-exchange adsorption processes (overview)
178
Ion-exchange equilibria 185
Ion-exchange resins 178
ionx_Material_connection 267
Isotherm assumed for layer (gas) 55
Isotherm assumed for layer (ionx) 186
Isotherm assumed for layer (liq) 200
Isotherm dependency (gas) 64
Isotherm list (gas) 55
Isotherm list (ionx) 186
Isotherm list (liq) 200
Isotherm tab (gas) 51
Isotherm tab (ionx) 185
Isotherm tab (liq) 200
Isothermal conditions (gas) 65
Isothermal conditions (liq) 207
Isotherms (gas) 55
Isotherms (ionx) 185
Isotherms (liq) 199
iUserDispersion submodel 182
iUserIsotherm submodel 187
iUserKinetic submodel 184
iUserMTC submodel 185
K
Karman-Kozeny equation (gas) 26
Karman-Kozeny equation (liq) 195
Kinetic model assumption (gas) 31
Kinetic model assumption (ionx) 184
Kinetic model assumption (liq) 197
Kinetic Model tab (gas) 31
Kinetic Model tab (ionx) 183
Kinetic Model tab (liq) 196
Knudson diffusion coefficient (gas) 48
L
Langmuir isotherms (gas) 55
Langmuir isotherms (liq) 200
Langmuir-Freundlich isotherm (gas) 57
Langmuir-Freundlich isotherms (liq) 202
Leonard Differencing Scheme 223
Linear isotherm (gas) 59
liq_Material_connection 267
liq_Material_Port 267
Liquid adsorption processes (overview) 191
Lumped resistance (gas) 32, 44, 46
Lumped resistance (ionx) 184
Lumped resistance (liq) 197
lUserDH submodel 209
lUserDispersion submodel 195
lUserGibbs submodel 206
lUserHTC submodel 210
lUserIsotherm submodel 205, 206
lUserKinetic submodel 198
lUserKl submodel 211
lUserMTC submodel 199
M
Mass action equilibrium isotherm (ionx) 186
Mass balance equations (gas)
additional solid phase 77, 81
factors affecting equations 79
gas phase 77
Mass balance equations (ionx) 188
Mass balance equations (liq) 213
Mass transfer (gas)
about 31
lumped resistance 32, 44
micro and macropore effects 32
molecular diffusivities 45
particle material balance 36, 39
procedures 43
submodels 43
Mass transfer (ionx) 183
Mass transfer (liq) 196
Mass transfer coefficient (gas) 46, 50
Index 304
Mass transfer coefficient (ionx) 185
Mass transfer coefficient (liq) 198
Mass transfer driving force (gas) 31
Mass transfer driving force (ionx) 183
Mass transfer driving force (liq) 197
Material balance assumption (gas) 23
Material balance assumption (ionx) 180
Material balance assumption (liq) 193
Material/Momentum Balance tab (gas) 22
Material/Momentum Balance tab (ionx) 180
Material/Momentum Balance tab (liq) 193
Maximum number of cycles 254
Micro and macropore effects (gas) 32, 34, 46
Micro and macropore effects (liq) 198
Microsoft Excel 235, 239
Mixed Differencing Scheme 226
Model configuration (defining) 280
Model specifications 280
Model types 262
Models
list of types 263
reversibility 263
types 262
Molecular diffusivities (gas) 45
Molecular diffusivity (ionx) 182
Momentum balance assumption (gas)
about 25
constant pressure options 25
pressure driven options 26
Multicomponent mixture isotherms (gas) 52
Myers isotherm (gas) 60
N
New Experiment dialog box
dynamic 237
steady-state 233
Nodes (gas) 21
Non-ideal gas (gas) 21
Non-isothermal conditions (gas) 65
Non-isothermal conditions (liq) 209, 210
Non-Isothermal conditions (liq) 207
Nonlinearity and numerical methods 218
Non-Reversible Delay models 263
Non-Reversible models 263
Number of heterogeneous reactions (gas) 75
Number of homogeneous reactions (gas) 75
Number of nodes (gas) 21
Number of nodes (ionx) 180
Number of nodes (liq) 193
Numerical methods
about 218
Biased Upwind Differencing Scheme 227
Central Differencing Schemes 222, 223
Flux Limited Differencing Scheme 229
Fromm's Scheme 228
Leonard Differencing Scheme 223
Mixed Differencing Scheme 226
Quadratic Upwind Differencing Scheme 224
recommended 219
selecting 219
Upwind differencing schemes 221
Upwind Differencing Schemes 222
O
Obtain Dynamic Measurements for Experiment
DynExpt From Clipboard dialog box 238
Obtain Steady State Experiments From
Clipboard dialog box 235
Overall material balance assumption (liq) 196
P
Particle material balance See Particle MB
options
Particle MB 2 option (gas) 39, 50
Particle MB option (gas) 36, 50
Particle resistance coefficients (gas) 34
PDE differencing schemes
Biased Upwind 227
Central 222, 223
Index 305
Flux Limited 229
Fromm's 228
Leonard 223
Mixed 226
Quadratic Upwind 224
Upwind 221, 222
Peclet number (gas) 23
Peclet number (ionx) 183
Physical property calculations
about 282
external applications 284
switching between methods 284
user Fortran 283
Port types 267
Prandl number (gas) 68
Prandl number (liq) 210
Presets for models 280
Pressure (gas) 25
Pressure (liq) 195
Pressure drop assumption (liq) 195
Pressure drop options (gas) 27
Pressure Interaction diagram 272
Pressure Interaction diagram example 272
Problem definition checks for flowsheets 281
Procedures (used in)
effective diffusivity 50
fluid thermal conductivity 211
gas thermal conductivity 69
heat of adsorbed phase 66
heat of adsorption 67, 209
heat transfer coefficient 68, 210
isotherms 62, 187, 205
kinetic model 43, 184, 198
mass transfer coefficient 49, 185, 199
material balance 24, 181, 194
molecular diffusivities 46
purecomponent isotherms 206
Procedures tab (gas) 76
Procedures tab (liq) 213
Properties Plus 284
pUser_Act_Coeff procedure 64
pUser_g_Cat_Rx_Heat procedure 83
pUser_g_Cat_Rx_Rate_C procedure 75, 83
pUser_g_Cat_Rx_Rate_C_Sol procedure 75, 83
pUser_g_Cat_Rx_Rate_Pp procedure 75, 76,
83
pUser_g_Cat_Rx_Rate_Pp_Sol procedure 75,
76, 81, 83
pUser_g_Compressibility procedure 22
pUser_g_Cpa procedure 66
pUser_g_De procedure 37, 41, 50
pUser_g_DH procedure 67
pUser_g_Diffusivity procedure 46
pUser_g_Dispersion procedure 24
pUser_g_Gas_Rx_Heat procedure 83
pUser_g_Gas_Rx_Rate_C procedure 74, 83
pUser_g_Gas_Rx_Rate_Pp procedure 74, 83
pUser_g_Gibbs procedure 62
pUser_g_HTC procedure 68
pUser_g_Isotherm_C procedure 62
pUser_g_Isotherm_P procedure 62
pUser_g_Isotherm_Poi procedure 62
pUser_g_Kg procedure 69
pUser_g_Kinetic procedure 35, 43
pUser_g_MTC procedure 49
pUser_i_Dispersion procedure 181
pUser_i_Isotherm_C procedure 187
pUser_i_Isotherm_W procedure 187
pUser_i_Kinetic procedure 184
pUser_i_MTC procedure 185
pUser_l_DH procedure 209
pUser_l_Dispersion procedure 194
pUser_l_Gibbs procedure 206
pUser_l_HTC procedure 210
pUser_l_Isotherm_C procedure 205
pUser_l_Isotherm_W procedure 205, 206
pUser_l_Kinetic procedure 198
pUser_l_Kl procedure 211
Index 306
pUser_l_MTC procedure 199
Q
Quadratic Upwind Differencing Scheme 224
R
Radial beds (gas) 18
Radial nodes (gas) 21
Rate dependency (gas) 74, 75
Reaction processes (gas) 73
Reaction tab (gas) 73
Reactions present? (gas) 74
Reactions type (gas) 74
Real Adsorbed Solution theory (gas) 64
Real Adsorbed Solution Theory (gas) 54
Recommended numerical methods 219
Recording cycle information 255
Reference list 292
Reversibility example 264
Reversibility of flow 263
Reversible Flow Setter models 263
Reversible models 263
Reversible Pressure Setter models 263
Rigorous multiple bed approach 272
Run time options (specifying) 279
Running end-of-step scripts 256
S
Sherwood number (gas) 47
Simple flowsheet 269
Simulation Messages window 254, 255
Single bed approach 252, 272
Single Layer B.E.T isotherm (gas) 61
Snapshots 255, 256
Solid phase energy balance (liq) 214
Solid reactant list (gas) 76
Solid reactants present? (gas) 76
Solver options (specifying) 277
Spatial dimensions of beds (gas) 18
Specifying flowsheets
checks 281
list of options 277
model specification 280
run time options 279
solver options 277
Static_isotherm model 233
Steady state testing (cyclic) 255
Steady-state estimation
about 233
entering data manually 233
importing data from clipboard 234
Step controls 256
Step dependent step control 249
Step interaction control 252
Step interactions 252, 275
Step variables 250
Stoichiometric Equilibrium isotherms (liq) 203
Submodels (used in)
component isotherms 206
effective diffusivity 50
fluid thermal conductivity 211
gas thermal conductivity 69
heat of adsorbed phase 66
heat of adsorption 67, 209
heat transfer coefficient 68, 210
isotherms 63, 187, 205
kinetic model 43, 184, 198
mass transfer coefficient 49, 185, 199
material balance 24, 182, 195
T
Task Language 257
Template Organizer 268
Templates 268
Time controls (reason for) 253
Time-driven step controls 246
Toth isotherm (gas) 57
Index 307
U
Upwind differencing schemes 221, 222
User Multicomponent Procedure isotherm (liq)
205
User Multicomponent Submodel isotherm (liq)
205
User Purecomponent Procedure with IAS
isotherm (liq) 206
User Purecomponent Submodel with IAS
isotherm (liq) 206
V
Variable fields 251
Variable Selector dialog box 250
Velocity (gas) 25
Velocity assumption (liq) 196
Vertical beds (gas) 16, 18, 27
Volmer isotherm (gas) 59
W
Wall energy balance (liq) 214
Water softening and purification (ionx) 178

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= = Gas wall heat transfer Peclet number

is taken to be the integral

Axial dispersion contribution

Gas phase accumulation

Adsorbed phase accumulation

= Quadratic Driving Force Approximation

Axial thermal conduction

P-V work compression

Thermal accumulation in gas phase

Axial thermal conduction

Thermal accumulation in solid phase

Axial thermal conduction along the wall

Thermal accumulation in the wall

is the density for component i in fluid phase, and T

can, for example, be determined by a solid film

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