Adsorption Reference

Guide

Version Number: 11.1

September 2001
Copyright (c) 2001 by Aspen Technology, Inc. All rights reserved.
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Contents
Introduction

About This Manual............................................................................................................... i

Associated Manuals.............................................................................................................. i
What You Need To Use This Manual .................................................................................. i
For More Information.......................................................................................................... ii
Online Help ............................................................................................................. ii
Printing the Portable Document Format Files (PDFs) ...........................................iii
World Wide Web ...................................................................................................iii
Technical Support ..................................................................................................iii
1

Gas Adsorption Processes

1-1

About Gas Adsorption Processes .....................................................................................1-2

Bed Model Assumptions for Gas Adsorption Processes..................................................1-3
About Aspen ADSIM's Bed Models ................................................................................1-4
Bed Model Ports...................................................................................................1-4
Configure Form (gas) .......................................................................................................1-4
Configure Form (gas): Bed Type..........................................................................1-5
Configure Form (gas): Spatial Dimensions..........................................................1-7
Configure Form (gas): Internal Heat Exchanger ..................................................1-7
Configure Layer Form (gas) .............................................................................................1-8
General Tab (gas) .............................................................................................................1-9
General Tab (gas): Discretization Method to be used..........................................1-9
General Tab (gas): Number of Nodes ..................................................................1-9
General Tab (gas): Number of Radial Nodes .......................................................1-9
General Tab (gas): Flux Limiter to be used..........................................................1-9
General Tab (gas): Gas Model Assumption .........................................................1-9
Material/Momentum Balance Tab (gas).........................................................................1-10
About Axial Dispersion in Gas Adsorption Processes.......................................1-10
Material/Momentum Balance Tab (gas): Material Balance Assumption...........1-12
Material/Momentum Balance Tab (gas): Momentum Balance Assumption......1-13
Material/Momentum Balance Tab (gas): 2-D Dispersive Properties .................1-16

Adsorption Reference Manual

Contents 1

Kinetic Model Tab (gas).................................................................................................1-20

Kinetic Model Tab (gas): Film Model Assumption ...........................................1-20
Kinetic Model Tab (gas): Kinetic Model Assumption.......................................1-20
Kinetic Model Tab (gas): Form of Lumped Resistance Model..........................1-34
Kinetic Model Tab (gas): Molecular Diffusivities .............................................1-34
Kinetic Model Tab (gas): Form of Mass Transfer Coefficients .........................1-36
Kinetic Model Tab (gas): Apply Cyclic Correction ...........................................1-39
Kinetic Model Tab (gas): Estimated Mass Transfer Coefficient Assumption ...1-40
Gas Adsorption Layer (gas): Particle Material Balance, Number of Nodes ......1-40
Kinetic Model Tab (gas): Particle Material Balance, Effective Diffusivity.......1-40
Isotherm Tab (gas)..........................................................................................................1-41
About Adsorption Isotherms for Gas Adsorption Processes..............................1-41
Guidelines for Choosing Aspen ADSIM Isotherm Models (gas).......................1-42
About Multi-Component Mixture Isotherms (gas) ............................................1-42
Isotherm Tab (gas): Isotherm Assumed for Layer..............................................1-45
Isotherm Tab (gas): Adsorbed Solution Theory.................................................1-55
Isotherm Tab (gas): Isotherm Dependency.........................................................1-55
Energy Balance Tab (gas)...............................................................................................1-56
Energy Balance Tab (gas): Energy Balance Assumption...................................1-56
Energy Balance Tab (gas): Consider Heat of Adsorbed Phase ..........................1-57
Energy Balance Tab (gas): Heat of Adsorption Assumption .............................1-58
Energy Balance Tab (gas): Form of Heat Transfer Coefficient..........................1-59
Energy Balance Tab (gas): Form of Gas Thermal Conductivity........................1-61
Energy Balance Tab (gas): Heat Transfer to Environment ................................1-62
Energy Balance Tab (gas): Form of Gas-Wall Heat Transfer Coefficient .........1-64
Reaction Tab (gas)..........................................................................................................1-65
About Gas Adsorption with Reaction Processes................................................1-65
Reaction Tab (gas): Reactions Present...............................................................1-66
Reaction Tab (gas): Homogeneous Rate Dependency .......................................1-66
Reaction Tab (gas): Number of Homogeneous Reactions .................................1-67
Reaction Tab (gas): Heterogeneous Rate Dependency ......................................1-67
Reaction Tab (gas): Number of Heterogeneous Reactions ................................1-67
Reaction Tab (gas): Are Solid Reactants Present...............................................1-67
Reaction Tab (gas): Solid Reactant List.............................................................1-68
Procedures Tab (gas) ......................................................................................................1-68

2 Contents

Adsorption Reference Manual

Gas Adsorption: Summary of Mass and Energy Balance Equations .............................1-68

Gas Adsorption: Mass Balance for Gas Phase ...................................................1-68
Gas Adsorption: Mass Balance for Additional Solid Phase...............................1-69
Gas Adsorption: Gas Phase Energy Balance......................................................1-69
Gas Adsorption: Solid Phase Energy Balance....................................................1-69
Gas Adsorption: Wall Energy Balance...............................................................1-70
Gas Adsorption: Summary of Factors that affect the Mass Balance Equations.1-70
Gas Adsorption: Defining the Mass Balance for Additional Solid Phases ........1-72
Gas Adsorption: Summary of Factors that affect the Energy Balance ...............1-72
Gas Adsorption: Defining the Energy Balance in the Gas Phase.......................1-72
Gas Adsorption: Defining the Energy Balance for the Solid Phase ...................1-75
Gas Adsorption: Defining Energy Balance for the Wall....................................1-77
Gas Adsorption: Explanation of Equation Symbols ......................................................1-79
2

Ion-Exchange Processes

2-1

About Ion-Exchange Processes ........................................................................................2-2

Bed Model Assumptions for Ion-Exchange .....................................................................2-3
Configure Form (ionx) .....................................................................................................2-3
Configure Layer Form (ionx) ...........................................................................................2-4
General Tab (ionx) ...........................................................................................................2-4
General Tab (ionx): Discretization Method to be Used .......................................2-4
General Tab (ionx): Number of Nodes.................................................................2-4
Material/Momentum Balance Tab (ionx)........................................................................2-5
Material/Momentum Balance Tab (ionx): Material Balance Assumption ...........2-5
About Axial Dispersion in Ion-Exchange Processes........................................................2-7
Deciding When to Use Axial Dispersion in Ion-Exchange Processes .................2-7
Kinetic Model Tab (ionx).................................................................................................2-8
Kinetic Model Tab (ionx): Film Model Assumption ...........................................2-8
Kinetic Model Tab (ionx): Kinetic Model Assumption .......................................2-9
Kinetic Model Tab (ionx): Form of Lumped Resistance .....................................2-9
Kinetic Model Tab (ionx): Form of Mass Transfer Coefficient.........................2-10
Isotherm Tab (ionx)........................................................................................................2-11
About Adsorption Isotherms for Ion-Exchange Processes.................................2-11
Isotherm Tab (ionx): Isotherm Assumed for Layer............................................2-11
Summary of Mass Balance Equations for Ion-Exchange Processes ..............................2-13
Explanation of Equation Symbols for Ion-Exchange Processes ........................2-14
3

Liquid Adsorption Processes

3-1

About Liquid Adsorption Processes.................................................................................3-2

Bed Model Assumptions for Liquid Adsorption..............................................................3-3
Configure Form (liq) ........................................................................................................3-3
Configure Layer Form (liq) ..............................................................................................3-4

Adsorption Reference Manual

Contents 3

General Tab (liq) ..............................................................................................................3-4

General Tab (liq): Discretization Method to be Used ..........................................3-4
General Tab (liq): Number of Nodes ...................................................................3-4
Material/Momentum Balance (liq)...................................................................................3-5
Material/Momentum Balance Tab (liq): Material Balance Assumption..............3-5
Material/Momentum Balance Tab (liq): Pressure Drop Assumption ..................3-6
Material/Momentum Balance Tab (liq): Velocity Assumption............................3-7
Material/Momentum Balance Tab (liq): Overall Material Balance Assumption.3-8
Kinetic Model Tab (liq)....................................................................................................3-8
Kinetic Model Tab (liq): Film Model Assumption ..............................................3-9
Kinetic Model Tab (liq): Kinetic Model Assumption..........................................3-9
Kinetic Model Tab (liq): Form of Mass Transfer Coefficient............................3-10
About Adsorption Isotherms for Liquid Adsorption ......................................................3-11
Guidelines for Choosing Aspen ADSIM Isotherm Models ...........................................3-11
The Ideal Adsorbed Solution Theory (IAS) .......................................................3-11
Isotherm Tab (liq): Isotherm Assumed for Layer...............................................3-12
Energy Balance Tab (liq)................................................................................................3-19
Energy Balance Tab (liq): Energy Balance Assumption ....................................3-19
Energy Balance Tab (liq): Consider Heat of Adsorbed Phase ...........................3-20
Energy Balance Tab (liq): Heat of Adsorption Assumption ..............................3-21
Energy Balance Tab (liq): Form of Heat Transfer Coefficient...........................3-22
Energy Balance Tab (liq): Form of Fluid Thermal Conductivity.......................3-23
Energy Balance Tab (liq): Heat Transfer to Environment .................................3-24
Procedures Tab (liq) .......................................................................................................3-26
Liquid Adsorption: Summary of Mass and Energy Balance ..........................................3-26
Liquid Adsorption: Mass Balance......................................................................3-26
Liquid Adsorption: Solid Phase Energy Balance ...............................................3-27
Liquid Adsorption: Fluid Phase Energy Balance ...............................................3-27
Liquid Adsorption: Wall Energy Balance ..........................................................3-27
Liquid Adsorption: Explanation of Equation Symbols ..................................................3-28
4

Numerical Methods

4-1

About Numerical Methods ...............................................................................................4-2

Choosing the Discretization Method................................................................................4-3
About the Discretization Methods....................................................................................4-4
Upwind Differencing Scheme 1 ...........................................................................4-5
Upwind Differencing Scheme 2 ...........................................................................4-6
Central Differencing Scheme 1 ............................................................................4-7
Central Differencing Scheme 2 ............................................................................4-8
Leonard Differencing Scheme..............................................................................4-8
Quadratic Upwind Differencing Scheme .............................................................4-9
Mixed Differencing Scheme ..............................................................................4-11
Biased Upwind Differencing Scheme ................................................................4-13
Fromms scheme ................................................................................................4-14
Flux Limited Discretization Scheme..................................................................4-14

4 Contents

Adsorption Reference Manual

Estimation with Aspen ADSIM

5-1

Two Estimation Tools in Aspen ADSIM 11.1.................................................................5-2

About the Estimation Module ..........................................................................................5-2
Defining Estimated Variables in the Estimation Module.................................................5-4
Steady-State Estimation Using the Estimation Module ...................................................5-5
Manually Entering Steady-State Experimental Data............................................5-5
Steady-State Experimental Data from the Clipboard ...........................................5-7
Dynamic Estimation Using the Estimation Module.........................................................5-9
Manually Entering Dynamic Experimental Data .................................................5-9
Dynamic Experimental Data from the Clipboard...............................................5-11
Performing Estimation Using the Estimation Module ...................................................5-13
Converting Estimation Module Data..............................................................................5-14
Recommendations When Using the Estimation Module ...............................................5-14
6

Cyclic Operation

6-1

Cyclic Operations in Aspen ADSIM 11.1........................................................................6-2

About the Cycle Organizer...............................................................................................6-2
Opening the Cycle Organizer ...........................................................................................6-3
Cycle Organizer Window.................................................................................................6-3
Step Control .....................................................................................................................6-4
Time Driven Step .................................................................................................6-5
Discrete Event Driven Step ..................................................................................6-5
Step Variables ..................................................................................................................6-9
Adding Step Variables .......................................................................................6-10
Removing Step Variables...................................................................................6-10
Changing Step Variable Values .........................................................................6-11
Interaction Control .........................................................................................................6-12
Defining a Step Interaction.................................................................................6-12
Deleting Interaction Steps ..................................................................................6-12
Adding Extra Interaction Steps ..........................................................................6-13
Interacting Steps and Time Controls ..................................................................6-13
Additional Cycle Controls..............................................................................................6-14
Maximum Cycles Box........................................................................................6-14
Record Initial and Record Frequency Boxes......................................................6-14
Take Snapshot Box.............................................................................................6-15
Cyclic Steady State Testing Box ........................................................................6-15
Additional Step Controls................................................................................................6-16
Execute End of Step Script Box.........................................................................6-16
Take Snapshot at End of Step Box.....................................................................6-17
Generating Cyclic Tasks.................................................................................................6-18
Activating and Deactivating Cyclic Tasks .....................................................................6-19
Cyclic Reports ................................................................................................................6-19
Preparing Aspen ADSIM for Cyclic Reporting .................................................6-20
Cyclic Stream Reports........................................................................................6-21
Cyclic Recovery Reports ....................................................................................6-22
Adsorption Reference Manual

Contents 5

Flowsheeting

7-1

About Model Types..........................................................................................................7-2

General Model Types .......................................................................................................7-3
Reversibility .....................................................................................................................7-4
About Flowsheets in Aspen ADSIM................................................................................7-7
Connectivity on Flowsheets .................................................................................7-7
Templates .............................................................................................................7-9
Demonstrations...................................................................................................7-10
Types of Flowsheet in Aspen ADSIM ...........................................................................7-11
Types of Flowsheet: Simple Flowsheet..............................................................7-11
Intermediate Flowsheet ......................................................................................7-12
Full Flowsheet ....................................................................................................7-13
Single Bed Approach......................................................................................................7-13
Pressure Interaction Diagram .........................................................................................7-14
Interactions .....................................................................................................................7-16
Specifications for Flowsheets.........................................................................................7-19
Solver Options....................................................................................................7-19
Run Time Options ..............................................................................................7-21
Model Specification ...........................................................................................7-21
Consistency and Problem Definition Checks.....................................................7-23
Physical Properties .........................................................................................................7-25
Use of User Fortran ............................................................................................7-26
Using a Physical Properties Application ............................................................7-26
Switching Between Methods..............................................................................7-27
Connecting to Aspen Dynamics Flowsheets ..................................................................7-28
Typical Workflows.............................................................................................7-28
Valid Flowsheet Combinations ..........................................................................7-31
Connecting to a Single Bed Approach Flowsheet..............................................7-35
8

Reference List for Adsorption Processes

6 Contents

8-1

Adsorption Reference Manual

Introduction

This chapter describes:

The contents of this manual
Associated manuals
Where to find further information

About This Manual

This manual describes how Aspen ADSIM handles gas, liquid and
ion-exchange processes. The manual also describes these other
Aspen ADSIM features:
Numerical methods for solving the partial differential equations
Estimation module
Cyclic Organizer
Flowsheeting strategies

Associated Manuals
Aspen ADSIM also has a Library Reference Manual, which
describes the models, streams, procedures and submodels available
in Aspen ADSIM.

What You Need To Use This Manual

To use this manual, you need Aspen ADSIM installed on your PC
or a PC file server running Windows 2000 or Windows NT. For
information on how to do this, read the AES Installation Guide
supplied with the product, or contact your system administrator.

Adsorption Reference Manual

Introduction i

For More Information

You can obtain information on AES products by:
Accessing the comprehensive online Help system
Reading the printed manuals supplied with your product
Printing the Portable Document Format (PDF) files supplied on
the installation CD
Accessing Aspen Technology's web page
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online Help and the PDF files, you can contact Technical Support.
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Online Help

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To

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Display a hierarchy of topics by

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Click the Contents tab

Display an index of all Help topics

Click the Index tab and then type

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Search for words or phrases within

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Click the Find tab and then type

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screen elements, click the What's This button:
or , at the top
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Printing Online Help
To display information on how to print online Help:
1. Open your Aspen ADSIM product and from the Help menu,
click Help Topics.
2. On the Contents tab, double-click Using Help and then
double-click Print Help Topics.

ii Introduction

Adsorption Reference Manual

Printing the Portable

Document Format
Files (PDFs)

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Technical Support

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Adsorption Reference Manual

Introduction iii

Customer support is also available by phone, fax, and email for

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iv Introduction

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Adsorption Reference Manual

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Adsorption Reference Manual

Introduction v

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

Adsorption Reference Manual

Gas Adsorption Processes 1-1

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.

1-2 Gas Adsorption Processes

Adsorption Reference Manual

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 micro- 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 multicomponent adsorption. IAS theory can be used for pure
component isotherms.

Adsorption Reference Manual

Gas Adsorption Processes 1-3

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.

1-4 Gas Adsorption Processes

Adsorption Reference Manual

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.

Adsorption Reference Manual

Gas Adsorption Processes 1-5

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
HB,2
DB

HB,1
Layer 2

H0,1

H0,2

Layer 1
z
W(z)

The effective width W(z) of the bed is given as:

W ( z ) = [4 z (DB z )]

0.5

Where:

DB

Column diameter

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.

1-6 Gas Adsorption Processes

Adsorption Reference Manual

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
Adsorbent
Layer 1

Inner Core

Adsorbent
Layer 2

Bed Shell

Feed

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

Adsorption Reference Manual

Gas Adsorption Processes 1-7

supplied in, or is condensed in order to use its heat of evaporation

to heat the bed.

Internal Heat
Exchanger

Heat Exchange
Jacket

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

1-8 Gas Adsorption Processes

Adsorption Reference Manual

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.
These discretization methods are available for gas phase adsorption
General Tab (gas):
Discretization Method processes:
to be used
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.

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:

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.

P = Z RTg g (overall) or
Py i = Z RTg ci (component)

Where:

Adsorption Reference Manual

Pressure

Compressibility factor

Universal gas constant

Gas Adsorption Processes 1-9

Tg

Gas phase temperature

Molar gas phase density

yi

Mole fraction of component i

ci

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
Adsorption
Processes

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, Ei .

1-10 Gas Adsorption Processes

Adsorption Reference Manual

The dispersion term in the material balance is typically expressed

as:
i E zk

2 ck
z 2

Where:

Interparticle voidage

E zk

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 E z ), typical bed velocities
( g ), and bed height ( H b ):
Pe =

vgH b
Ez

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

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.

Adsorption Reference Manual

Gas Adsorption Processes 1-11

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):
E zk = 0.73Dmk +

v g rp

D
i 1 + 9.49 i mk
2v g r p

Where:

1-12 Gas Adsorption Processes

Gas velocity

Dmk

Molecular diffusivity

E zk

Axial dispersion coefficient

Interparticle voidage

rp

Particle radius

Adsorption Reference Manual

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 usersupplied Fortran subroutine, which Aspen ADSIM interfaces
through the procedure pUser_g_Dispersion.
Material/Momentum
Balance Tab (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 pressuredrop 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

Adsorption Reference Manual

Gas Adsorption Processes 1-13

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:

P
= Kpg
z
Where:

1-14 Gas Adsorption Processes

Kp

Darcys law proportionality constant

Gas velocity

Adsorption Reference Manual

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:

P 1.5 10 3 (1 i ) 2
=
vg
z
(2 rp )2 i3
For details of the Karman-Kozeny model see Bird et al. (1960).
Where:

Shape factor

Dynamic gas viscosity

Momentum Balance Assumption (gas): Burke-Plummer

Equation

This option uses the Burke-Plummer equation to relate velocity to

pressure gradient:
M g (1 i ) 2
P
= 1.75 10 5
vg
z
2rp i3
Where:
M

Molecular weight

The equation is valid for fully turbulent conditions when the

particle Reynolds number Re is:

Re =

M g 2rp v g

> 1000

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.
1.5 10 3 (1 i ) 2
(1 i ) 2
P
5
v
M
v

1
.
75
10

=
+

g
g
2 3
3 g

z
r
2

(
)
r
2

p
i
p
i

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).

Adsorption Reference Manual

Gas Adsorption Processes 1-15

Set Variables for Pressure-Drop Options (gas)

This table shows the variables you need to specify for the pressure
drop options:

Material/Momentum
Balance Tab (gas): 2D Dispersive
Properties

Equation Symbol

Variable

Definition

Kp

Kp

Proportionality constant

Sfac

Sphericity

rp

Rp

Particle radius

Ei

Interparticle voidage

The 2-D Dispersive Properties option is available only if you

selected vertical bed and two-dimensional discretization. The axial
dispersion is calculated from:
i E zk

2 ck
z 2

Additionally, a radial dispersion term is also evaluated:

i E rk

1 c k
r

r r r

If you later specify the process as non-isothermal, equivalent

dispersive terms are evaluated for the gas and solid phase energy
balances. Namely:
2Tg
Gas phase thermal conduction in axial direction: i k gz
z 2
Gas phase thermal conduction in radial direction:
1 Tg
r

i k gr
r r r

Solid phase thermal conduction in axial direction: k sz

Solid phase thermal conduction in radial direction:

1 Ts
k sr
r

r r r

2Ts
z 2

Choose from:
Fixed
Estimated

1-16 Gas Adsorption Processes

Adsorption Reference Manual

2-D Dispersive Properties (gas): Fixed

Choose this option if the dispersive properties are constant

throughout the packed bed. You must supply values for:
E zk : the dispersion coefficient of component k for the axial
direction
Erk : the dispersion coefficient of component k for the radial
direction
For non-isothermal operation, you must give values for the
following thermal conductivities:
k g : the effective thermal conductivity of the gas phase

k s : 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):
E zk = 0.73Dmk +

v g rp

D
i 1 + 9.49 i mk
2v g r p

Where:

Adsorption Reference Manual

Gas Velocity

Dmk

Molecular diffusivity of component k

E zk

Axial dispersion coefficient of component k

Interparticle voidage

rp

Particle radius

Gas Adsorption Processes 1-17

The radial dispersion coefficient is evaluated according to

(Carberry, 1976):
E rk =

rp v g
4

Where:
Erk

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

k gz = g C pg (Ez ,i yi )
i =1

Where:
=

k gz

Effective gas phase thermal conductivity in

axial direction

Molar gas density

C pg

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 grdyn = i g C pg (Erk yk )
k =1

Where:

k grdyn

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.

1-18 Gas Adsorption Processes

Adsorption Reference Manual

The static contribution of the gas phase effective thermal

conductivity in the radial direction is:

k grstat = i (k g + 2r p rg )

Where:

= 1 .0

rg

= Factor

0.227 10 3 T
=

1 p 100
1+
2(1 ) p

= Radiation contribution

Emissivity

kg

Thermal conductivity of the gas.

The total effective radial gas phase thermal conductivity is now

given by:
k gr = k grdyn + k grstat
The effective radial solid phase thermal conductivity comes from:
k sr = k srstat =

(1 i )
1

+
kg
ks
+ rs 2rp

Where:
p T
rs = 0.227 10

2 p 100
3

= 0.28
=
ks

= Radiation contribution

= Function of the packing density

2
= Factor
3

= 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 k s is constant through the simulation.

Adsorption Reference Manual

Gas Adsorption Processes 1-19

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

1-20 Gas Adsorption Processes

Adsorption Reference Manual

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

Uniform

Activated carbon alumina High

silica molecular sieve
carbon

Negligible

Composite

Zeolites

High

High

Macropore
Diffusional Resistance

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.

Adsorption Reference Manual

Gas Adsorption Processes 1-21

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:
w
J ads ,i s = i = f (ci )
t
Where:
s
=
Adsorbent bulk density
wi
=
Loading of component i due to adsorption
J ads ,i
=
Mass transfer rate of component i

1-22 Gas Adsorption Processes

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.

Adsorption Reference Manual

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:

Bulk:
cbk, B, w*bk

Macropores:
w*msk, cmsk

Interpellet
Voidage: i

Pellet
(macroparticle)

rP
2rc
Intrapellet
Porosity P

Solid
Microporous
Particles: wk, ck*
cbk, B, w*bk
Bulk Gas

*
cmsk, (1-i) P, wmsk

c*k, wk

Macropore

Solid
Surface

i
Interpellet
porosity

Micropore

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

Adsorption Reference Manual

Gas Adsorption Processes 1-23

Gas Phase

The component balance in the bulk gas phase is of the form:

(cbk vg )
z

+ B

cbk
w
c
+ (1 p ) s k + (1 i ) p msk = 0
t
t
t

[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:

(1 i ) p cmsk + (1 p ) s wk
t

= K mac (cbk cmsk )

[accumulation] + [mass transfer to micropore] = [rate of mass

transfer from bulk gas]
Solid Film Model:

(1 i ) p

c msk
wk
*
*
+ (1 p ) s
= (1 p ) s K mac (wbk
wmsk
)
t
t

Micropore (Particle)

Fluid Film Model:

(1 )
p

wk
= K mic (c msk c k* )
t

[accumulation] = [rate of mass transfer from macropore]

Solid Film Model:

(1 )
p

wk
= (1 p ) s K mic (wsk* wk )
t

[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: K mac and K mic .
The following options are available in the Form of Mass Transfer
Coefficient field.

1-24 Gas Adsorption Processes

Adsorption Reference Manual

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 K mac is given by:
K mac = 15.0

DefP
rP2

Where:
DefP

Component diffusivities in macropores

rp

Particle radius

The micropore constant K mic is given by:

K mic = 15.0

Defc
rc2

Where:
Defc

Component diffusivities in micropores

rc

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.

wi
= f (Tg , P, ci , Ts , wi , v g )
t
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.

Adsorption Reference Manual

Gas Adsorption Processes 1-25

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.

1-26 Gas Adsorption Processes

Adsorption Reference Manual

The following figure illustrates these resistances:

Boundary
Layer

Adsorbent
Particle (Uniform
Pore Structure)

Bulk
Gas
w i
wi* r

Ji = asDei

r =rp

wi(r)
ci

w i
r

Ji

w i
r

= a(1 )k f c i c i*
r =rp

=0
r =0

c*i
r

rp
The particle material balance is expressed as:

2 wk 2 wk
wk
+
Dek
=0
t
r 2
r r
Where:
wk

Loading

Dek

Effective adsorbed phase diffusion coefficient

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.

Adsorption Reference Manual

Gas Adsorption Processes 1-27

The boundary conditions for this partial differential equation come

from both the symmetry condition at r=0:
wi
r

=0
r =0

and the material flux through the boundary layer at r = r p :

wk
r

a s Dek

= a(1 i )k fk c k c k*

r = rp

Where:
a

Specific particle surface

Bulk density of solid

Interparticle voidage

k fk

Boundary layer mass transfer coefficient

ck

Gas phase concentration

c k*

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:

wi* = wi

r = rp

( )

= f eq ci*

Where:
f eq

Isotherm equation

wi*

Loading at r = r p

The boundary layer mass transfer coefficient is expressed using the

following Sherwood number correlation:
Shi = 2 + 1.1Sci1/ 3 Re 0.6

Where:

Shi =
Sci =

1-28 Gas Adsorption Processes

k fi 2rp
Dmi

Dmi g M

Sherwood number

Schmidt number

Adsorption Reference Manual

Re =

v g 2rp M g

Reynolds number

Dmi

Mean molecular diffusion coefficient

Gas phase dynamic viscosity

Molar gas phase density

Mean molecular weight

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.

Adsorption Reference Manual

Gas Adsorption Processes 1-29

The following figure illustrates these resistances:

Boundary
Layer

Adsorbent
Particle (Uniform
Pore Structure)

Bulk
Gas
w i
wi* r

w
s
Dei i
(1 ) r

cip
r

= k f ci ci*
r = rp
rp

w
c p
3 i r 2 dr
3 i r 2 dr
t
t
+ (1 ) p 0 3
Ji = s 0 3
rp
rp

r =rp

w i
r

Ji
c
c*i r

r = rp

rp

wi(r)
ci

+ D p ,i

=0
r =0

p
i

r = rp

c pi (r)

cip
r

rp

=0
r = rp

The particle material balance is given by:

2 ckp 2 ckp
s wk

ckp
p
+
Dek s
+
D pk
2
r
1
t 1 t
r r

2 wk 2 wk
+

=0
r 2
r r

Where:

1-30 Gas Adsorption Processes

Interparticle voidage

Intraparticle voidage

Bulk density

wk

Loading

ckp

Gas phase concentration

Adsorption Reference Manual

Dek

Effective adsorbed phase diffusion coefficient

D pk

Effective pore gas phase diffusion coefficient

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:
1
1
Tort 1

=
+
D pi
p DKi Dmi
and
T
DKi = 97 rPore
Mi

0.5

Where:

Tort

Tortuosity of adsorbent

D pi

Effective pore gas diffusion coefficient

DKi

Knudsen diffusion coefficient

Dmi
=
the mixture

Molecular diffusion coefficient of component i in

rPore

Pore radius in adsorbent

Adsorbent temperature

Mi

Molecular weight of component i

The boundary conditions for this partial differential equation come

from both the symmetry condition at r=0:

wi
r

=0
r =0

and

cip
r

Adsorption Reference Manual

=0
r =0

Gas Adsorption Processes 1-31

and the material flux through the boundary layer at r = r p :

w
s
Dei i
(1 ) r

+ D p ,i
r = rp

cip
r

= k fi ci ci*

r = rp

rp

rp

w
c p
3 i r 2 dr
3 i r 2 dr
t
t
Ji = s 0 3
+ (1 ) p 0 3
rp
rp

Where:

Bulk density of solid

Interparticle voidage

Interparticle voidage

k fi

Boundary layer mass transfer coefficient

ci

Bulk gas phase concentration

ci*

Interface gas phase concentration

cip

Pore gas phase concentration

wi

Loading

Ji

Material flux

rp

particle radius

D pi

Effective gas phase pore diffusion coefficient

Dei

Effective adsorbed phase diffusion coefficient

The gas phase concentration and the loading are coupled by the
condition that thermodynamic equilibrium has been at each radial
location inside particle, so:

( )

wi = f eq cip
Where:
f eq

Isotherm equation

cip

Pore gas phase concentration

wi

Loading

These calculations give the isotherm correlation at each radial

node, which increases the computational effort.

1-32 Gas Adsorption Processes

Adsorption Reference Manual

The boundary layer mass transfer coefficient is given by the

following Sherwood number correlation:
Shi = 2 + 1.1Sci1/ 3 Re 0.6

Where:

Shi =
Sci =
Re =

k fi 2rp
Dmi

Dmi g M
v g 2rp M g

Sherwood number

Schmidt number

Reynolds number

Dmi

Mean molecular diffusion coefficient

Gas phase dynamic viscosity

Molar gas phase density

Mean molecular weight

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.

wi
= f (Tg , P, ci , Ts , wi , v g )
t
Note: Langmuir adsorption kinetics is quite a popular option, and
can be applied with such a procedure.
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.

wi
= f (Tg , P, ci , Ts , wi , v g )
t
Note: Langmuir adsorption kinetics is quite a popular option, and
can be applied with such a procedure.

Adsorption Reference Manual

Gas Adsorption Processes 1-33

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 ( J ads ,i ), to the local
gas and solid states. The mass transfer rate is related to the
adsorbent uptake, as follows:

wi
= J ads ,i
t

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:

wi
= MTC gi (ci ci* )
t

Solid:
wi
= MTC si (wi* wi )
t

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:

(c ) (ci* )
w
s i = MTC gi i
2ci
t

Solid:

(w* ) (wi )
wi
= MTC si i
2wi
t
2

Kinetic Model Tab

(gas): Molecular
Diffusivities

1-34 Gas Adsorption Processes

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

Adsorption Reference Manual

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.

Bulk:
cbk, B, w*bk

Macropores:
w*msk, cmsk

Interpellet
Voidage: i

Pellet
(macroparticle)

rP
2rc
Intrapellet
Porosity P

Solid
Microporous
Particles: wk, ck*
cbk, B, w*bk
Bulk Gas

*
cmsk, (1-i) P, wmsk

c*k, wk

Macropore

Solid
Surface

i
Interpellet
porosity

Micropore

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.

Adsorption Reference Manual

Gas Adsorption Processes 1-35

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:
E acti
MTC i = k 0i exp

RT

To use this option, you must supply the pre-exponential factor k 0i

and the activation energy E acti 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 finetune the values by adjusting the estimated values until the timing
and shape of the simulated breakthrough curves match the
experimentally measured breakthrough curves.

1-36 Gas Adsorption Processes

Adsorption Reference Manual

In general, the adsorption rate model for component i can be

expressed as:
wi
= ki wi* wi = k i K Ki ci ci*
t

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:

rp
rp2
rc2
1
=
+
+
k i 3k fi 15 p K pi 15K Ki Dci
The Henry's coefficient K Ki is obtained from the isotherm as:

K Ki =

w*
wi*
= RT i
Pi
ci

The dimensionless Henrys coefficient, K Ki , is obtained by:

K Ki = K Ki

s
i

The film resistance coefficient k fi is obtained from the Sherwood

number as:

k fi = Shi

Dmi
2rp

Where:

Shi =

2.0 + 1.1Sci1 / 3 Re 0.6

Re

Reynolds number

Sci

Schmidt number

(Dmi s )

The macropore diffusion coefficient K pi is obtained from:

1
1
1

= Tort
+
K pi
D
D
mi
Ki
The Knudsen diffusion coefficient DKi is:
T
DKi = 97 rPore
Mi

Adsorption Reference Manual

0.5

Gas Adsorption Processes 1-37

Where:

Gas density

Dci

Micropore diffusion coefficient

DKi

Knudsen diffusion coefficient

Dmi

Multi-component molecular diffusion coefficient

ep

particle (macro) porosity

ki

effective mass transfer coefficient

K Ki

Henry's coefficient

k fi

Film resistance coefficient

K pi

Macropore diffusion coefficient

Loading

Universal Gas Constant

rc

Radius of crystalline or primary micropore

rp

Particle radius

Tort

Tortuosity factor

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.

MTC i =

1-38 Gas Adsorption Processes

k 0 Pi
E acti
exp

P
RT

Adsorption Reference Manual

You have to supply the pre-exponential factor k 0 Pi and the

activation energy E acti 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:
MTC s ,i =

Dei
rP2

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:

= 0 .5

De
t Cycle
rP2

The parameter is a function of :

0.1

: = 15
5.14
0.001 < 0.1: =

0.001
: = 162.5
The above equations are evaluated automatically by Aspen ADSIM
when you select this option.

Adsorption Reference Manual

Gas Adsorption Processes 1-39

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:
1 2 w 2 wk +1 wk 1 wk +1 2wk + wk 1
+

r
2(r )
r 2 r r rk
(r )2

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.

1-40 Gas Adsorption Processes

Adsorption Reference Manual

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 multicomponent 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:

About Adsorption
Isotherms for Gas
Adsorption
Processes

Variable

Unit of measurement

Loading (w)

kmol/kg

Gas phase concentration (c)

kmol/m3

Pressure (P)

bar

Temperature (T)

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).

Adsorption Reference Manual

Gas Adsorption Processes 1-41

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 MultiComponent 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.

1-42 Gas Adsorption Processes

Adsorption Reference Manual

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 interspecies 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.
Adsorption Reference Manual

Gas Adsorption Processes 1-43

The chemical potential for an adsorbed phase can be written as

(Kast, 1988):

ads ,i (T , , xi ) = i0 (T ) + RT ln (Pi 0 ( )) + RT ln ( i xi )

The chemical potential for an ideal gas phase is given by:

gas ,i = i0 (T ) + RT ln ( yi P )
The equilibrium condition is:

gas ,i = ads ,i
Assuming ideal behavior in the adsorbed phase (that is, i = 1 ), an
expression analogous to Raoults law can be derived:
yi P = xi Pi 0 ( )

The pressure Pi 0 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 Pi 0 and the
spreading pressure i0 is derived using the Gibbs-Duhem equation
for a single adsorbed component:

Ad i0 = wi0 d i0 = wi0 RTd ln( Pi 0 ( )

On integrating and using the pure component isotherm to replace

wi0 :
A i0
=
RT

Pi0

f eq (T , P, IP )
dP
P

The equation set is completed with the following conditions:

n

x
i =1

=1

y
i =1

=1

i0 = 0j = k0 = ...
The total loading and component loadings are calculated from:
n

xi

w
i =1

0
i

1
wtot

and

wi = xi wtot

1-44 Gas Adsorption Processes

Adsorption Reference Manual

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 ( i = 1 ).
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 g E 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
yi P = i xi Pi 0 ( )

can be evaluated.
Isotherm Tab (gas):
Isotherm Assumed
for Layer

Adsorption Reference Manual

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

Gas Adsorption Processes 1-45

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:

wi =

IP1 Pi
1 + IP2 Pi

(partial pressure)

IP1ci
1 + IP2 ci

(concentration)

or

wi =

Langmuir 2. The isotherm is a function of temperature, and one of

partial pressure or concentration:

IP1e IP2 / Ts Pi
wi =
1 + IP3 e IP4 / Ts Pi

(partial pressure)

or

wi =

IP1e IP2 / Ts ci
1 + IP3 e IP4 / Ts ci

(concentration)

Langmuir 3. The isotherm is a function of temperature, and one of

partial pressure or concentration. Unlike Langmuir2, the maximum
loading, expressed by (IP1 IP2Ts ) , is a function of temperature, so
reflects more accurately the physical reality of numerous adsorption
processes:

wi =

(IP1 IP2Ts )IP3 e IP / T Pi

4

1 + IP3 e IP4 / Ts Pi

(partial pressure)

or

wi =

1-46 Gas Adsorption Processes

(IP1 IP2Ts )IP3 e IP / T ci

4

1 + IP3 e IP4 / Ts ci

(concentration)

Adsorption Reference Manual

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:
wi = IP1 Pi IP2

(partial pressure)

or
wi = IP1C iIP2

(concentration)

Freundlich 2. The isotherm is a function of temperature, and one

of partial pressure or concentration:
wi = IP1e IP3 / Ts Pi IP2

(partial pressure)

or
wi = IP1e IP3 / Ts ciIP2

(concentration)

Isotherm Assumed for Layer (gas): Langmuir-Freundlich

Model

This isotherm is a function of temperature, and one of partial

pressure or concentration:

IP1 IP2 PiIP3 e IP4 / Ts

wi =
1 + IP5 PiIP3 e IP6 / Ts

(partial pressure)

or

wi =

IP1 IP2 ciIP3 e IP4 / Ts

1 + IP5 ciIP3 e IP6 / Ts

(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:

wi = IP1Pi

(partial pressure)

or

wi = IP1ci

Adsorption Reference Manual

(concentration)

Gas Adsorption Processes 1-47

Henry 2. The isotherm is a function of temperature, and one of

partial pressure or concentration:
wi = IP1e IP2 / Ts Pi

(partial pressure)

or
wi = IP1e IP2 / Ts ci

(concentration)

Isotherm Assumed for Layer (gas): Toth Model

The isotherm is a function of partial pressure or concentration:

1

( IP1 Pi )

wi =
IP2
1 + ( IP3 Pi )
IP2

IP2

(partial pressure)

or
1

( IP1ci )

wi =
IP2
1 + ( IP3 ci )
IP2

IP2

(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:
IP
IP1 Pi exp 2
Ts
wi =

IP4
IP
1 IP5 Pi exp 6
1 + IP3 Pi exp
Ts
Ts

(partial pressure)

or
IP
IP1ci exp 2
Ts
wi =

IP4
IP
1 IP5 ci exp 6
1 + IP3 ci exp
Ts
Ts

1-48 Gas Adsorption Processes

(concentration)

Adsorption Reference Manual

Isotherm Assumed for Layer (gas): BET Multilayer

The BET Multilayer isotherm is similar to the BET isotherm, but

has an additional parameter, IP4 , 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:

i =

Pi
Psat

If you selected concentration dependency, the following equation is

used to calculate the partial pressure:
Pi = ci RTg

The saturation pressure Psat is calculated according to a base 10

Antoine equation, using degrees Celsius or Kelvin as temperature
units of measurement. The parameter IP8 is then a conversion
factor for calculating Psat in bar.
Psat = IP8 10

IP5

IP6
IP7 + Ts

The kinetic factor b is:

IP
b = IP2 exp 3
Ts
The isotherm is:

IPb 1 (IP4 + 1) IP4 + IP4 IP4

wi = 1
IP4 +1
1 1 + (b 1) b

Isotherm Assumed for Layer (gas): Dubinin-Astakov Model

This isotherm is a function of temperature, and one of partial

pressure or concentration:

wi = IP1 exp ( AA / IP2 ) 2 + IP3 exp ( AA / IP4 ) 2

Where:

P
AA = RTs ln i
Psat

(partial pressure)

or
Adsorption Reference Manual

Gas Adsorption Processes 1-49

 c RT
AA = RTs ln i s
Psat

(concentration)

and
Psat = IP8 10

IP6
IP5
Ts IP7

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:

wi = IP1 Pi + IP2

(partial pressure)

or
wi = IP1ci + IP2

(concentration)

Isotherm Assumed for Layer (gas): Volmer Model

The Volmer isotherm expresses concentration as a function of

loading:
ci =

IP1 wi
IP1 wi
exp
IP2 IP1 wi
IP2 IP1 wi

Isotherm Assumed for Layer (gas): Myers Model

TheMyers isotherm expresses concentration as a function of

loading:

w
ci = IP1 exp IP2 i
IP1

1-50 Gas Adsorption Processes

Adsorption Reference Manual

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:
wi =

IP1i Pi
1 + (IP2 k Pk )

(partial pressure)

IP1i ci
1 + (IP2 k c k )

(concentration)

or
wi =

Extended Langmuir 2. This isotherm is a function of temperature,

and one of partial pressure or concentration:

wi =

IP1i e IP2 i / Ts Pi
1 + IP3k e IP4 k / Ts Pk

(partial pressure)

IP1i e IP2 i / Ts ci
1 + IP3k e IP4 k / Ts c k

(concentration)

or
wi =

Extended Langmuir 3. This isotherm is a function of temperature,

and one of partial pressure or concentration:

wi =

( IP1i IP2i Ts ) IP3i e IP4 i / Ts Pi

1 + IP3k e IP4 k / Ts Pk

(partial pressure)

( IP1i IP2i Ts ) IP3i e IP4 i / Ts ci

1 + IP3k e IP4 k / Ts c k

(concentration)

or
wi =

Adsorption Reference Manual

Gas Adsorption Processes 1-51

Isotherm Assumed for Layer (gas): Extended LangmuirFreundlich Model

This isotherm is a function of temperature, and one of partial

pressure or concentration:
IP1i IP2i Pi IP3 i e IP4 i / Ts
wi =
1 + IP5k PkIP3 k e IP4 k / Ts
k

(partial pressure)

(concentration)

or
wi =

IP1i IP2i ciIP3 i e IP4 i / Ts

1 + IP5k c kIP3 k e IP4 k / Ts
k

Isotherm Assumed for Layer (gas): Dual-Site Langmuir Model

This isotherm is a function of temperature, and one of partial

pressure or concentration:

Wi =

IP1i e IP2 i / Ts Pi
IP5i e IP6 i / Ts Pi
+
1 + ( IP3k e IP4 k / Ts Pk ) 1 + ( IP7 k e IP8 k / Ts Pk )
k

(partial pressure)
or
Wi =

IP1i e IP2 i / Ts ci
IP5i e IP6 i / Ts ci
+
1 + ( IP3k e IP4 k / Ts ck ) 1 + ( IP7 k e IP8 k / Tk ck )
k

(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:
IP1i IP2i Pi e IP3 i / Ts
1 + IP2 k Pk e IP3 k / Ts

(partial pressure)

IP1i IP2i ci e IP3 i / Ts

wi =
1 + IP2 k ck e IP3 k / Ts

(concentration)

wi =

or

1-52 Gas Adsorption Processes

Adsorption Reference Manual

Isotherm Assumed for Layer (gas): Dual Layer B.E.T.

This isotherm is a function of temperature, and one of partial

pressure or concentration:

IP2i e IP3i / Ts IP4i IP2 k Pk e IP3 k / Ts

IP1i IP2i Pi e IP3i / Ts
k
wi =
+
IP3 k / Ts
1 + IP2 k Pk e

IP3 k / Ts
IP3 k / Ts
k
1 + IP2 k Pk e
1 + IP4 k IP2 k Pk e

k
k

(partial pressure)

or
IP3 i / Ts

IP2i e IP3 i / Ts IP4i IP2 k ck e IP3 k / Ts

IP1i IP2i ci e
k
+
wi =
IP3 k / Ts

1 + IP2 k ck e
IP3 k / Ts
IP3 k / Ts
k
1 + IP2 k ck e
1 + IP4 k IP2 k ck e

k
k

(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:
wi = f eq (T , P, y1 ... y nc , IP )

(partial pressure)

or
wi = f eq (T , c1 ...cnc , IP )

Adsorption Reference Manual

(concentration)

Gas Adsorption Processes 1-53

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 Pi 0 (resulting in the same
spread pressure as the mixture at pressure P), to the loading wi0
by means of a pure component isotherm:
wi0 = f eq T , Pi 0 , IP

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:
A i0
= g T , Pi 0 , IP with g =
RT

Pi0

f eq (T , P, IP )
P

dP

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)
The functional relationship is:
wi = f eq (T , P, y1 ... y nc , IP )

(partial pressure)

or
wi = f eq (T , c1 ...cnc , IP )

(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 Pi 0 (resulting in the
same spread pressure as the mixture at pressure P), to the
loading wi0 by means of a pure component isotherm:

wi0 = f eq T , Pi 0 , IP

The second submodel is gUserGibbs. This integrates the Gibbs

isotherm to give the spread pressure. The relationship to be
evaluated is:
A i0
= g T , Pi 0 , IP with g =
RT

1-54 Gas Adsorption Processes

Pi0

f eq (T , P, IP )
P

dP

Adsorption Reference Manual

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:

i = f (T , p, x1 ,..., xnc )
In the isotherm dependency box, choose from:
Isotherm Tab (gas):
Isotherm Dependency Concentration The adsorption isotherm model is a function
of concentration.
Partial Pressure The adsorption isotherm model is a function
of partial pressure

Adsorption Reference Manual

Gas Adsorption Processes 1-55

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 Tg and the solid temperature Ts 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:
i k gz

2T
z 2

You need to define the form of the gas thermal conductivity.

1-56 Gas Adsorption Processes

Adsorption Reference Manual

Energy Balance Assumption (gas): Non-Isothermal with Solid

Conduction

This option includes the thermal conduction term in the solid

energy balance:
k sz

2Ts
z 2

You must supply a value for k sz 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:
H i = s C pai wi

Ts
t

The total contribution is the sum for all components:

(H )
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.

Adsorption Reference Manual

Gas Adsorption Processes 1-57

Consider Heat of Adsorbed Phase(gas): Constant

Here, the heat capacities of the adsorbed phase components C pai

are constant.
Consider Heat of Adsorbed Phase(gas): User Procedure

With this option, the heat capacities of the adsorbed phase

components C pai 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 C pai 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):
HTi =

w
H i
t
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:

( HT )
i

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.

1-58 Gas Adsorption Processes

Adsorption Reference Manual

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:

H ij = f (Tsj , Pj , wij )
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:

H ij = f (Tsj , Pj , wij )
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:
rate of heat transferred per m 3 of bed = HTC a p (Tg Ts )
If there is no such heat transfer resistance, the gas and solid
temperatures are equal (lumped):
Tgj = Tsj 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.

Adsorption Reference Manual

Gas Adsorption Processes 1-59

Form of Heat Transfer Coefficient (gas): Estimated

The heat transfer coefficient is estimated as follows:

1. Calculate the Reynolds number:
2r M g v g
Re = p

If the calculated value falls below 1E-10, it is reset to this

value.
2. Calculate the Prandl number:
C pg
Pr =
kg M
If the calculated value falls below 1E-10, it is reset to this
value.
3. Calculate the j-factor:
If Re < 190 then j = 1.66 Re 0.51 otherwise j = 0.983Re 0.41
4. Calculate the heat transfer coefficient:
HTC = jC pg v g g Pr

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:
HTC j = f (Tgj , Pj , c j , vgj )

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.

1-60 Gas Adsorption Processes

Adsorption Reference Manual

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 k g 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:
k gz

(Heat capacity) x (Averaged Axial dispersion

coefficient) x (Molar density)

k gz = C pg (Ezk yk ) g
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.

Adsorption Reference Manual

Gas Adsorption Processes 1-61

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:
4H w
(Tg Tamb )
DB

The conductivity along the wall and the heat accumulation in the
wall are neglected. H w 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 H w for the
column cross section shown in the Heat Transfer to Environment
figure (on the next page).

ln D1 ln Do

D
D
D
1
1

i
1
Hw = i
+
+
+

Do
k1
k2
2 Di H

H
wo
wi
2
2

1-62 Gas Adsorption Processes

Adsorption Reference Manual

Do D1 Di

Tg

Tamb

Hwi

Adsorption Reference Manual

k1

k2

Hwo

Gas Adsorption Processes 1-63

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 GasWall Heat Transfer
Coefficient

There are two options available for the definition of the gas-wall
heat transfer coefficient H w :
Constant
Estimated
Form of Gas-Wall Heat Transfer Coefficient (gas): Constant

In the Specify table for the layer, set the heat transfer coefficient
H w 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:

C sphere H B
Nu w 1 +
DB Pe H

= 2 10 6 (Pe H )2 + 0.0477 Pe H + 22.11

where:
C sphere =

12 for a packed bed of spheres

H w xchar
kg

Nu w =

= Nusselt number for gas-wall heat

transfer
xchar v g g MC pg

Pe H =

kg

= Gas wall heat transfer Peclet

number
xchar

1-64 Gas Adsorption Processes

1.15(2 rp )

= Characteristic length for a sphere

Adsorption Reference Manual

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

Adsorption Reference Manual

Gas Adsorption Processes 1-65

xenon and krypton until sufficient time has elapsed for the shortlived 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

Thereaction 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.

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Adsorption Reference Manual

Reaction Tab (gas):

Number of
Homogeneous
Reactions
Reaction Tab (gas):
Heterogeneous Rate
Dependency

In the Number of Homogeneous Reactions box, select the number

of reactions that occur in the gas phase.

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:

Adsorption Reference Manual

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

Gas Adsorption Processes 1-67

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 userdefined 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.
The overall mass balance for a multi-component gas phase
Gas Adsorption:
Mass Balance for Gas accounts for the convection of material and mass transfer, from the
Phase
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:

(v g g )
w
+ s k = 0
k t
z

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):

c
2 ck
1 c k (v g c k )
i E zk

E
+ B k + Jk = 0
r
+
i
rk
2
z
t
r r r
z

1-68 Gas Adsorption Processes

Adsorption Reference Manual

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:

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.

c sol ,i
t

Rsol ,i = 0

The governing partial differential equation is:

2Tg
T g
T g
v g
+ Cvg v g g
+ B C vg g
+P
2
z
t
z
z
4H w
(Tg To ) + H r + s,cat C p,cat Tg + aHx QHx = 0
+ HTCa p (Tg Ts ) +
DB
t

k ga i

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

Adsorption Reference Manual

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)

Gas Adsorption Processes 1-69

The solid phase energy balance is:

n
1 1 Ts
T
T
2Ts
k sa 2 k sr

+ sC ps s + s (C pai wi ) s
t
t
z
r r r r
i =1
n
w

+ s H i i HTCa p (Tg Ts ) = 0
t
i =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:

2
2 Tw
Tw
4 DB
4(DB + WT )
(T T ) + H amb
(T T ) = 0
kw
+ w c pw
Hw
t
z 2
(DB + WT )2 DB2 w amb
(DB + WT )2 DB2 g w

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 ck
i E zk
z 2
Gas Adsorption: Radial Dispersion Term

This term is only active if you chose vertical bed and twodimensional spatial discretization:
i E rk

1 c k
r

r r r

Gas Adsorption: Convection Term

The convection term is:

(v g c k )
z

1-70 Gas Adsorption Processes

Adsorption Reference Manual

Gas Adsorption: Gas Phase Accumulation Term

The accumulation term is:

ck
t

Gas Adsorption: Rate of Flux to Solid Surface

The rate of flux to the solid surface is given by:

J = S

w
t

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:
J
wk
= MTCs k (wk wk* ) = ads ,k
t
s
There are analogous expressions for gas films and quadratic

wk
t
is taken to be the integral uptake of the particle as determined by
the flux through the boundary layer. (See Also Particle MB.)

driving forces. If a particle material balance was considered,

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:
J cat ,reac ,k + i J gas ,reac ,k

Where:
J cat ,reac ,k

rate of consumption or production of k by

heterogeneous (catalytic) reactions

J gas ,reac ,k

rate of consumption or production of k by

homogeneous (gas phase) reactions.

J gas ,reac , k =

n reacgas

gas , j ,k R gas , j

j =1

Adsorption Reference Manual

Gas Adsorption Processes 1-71

J cat ,reac ,k = s,cat

n reaccat

cat , j ,k Rcat , j

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:
J k = J ads ,k + J cat ,reac ,k + i J gas ,reac ,k
Jk = s

Gas Adsorption:
Defining the Mass
Balance for
Additional Solid
Phases

wk
+ J cat , reac ,k + i J gas ,reac , k
t

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:
c sol ,i
t

Rsol ,i = 0

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:
P

v g
z

Gas Adsorption: Convective Term

The gas convective term is always included in the gas phase energy
balance:
C vg v g g

1-72 Gas Adsorption Processes

T g
z

Adsorption Reference Manual

Gas Adsorption: Accumulation in Gas Phase

The enthalpy accumulation in the gas phase is represented as:

i C vg g

T g
t

Gas Adsorption: Axial Thermal Conduction in Gas Phase

The axial gas thermal conduction (axial thermal dispersion) term is

given by:
i k gz

2Tg
z 2

Where k gz 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:
i k gr

1 Tg
r
r r r

Where k gr 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 solidsl:
Rate of heat transferred per unit volume = HTCa p (Tg Ts )
with:
a p = (1 i )

3
rp

This is for adsorption only. You set a p for adsorption and reaction.

Adsorption Reference Manual

Gas Adsorption Processes 1-73

Gas Adsorption: Heat Exchange between Gas and Internal

Wall

For one-dimensional vertical and horizontal bed models:

4

Hw
(Tg To)
DB

Where:
To = Tamb for adiabatic/thin walls and
To = Tw 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:
H R = i

nreac , gas

H
k =1

Rgas , k

R gas ,k + s ,cat

nreac ,cat

H
l =1

Rcat ,l

Rcat ,l

Where:
k

index for the set of homogenous reactions

index for the set of heterogeneous reactions

H Rgas ,k , H Rcat ,l =

molar heats of reactions k and l, typically in

MJ/kmol

Rgas , k

rate of homogenous reaction k, typically in

kmol/(m3 s)

Rcat ,l

rate of heterogeneous reaction l, typically in

kmol/(kg s)

s,cat

1-74 Gas Adsorption Processes

catalyst bulk density

Adsorption Reference Manual

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 manual:
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:
a Hx QHx
Where a Hx is the specific heat exchange area per unit bed volume
and QHx the energy flux exchanged, given by:
QHx = U Hx (Tg THx )

for single phase exchange media, and

QHx = U Hx ,Cw (Tg TCw ) + U Hx , St (Tg TSt )

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:

s C ps

Adsorption Reference Manual

Ts
t

Gas Adsorption Processes 1-75

Gas Adsorption: Axial Thermal Conductivity in Solid Phase

The solid thermal conduction term is:

k sz

2Ts
z 2

Gas Adsorption: Radial Thermal Conductivity in Solid Phase

This term is active only for vertical beds and two-dimensional

spatial discretization:
k sr

1 Ts
r

r r r

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:
HTi = H i

wi
t

These rates are held in vectors HTi and summed for all
components to give the total rate of heat generation by adsorption
per unit volume of solid:

s ( HTi )
i

Gas Adsorption: Heat of Adsorbed Phase

The term for each component is a function of the loading and the
temperature in the solid phase:
H i = s C pai wi

Ts
t

The total contribution comes from the sum for all components:
(H i )
i

You supply C pai (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 T << Tc use C pai for liquid
For T just below Tc use system knowledge to specify C pai
For T > Tc use C pai for compressed gas

1-76 Gas Adsorption Processes

Adsorption Reference Manual

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:
HTC a p (Tg Ts )

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:
Hw

4 DB

(DB + WT )2 DB2

(T

Tw )

Where
DB

Internal diameter of layer

WT

Width of column wall

The supply of H w 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:
4

Adsorption Reference Manual

Hw
(Tg Tw )
DB

Gas Adsorption Processes 1-77

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:
4 Hamb (D B + WT )

(D B + WT )2 DB2

(Tw Tamb )

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:
kw

2 Tw
z 2

You must specify the value of the wall thermal conductivity k w 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

T
energy balance: w C pw w
t
You must specify the value of the wall density w and the specific
heat capacity of the wall C pw in the Specify table for the layer.

1-78 Gas Adsorption Processes

Adsorption Reference Manual

Gas Adsorption: Explanation of

Equation Symbols
Symbol

Explanation

Aspen ADSIM Base Units

Specific particle surface

m2/m3

aHx

Specific heat exchanger surface

m2(HX area)/m3(Bed)

aP

Specific particle surface per unit volume m2(Particle area)/m3(Bed)

bed

Area

AA

Placeholder variable used for DubininAstakhov isotherm evaluation

Kinetic Langmuir factor

1/bar

cbk

Bulk gas phase concentration

kmol/m3

ck

Molar concentration of component k

kmol/m3

cmsk

Macropore gas phase concentration

kmol/m3

csol

Concentration of solid phase reactant

kmol/kg

c pai

Specific heat capacity of adsorbed phase MJ/kmol/K

c p ,cat

Specific heat capacity of catalyst

MJ/kg/K

c pg

Specific gas phase heat capacity at

constant pressure

MJ/kmol/K

c ps

Specific heat capacity of adsorbent

MJ/kmol/K

c pW

Specific heat capacity of column wall

MJ/kg/K

cvg

Specific gas phase heat capacity at

constant volume

MJ/kmol/K

DB

Bed diameter

Defc

Effective micropore diffusion coefficient m2/s

DefP

Effective macropore diffusion coefficient m2/s

Dek

Effective adsorbed phase diffusivity of

component k

m2/s

Dki

Knudsen diffusion coefficient of

component i

m2/s

m2

Continued overleaf

Adsorption Reference Manual

Gas Adsorption Processes 1-79

Dmk

Mean molecular diffusion coefficient of

component k

m2/s

Eact ,k

Activation energy for Arrhenius

relationship

MJ/kmol

Eik

Radial dispersion coefficient of

component k

m2/s

E zk

Axial dispersion coefficient of component m2/s

k

Function

f eq

Equilibrium (isotherm) relationship

H amb

Wall-ambient heat transfer coefficient

MW/m2/K

HB

Height of adsorbent layer

Hi

Rate of change of heat of adsorbed phase MJ/m3/s

HR

Combined heats of homogenous and

heterogeneous reactions

MJ/m3 (Bed)/s

H Rcat

Heat of catalytic reaction

MJ/kmol

H Rgas

Gas phase heat of reaction

MJ/kmol

H Ti

Heat of adsorption contribution to solid

phase energy balance

MJ/m3/s

Hw

Gas-wall heat transfer coefficient

MJ/m2/s

H i

Heat of adsorption of component i

MJ/kmol

HTC

Gas-solid heat transfer coefficient

MJ/m2/s

IP

Isotherm parameter, units depend on

isotherm

Colburn j-factor for heat or mass transfer -

J ads ,k

Mass transfer rate of component k owing kmol/m3 (Bed)/s

to adsorption

J cat ,reac , k

Mass transfer rate of component k owing kmol/m3 (Bed)/s

to heterogeneous catalytic reactions

J gas ,reac

Mass transfer rate of component k owing kmol/m3 (Void)/s

to homogenous, gas phase reactions

Jk

Mass transfer rate of component k to/from kmol/m3 (Bed)/s

adsorbent

k0 k

Pre-exponential factor for Arrhenius

relationship

m/s

Continued overleaf

1-80 Gas Adsorption Processes

Adsorption Reference Manual

k0 Pk

Pre-exponential factor for pressure

dependent Arrhenius relationship

m/s

k fk

Film mass transfer coefficient of

component k

m/s

kg

Gas phase thermal conductivity

MW/m/K

k gr

Effective radial gas phase thermal

conductivity

MW/m/K

k grdyn

Dynamic contribution to k gr

MW/m/K

k grstat

Static contribution to k sr

MW/m/K

ki

Effective, lumped mass transfer

coefficient of component i

1/s

ks

Solid thermal conductivity

MW/m/K

k gz

Effective axial gas phase thermal

conductivity

MW/m/K

k sr

Effective radial solid phase thermal

conductivity

MW/m/K

k srstat

Static contribution to k gr

MW/m/K

k sz

Effective axial solid phase thermal

conductivity

MW/m/K

kW

Thermal conductivity of column wall

MW/m/K

K Ki

Isotherm slope of component i (Henrys

coefficient)

m3/kg

K Ki

Dimensionless isotherm slope of

component i (Henrys coefficient)

K mac

Macropore mass transfer coefficient

1/s

K mic

Micropore mass transfer coefficient

1/s

Kp

Darcys constant

bar s/m2

K Pi

Macropore diffusion coefficient

m2/s

Length of horizontal bed

Molecular weight

kg/kmol

MTC g

Gas film mass transfer coefficient

1/s

MTCs

Solid film mass transfer coefficient

1/s

Emissivity in calculation of effective

thermal conductivities

Continued overleaf

Adsorption Reference Manual

Gas Adsorption Processes 1-81

Pressure

bar

IAS vapor pressure

bar

Psat

Saturation pressure

bar

QHx

Heat transfer rate to internal heat

exchanger

MJ/m2/s

Radial co-ordinate (in packed bed or

particle)

rc

Microparticle (crystal) radius

rp

Particle radius

Universal gas constant

bar m3/kmol/K

Rcat

Catalytic reaction rate

kmol/kg/s

Rgas

Gas phase reaction rate

kmol/m3/s

Rsol

Solid phase reaction rate

kmol/kg/s

Time

tcycle

Adsorption cycle time

Temperature

T0

Equal to Tamb or TW , depending on

context used

Tamb

Ambient temperature

Tc

Critical temperature

TCW

Cooling water temperature

Ts

Solid phase temperature

Tg

Gas phase temperature

THx

Heat exchange medium temperature

TSt

Steam temperature

TW

Wall temperature

Tort

Adsorbent tortuosity

U Hx

Overall heat transfer coefficient: gas to

heat exchange medium

MW/m2/K

U Hx ,cw

Overall heat transfer coefficient: gas to

cooling water

MW/m2/K

Pi

Continued overleaf

1-82 Gas Adsorption Processes

Adsorption Reference Manual

U Hx , St

Overall heat transfer coefficient: gas to

steam

MW/m2/K

vg

Gas phase superficial velocity

m/s

wk

Loading

kmol/kg

wk0

Pure component loading of component k kmol/kg

Width of horizontal bed

WT

Width of column wall

xchar

Characteristic length

xk

Mole fraction of component k in the

adsorbed phase

yk

Mole fraction of component k in the gas phase

Axial co-ordinate

Gas compressibility factor

Adsorption Reference Manual

Gas Adsorption Processes 1-83

Symbol

Explanation

rg

Radiation contribution to k grstat

rs

Radiation contribution to k srstat

Factor used in k grstat calculation

Radial discretization distance

Total bed voidage

m3 (Void+Pore)/m3 (Bed)

Interparticle voidage

m3 (Void)/m3 (Bed)

Intraparticle voidage

m3 (Pore)/m3 (Particle)

Function of packing density, used in k srstat

calculation

Relative pressure: Pk / Psat , k

Factor used in k srstat calculation

Activity coefficient of component i

Dynamic viscosity

N s/m2

ads,i

Chemical potential of component i in the MJ/kmol

adsorbed phase

gas,i

Chemical potential of component i in the MJ/kmol

gas phase

jk

Stoichiometric coefficient of component k in reaction j

i0

Spreading pressure of component i

bar m

Time constant for adsorption cycle

Gas phase molar density

kmol/m3

Adsorbent bulk density

kg/m3

s,cat

Catalyst bulk density

kg/m3

Wall density

kg/m3

Parameter in Glueckauf expression

Particle shape factor

1-84 Gas Adsorption Processes

Aspen ADSIM Base Units

Adsorption Reference Manual

Dimensionless number

Defining expression

Description

NuW

H w xchar
kg

Nusselt number for gas wall heat transfer

PeH

xchar vg g MC pg

Gas-wall heat transfer Peclet number

PeK

vgH b
Ez

Component Peclet number for mass

transfer

Pr

C pg
kg M

Prandl number

Sck

Dmi g M

Component Schmidt number

Shk

k fi 2rp
Dmi

Component Sherwood number

Re

2rp M g vg

Particle Reynolds number

Adsorption Reference Manual

kg

Gas Adsorption Processes 1-85

2 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
Material/Momentum Balance Tab
About Axial Dispersion in Ion-Exchange Processes
Kinetic Model Tab
Isotherm Tab
Summary of Mass Balance Equations for Ion-Exchange
Processes

Adsorption Reference Manual

Ion-Exchange Processes 2-1

About Ion-Exchange Processes

In ion-exchange processes, a fluid phase (such as an aqueous
solution) containing cations and anions, is contacted with an ionexchange 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 2+ + 2 NaR CaR2 + 2 Na +
Where R is a stationary, univalent, anionic group in the polyelectrolyte network of the exchange phase.

2-2 Ion-Exchange Processes

Adsorption Reference Manual

Bed Model Assumptions for IonExchange

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 solidfilm resistance. This resistance is either linear, quadratic, or
user-defined.
The mass-action equilibrium is one alternative model for ionexchange 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.

Adsorption Reference Manual

Ion-Exchange Processes 2-3

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 ionexchange 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
These discretization methods are available for ion-exchange
General Tab (ionx):
Discretization Method processes:
to be Used
UDS1
UDS2
CDS1
LDS
QDS
MIXED
BUDS
General Tab (ionx):
Number of Nodes

2-4 Ion-Exchange Processes

In the Number of Nodes box, choose an appropriate number of

nodes for your chosen discretization method.

Adsorption Reference Manual

Material/Momentum Balance Tab

(ionx)
Use the Material/Momentum Balance tab to specify the basic
assumptions about material dispersion in the liquid phase for ionexchange processes.
Material/Momentum
Balance Tab (ionx):
Material Balance
Assumption

In the Material Balance Assumption box, choose from one of the

following options:
Convection Only
Convection with Constant Dispersion
Convection with Estimated Dispersion
Convection with User Procedure Dispersion
Convection with User Submodel Dispersion
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, E z .
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):
Re
vl d P
= 0.2 + 0.011
Ez
i

Adsorption Reference Manual

0.48

Ion-Exchange Processes 2-5

Where:

Ez

Axial dispersion coefficient

vl

Liquid Velocity

Interparticle voidage

dp

Particle diameter

Re =

l M l d P vl

Reynolds number

Liquid viscosity

Liquid molar density

Ml

Liquid molecular weight

Material Balance Assumption (ionx): Convection with User

Procedure Dispersion
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 term in the material balance for the bed.
The dispersion coefficient varies with axial position according to
the user-supplied submodel iUserDispersion.

2-6 Ion-Exchange Processes

Adsorption Reference Manual

About Axial Dispersion in IonExchange 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, E z . The dispersion term in the material
balance is usually expressed as:
i Ez

2 ck
z 2

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 ( E z ), a liquid superficial velocity ( vl ), and a
bed height ( H b ):

Pe =

vl H b
Ez

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.

Adsorption Reference Manual

Ion-Exchange Processes 2-7

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

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

2-8 Ion-Exchange Processes

In the Film Model Assumption box, choose from:

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).

Adsorption Reference Manual

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.

Adsorption Reference Manual

wk
= MTCl k (c k c k* )
t

(fluid film)

wk
= MTCs k ( wk* wk )
t

(solid film)

Ion-Exchange Processes 2-9

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).

Kinetic Model Tab

(ionx): Form of Mass
Transfer Coefficient

wk
(c k2 (c k* ) 2 )
= MTCl k
t
2c k

(fluid film)

wk
(( wk* ) 2 wk2 )
= MTCs k
t
2 wk

(solid film)

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.

2-10 Ion-Exchange Processes

Adsorption Reference Manual

Isotherm Tab (ionx)

Use the Isotherm tab to specify the adsorption isotherms for use in
your ion-exchange process.
About Adsorption
Isotherms for IonExchange 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 ionexchangers. 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
++
B B

B
R

Adsorption Reference Manual

+ +
A

Ion-Exchange Processes 2-11

The exchange reaction in the ion-exchange process is typically

takes the form:
A + mBR ARm + mB

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:
y x
1
= A B
K AB x A y B

Q

c0

m 1

Where:

K AB

Equilibrium constant or selectivity coefficient

Equivalent mole fraction in the adsorbed phase

Equivalent mole fraction in the aqueous phase

c0

Total ionic concentration

Ion-exchange resin capacity

In Aspen ADSIM, the parameter IP1 equals K AB , and the

parameter m equals IP2 . The equation now becomes:
y x
IP1 A A B
x A y B

IP2 A

Q

c0

IP2 A 1

= 1 .0

Isotherm Assumed for Layer (ionx): Extended Langmuir

The extended Langmuir isotherm was found to represent some
experimental data satisfactorily:
wi =

IP1i ci
1 + (IP2 k c k ) + IP2b cb
k

Where b refers to the (original) counter-ion.

2-12 Ion-Exchange Processes

Adsorption Reference Manual

Isotherm Assumed for Layer (ionx): Extended LangmuirFreundlich

This isotherm is based on the Langmuir isotherm and expressed as:

wi =

1+
k

IP1i ciIP2 i
IP3k c kIP4 k + IP3b cbIP4 b

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:
vl

+ i l = 0
z
t

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:

2 ck
c
c
i Ez
+ vl k + i k + J k = 0
2
z
z
t

Adsorption Reference Manual

Ion-Exchange Processes 2-13

The mass transfer rate J k between the bulk liquid and the resin is
given by:
J k = (1 i )

wk
t

wk
can, for example, be determined by a
t
solid film linear driving force relationship, such as:

Where the uptake rate

wk
= MTC sk wk* wk
t

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

Jb = Jk
k =1
k b

Hence the behavior of the exchanged counter ion in the liquid

phase can be described by:

2 cb
cb
cb nc

i Ez
+
v
+
Jk = 0
l
i
z 2
z
t k =1
k b

The tables explain the equation symbols used in Aspen ADSIM's

Explanation of
Equation Symbols for ion-exchange mass balance equations.
Ion-Exchange
Symbol
Explanation
Aspen ADSIM
Processes
Base Units

cb

Counter ion concentration in liquid phase

eq/m3

ck

Ion concentration in liquid phase

eq/m3

c k*

Liquid phase ion concentration in equilibrium eq/m3

with resin phase

c0

Total liquid phase ion concentration

eq/m3

dp

Resin particle diameter

Ez

Axial dispersion coefficient

m2/s

HB

Bed height

IP

Isotherm parameter

Continued overleaf

2-14 Ion-Exchange Processes

Adsorption Reference Manual

Adsorption Reference Manual

Jb

Counter ion material transfer rate

eq/m3/s

Jk

Ion material transfer rate

eq/m3/s

K AB

Mass action equilibrium constant

Stoichiometric coefficient used in mass action

equilibrium

Ml

Solvent molecular weight

kg/kmol

MTCl

Liquid film mass transfer coefficient

1/s

MTCs

Solid film mass transfer coefficient

1/s

Total resin ion capacity

eq/m3

Time

wk

Ion loading on resin

eq/m3

wk*

Ion loading in equilibrium with liquid phase eq/m3

ion concentration

xk

Ion mole fraction in adsorbed (resin) phase

yk

Ion mole fraction in liquid phase

Axial co-ordinate

Bed voidage

Solvent viscosity

N/m2/s

Solvent molar density

kmol/m3

Dimensionless
number

Defining expression

Description

Pe

vl H B
Ez

Peclet number

Re

M l l d P vl

Reynolds number

Ion-Exchange Processes 2-15

3 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
Material/Momentum Balance 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

Adsorption Reference Manual

Liquid Adsorption Processes 3-1

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 wastewater. 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 ionexchange resins, and the development of novel process concepts
have been the two significant factors in the success of these
processes.

3-2 Liquid Adsorption Processes

Adsorption Reference Manual

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 userdefined.
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.

Adsorption Reference Manual

Liquid Adsorption Processes 3-3

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
Material/Momentum Balance 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.
These discretization methods are available for liquid adsorption
General Tab (liq):
Discretization Method processes:
to be Used
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.

3-4 Liquid Adsorption Processes

Adsorption Reference Manual

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
Convection with Constant Dispersion
Convection with Estimated Dispersion
Convection with User Procedure Dispersion
Convection with User Submodel Dispersion
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, E z .
With this option, the dispersion coefficient is constant for all
components throughout the bed.

Adsorption Reference Manual

Liquid Adsorption Processes 3-5

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):
vl rP
0.2 0.011 Re

=
+
i Ez i
i i

0.48

Where:

Ez

Axial dispersion coefficient

vl

Liquid Velocity

Interparticle voidage

rp

Particle radius

Re

Reynolds number

Material Balance Assumption (liq): Convection with User

Procedure Dispersion
The Convection with User Procedure Dispersion option includes
the dispersion term in the material balance for the bed.
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 term in the material balance for the bed.
With this option, the dispersion coefficient varies according to the
submodel lUserDispersion.
Material/Momentum
Balance Tab (liq):
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.

3-6 Liquid Adsorption Processes

Adsorption Reference Manual

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:
p
= K P vl
z

Where:
Kp

Proportionality constant

Pressure Drop Assumption (liq): Karman-Kozeny

Select the Karman-Kozeny option to relate velocity to pressure
drop:
3
1.5 10 3 (1 i )
p 2rp i
=
z vl (1 i )
2rp

Material/Momentum
Balance Tab (liq):
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.

Adsorption Reference Manual

Liquid Adsorption Processes 3-7

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.
Material/Momentum
Balance Tab (liq):
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 bidisperse 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.

3-8 Liquid Adsorption Processes

Adsorption Reference Manual

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

In the Film Model Assumption box, choose from:

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.

wi
= MTCli (ci ci* )
t

(fluid)

wi
= MTC si (wi* wi )
t

(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.

wi MTCli ci2 (ci* )

S
=
t
2ci

(
wi
wi* ) wi2
= MTC si
2wi
t

Adsorption Reference Manual

(fluid)

(solid)

Liquid Adsorption Processes 3-9

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.

3-10 Liquid Adsorption Processes

Adsorption Reference Manual

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 3-8), 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)

Adsorption Reference Manual

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.

Liquid Adsorption Processes 3-11

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

3-12 Liquid Adsorption Processes

Adsorption Reference Manual

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:

wi =

IP1i IP2i ci
1 + IP2i ci

Langmuir 2

This isotherm is expressed as:

IP
IP1i IP2i exp 3i ci
Ts
wi =
IP
1 + IP2i exp 3i ci
Ts
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
Dual-Site Langmuir 1

This isotherm is expressed as:

wi =

IP1i IP2i ci
nc

1 + IP2 k ck
k =1

IP3i IP4i ci
nc

1 + IP4 k ck
k =1

Dual-Site Langmuir 2

This isotherm is expressed as:

IP
IP
IP1i IP2i exp 3i ci
IP4i IP5i exp 6i ci
Ts
Ts
+
wi =
nc
nc
IP
IP
1 + IP2 k exp 3k ck 1 + IP5 k exp 6 k ck
k =1
k =1
Ts
Ts

Adsorption Reference Manual

Liquid Adsorption Processes 3-13

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

This isotherm is expressed as:

wi =

IP1i IP2i ci
nc

1 + IP2 k ck
k =1

Extended Langmuir 2

This isotherm is expressed as:

IP
IP1i IP2i exp 3i ci
Ts
wi =
nc
IP
1 + IP2 k exp 3k ck
k =1
Ts
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

This isotherm is expressed as:

wi = IP1i ciIP2 i

Freundlich 2

This isotherm is expressed as:

IP
wi = IP1i ciIP2 i exp 3i
Ts

3-14 Liquid Adsorption Processes

Adsorption Reference Manual

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

This isotherm is expressed as:

wi =

IP1i IP2i ciIP3i

1 + IP2i ciIP3i

Langmuir-Freundlich 2

This isotherm is expressed as:

IP
IP1i IP2i ciIP3 i exp 4i
Ts
wi =
IP
1 + IP2i ciIP3 i exp 4i
Ts
Isotherm Assumed for Layer (liq): Extended LangmuirFreundlich 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

This isotherm is expressed as:

wi =

IP1i IP2i ciIP3 i

n

1 + IP2 j c j 3 j
j =1

IP

Extended Langmuir-Freundlich 2

This isotherm is expressed as:

IP
IP1i IP2i ciIP3i exp 4i
Ts
wi =
n
IP
IP
1 + IP2 j c j 3 j exp 4 j
j =1
Ts
Adsorption Reference Manual

Liquid Adsorption Processes 3-15

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

This isotherm is expressed as:

wi =

IP1i IP2i ci
nc

IP
k =1

2k k

Stoichiometric Equilibrium 2

This isotherm is expressed as:

IP
IP1i IP2i exp 3i ci
Ts
wi = nc
IP
IP2 k exp 3k ck

k =1
Ts
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

This isotherm is expressed as:

wi =

IP1i IP2i ci
1 + IP2i ci

IAS Langmuir 2

This isotherm is expressed as:

IP
IP1i IP2i exp 3i ci
Ts
wi =
IP
1 + IP2i exp 3i ci
Ts

3-16 Liquid Adsorption Processes

Adsorption Reference Manual

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

This isotherm is expressed as:

wi = IP1i ciIP2 i

IAS Freundlich 2

This isotherm is expressed as:

IP
wi = IP1i ciIP2 i exp 3i
Ts

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 LangmuirFreundlich model:
IAS Langmuir-Freundlich 1, which is temperature independent
IAS Langmuir-Freundlich 2, which is temperature dependent
IAS Langmuir-Freundlich 1

This isotherm is expressed as:

wi =

IP1i IP2i ciIP3 i

1+ IP2i ciIP3 i

IAS Langmuir-Freundlich 2

This isotherm is expressed as:

IP
IP1i IP2i ciIP3 i exp 4i
Ts
wi =
IP
1 + IP2i ciIP3 i exp 4i
Ts

Adsorption Reference Manual

Liquid Adsorption Processes 3-17

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
The functional relationship is:
wi = f eq (T , c1 ...cnc , IP )

Isotherm Assumed for Layer (liq): User Multicomponent

Submodel

You can supply your own, proprietary isotherm relationships using

the submodel lUserIsotherm.
The functional relationship is:
wi = f eq (T , c1 ...cnc , IP )

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 ci0 (resulting in the same spread pressure as the
mixture at total concentration ctot ), to the loading wi0 , using the
pure component isotherm:

wi0 = f eq T , ci0 , IP

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:
A i0
= g T , ci0 , IP with g =
RT

3-18 Liquid Adsorption Processes

ci0

f eq (T , c, IP )
c

dc

Adsorption Reference Manual

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 ci0 (resulting in the same spread pressure
as the mixture at total concentration ctot ), to the loading wi0 , using
a pure component isotherm:

wi0 = f eq T , ci0 , IP

The second submodel, lUserGibbs, evaluates the integral of the

Gibbs isotherm to give the spread pressure. The relationship to be
evaluated is:
A i0
= g T , ci0 , IP with g =
RT

ci0

f eq (T , c, IP )
c

dc

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.

Adsorption Reference Manual

Liquid Adsorption Processes 3-19

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:
kl

2T
z 2

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:
kS

2TS
z 2

You must supply a value for k s .

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.
Aspen ADSIM models enable you to include the heat capacity of
Energy Balance Tab
(liq): Consider Heat of the adsorbed phase in the solid-phase energy balance. The Heat of
Adsorbed Phase term is optional.
Adsorbed Phase
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.

3-20 Liquid Adsorption Processes

Adsorption Reference Manual

The term for each component is a function of the loading and

the temperature in the solid phase:
T
H ads ,i = p C Pi wi S
t
The total contribution is the sum for all components:

nc

H
i =1

Energy Balance Tab

(liq): Heat of
Adsorption
Assumption

ads ,i

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:
HTi =

wi
H i
t

These rates are held in vectors and summed for all components to
obtain the total rate of heat generation, by adsorption, per unit
nc

volume of solid: p (HTi )

i =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:

H = f (Ts , P, w)

Adsorption Reference Manual

Liquid Adsorption Processes 3-21

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:

H = f (Ts , P, w)
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
= a P (1 i )HTC (Tl TS )
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/m2/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:
2rp M l vl
Re =

If the calculated value falls below 1E-10, reset it to this value.

2. Calculate the Prandl number:
C pl
Pr =
kl M
If the calculated value falls below 1E-10, reset it to this value.

3-22 Liquid Adsorption Processes

Adsorption Reference Manual

3. Calculate the j-factor:

If Re < 190 then j = 1.66 Re 0.51 otherwise j = 0.983Re 0.41
4. Calculate the heat transfer coefficient:
HTC = jC pl vl l Pr

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:
HTC = f (Tl , P, C , vl )
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:
k l = C Pl E z l
This method applies the analogy between heat and mass transfer.

Adsorption Reference Manual

Liquid Adsorption Processes 3-23

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:
4H w
(Tl Tamb )
DB

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
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
non-conductive, or there is an infinite heat transfer resistance
between the liquid and the wall surface.

3-24 Liquid Adsorption Processes

Adsorption Reference Manual

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:
Hw

4 Dwi
(Tl Tw )
D Dwi2
2
wo

You must define the value of the liquid-to-wall heat transfer

coefficient, H w . 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:
Hw

4
(Tl Tw )
Dwi

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:
H amb

4 Dwo
(Tw Tamb )
D Dwi2
2
wo

You must define the value of the heat transfer coefficient to the
environment H amb and the temperature of the environment, Tamb .
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:
kw

2Tw
z 2

You must specify the thermal conductivity of the wall material,

kw .

Adsorption Reference Manual

Liquid Adsorption Processes 3-25

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:

wC pw

Tw
t

You must specify the value of the wall density, w , and the
specific heat capacity of the wall, C pw .

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
The governing partial differential equation is:

nc
Ml
w

+ (vl Ml ) + s M i i = 0
t
z
t
i =1

Each component in the liquid phase is governed by a material

balance:
i Ez

3-26 Liquid Adsorption Processes

c
w
2 ci
+ (vl ci ) + i i + s i = 0
2
z
t
t
z

Adsorption Reference Manual

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:

ks

2Ts
T
T
+ p C ps s + p s
2
z
t
t

Liquid Adsorption:
Fluid Phase Energy
Balance

(C
nc

i =1

nc
wi

)
w
+

a p HTC (Tl Ts ) = 0
pli i
p H i
t
i =1

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
The governing partial differential equation is:

kl i

2Tl
T
T
4H w
+ C pl l vl l + i C pl l l + a p (1 i )HTC (Tl Ts ) +
(Tl Tw ) = 0
2
z
z
t
Dwi

Liquid 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 partial differential equation is:

2Tw
T
4D
4D
kw
+ w C pw w H w 2 wi 2 (Tl Tw ) + H amb 2 wo 2 (Tw Tamb ) = 0
2
z
t
Dwo Dwi
Dwo Dwi

Adsorption Reference Manual

Liquid Adsorption Processes 3-27

Liquid Adsorption: Explanation of

Equation Symbols
Symbol

Explanation

Aspen ADSIM Base Units

ap

Specific particle surface

m2/m3

Area

m2

ck

Molar concentration of component k

kmol/m3

ci0

IAS pure component concentration

kmol/m3

C pl

Specific liquid phase heat capacity

MJ/kmol/K

C ps

Specific heat capacity of adsorbent

MJ/kmol/K

C pW

Specific heat capacity of column wall

MJ/kg/K

DB

Bed diameter

Dwi

Inner bed diameter

Dwo

Outer bed diameter

Ez

Axial dispersion coefficient

m2/s

f eq

Equilibrium (isotherm) relationship

Function

H ads ,i

Heat of component i in adsorbed phase

MJ/m3/s

H amb

Wall-ambient heat transfer coefficient

MW/m2/K

HB

Height of adsorbent layer

HTi

Heat of adsorption contribution to solid

phase energy balance

MJ/m3/s

Hw

Gas-wall heat transfer coefficient

MJ/m2/s

H i

Heat of adsorption of component i

MJ/kmol

HTC

Liquid-solid heat transfer coefficient

MJ/m2/s

IP

Isotherm parameter, units depend on

isotherm

Colburn j-factor for heat or mass transfer

kl

Liquid phase thermal conductivity

MW/m/K

Continued overleaf

3-28 Liquid Adsorption Processes

Adsorption Reference Manual

ks

Solid thermal conductivity

MW/m/K

KP

Darcys constant

bar s/m2

Molecular weight

kg/kmol

MTCl

Liquid film mass transfer coefficient

1/s

MTCs

Solid film mass transfer coefficient

1/s

Pressure

bar

rp

Particle radius

Universal gas constant

bar m3/kmol/K

Time

Temperature

Tamb

Ambient temperature

Ts

Solid phase temperature

Tl

Liquid phase temperature

TW

Wall temperature

vl

liquid phase superficial velocity

m/s

wk

Loading

kmol/kg

wk0

Pure component loading of component k

kmol/kg

Width of horizontal bed

WT

Width of column wall

Axial co-ordinate

Symbol

Explanation

Aspen ADSIM Base Units

Interparticle voidage

m3 (Void)/m3 (Bed)

Dynamic viscosity

N s/m2

i0

Spreading pressure of component i

bar m

M,I

Liquid phase mass density

kg/m3

Liquid phase molar density

kmol/m3

Adsorbent apparent density

kg/m3

Adsorbent bulk density

kg/m3

Wall density

kg/m3

Particle shape factor

Adsorption Reference Manual

Liquid Adsorption Processes 3-29

Dimensionless number

Defining expression

Description

Pe

vl H b
Ez

Peclet number for mass transfer

Pr

C pl

Prandl number

kl M

Re

2r p M , l v l

Particle Reynolds number

3-30 Liquid Adsorption Processes

Adsorption Reference Manual

4 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

Adsorption Reference Manual

Numerical Methods 4-1

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.

4-2 Numerical Methods

Adsorption Reference Manual

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.

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Numerical Methods 4-3

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

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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:

Upwind Differencing
Scheme 1

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
i_Loading_Eq

Set the lower bound to minus the upper bound

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 (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:

i i i 1
=
z
z

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Numerical Methods 4-5

Second-order (dispersion) term is approximated with a secondorder accurate central differencing scheme:

2 i i +1 2 i + i 1
=
z 2
z 2
Evaluation of Upwind Differencing Scheme 1
Upwind Differencing Scheme 1 has the following advantages
(+)and disadvantages ():

Upwind Differencing
Scheme 2

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.)

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:

i 3 i 4 i 1 + i 2
=
z
2z
Second-order (dispersion) term is approximated with a secondorder accurate central differencing scheme:

2 i i +1 2 i + i 1
=
z 2
z 2

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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:
i +1 i 1
=
z
2 z

Second-order (dispersion) term is approximated with a secondorder accurate central differencing scheme:

2 i i +1 2 i + i 1
=
z 2
z 2
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.

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Numerical Methods 4-7

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:

i i + 2 + 8 i +1 8 i 1 + i 1
=
z
12z
Second-order (dispersion) term is approximated with a secondorder accurate central differencing scheme:

2 i i +1 2 i + i 1
=
z 2
z 2
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:
First-order derivative:

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

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Second-order (dispersion) term is approximated with a secondorder accurate central differencing scheme:

2 i i +1 2 i + i 1
=
z 2
z 2
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.
First-order derivative:

i 3 i +1 + 3 i 7 i 1 + i 2
=
z
8z
Second-order (dispersion) term is approximated with a secondorder accurate central differencing scheme:

2 i i +1 2 i + i 1
=
z 2
z 2
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

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Numerical Methods 4-9

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.

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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.
First-order derivative:

3 i +1 + 7 i 11 i 1 + i 2
=
z
12z
Second-order (dispersion) term is approximated with a secondorder accurate central differencing scheme:

2 i i +1 2 i + i 1
=
z 2
z 2
Evaluation of Mixed Differencing Scheme
The Mixed Differencing Scheme has the following advantages
(+)and disadvantages ():
+ Accurate

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Numerical Methods 4-11

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.

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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:

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

2 i i +1 2 i + i 1
=
z 2
z 2

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Numerical Methods 4-13

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:
i ( i i 1 ) + 0.25({ i +1 i } { i 1 i 2 })
=
z
z

Second order (dispersion) term is based on a second-order accurate

central differencing scheme:

2 i i +1 2 i + i 1
=
z 2
z 2
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:

i 2
i i i 1 1
i 1 1
=
+ (ri ) i
(ri 1 ) i 1
2
2
z
z
z
z
Here is the flux-limiter function and r the gradient ratio,
calculated as:

ri =

4-14 Numerical Methods

i +1 i
i i 1

Adsorption Reference Manual

There are three versions of the flux-limiter function to choose

from:
van Leer
OSPRE
SMART
Second order (dispersion) term is based on a second-order accurate
central differencing scheme:

2 i i +1 2 i + i 1
=
z 2
z 2

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Numerical Methods 4-15

5 Estimation with Aspen ADSIM

The chapter contains the following information about the

Estimation Module:
Two Estimation Tools in Aspen ADSIM 11.1
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

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Estimation with Aspen ADSIM 5-1

Two Estimation Tools in Aspen

ADSIM 11.1
Aspen ADSIM 11.1 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 11.1
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 11.1 help file, navigate to the topic 'Two Estimation
Tools in Aspen ADSIM 11.1', 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.

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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:

Adsorption Reference Manual

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

Estimation with Aspen ADSIM 5-3

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.

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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.

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Estimation with Aspen ADSIM 5-5

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

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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
5-5. 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.

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Estimation with Aspen ADSIM 5-7

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.

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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 timedependent, 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

Adsorption Reference Manual

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.

Estimation with Aspen ADSIM 5-9

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.

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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, as described in Manually
Entering Dynamic Experimental Data on page 5-9. 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.

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Estimation with Aspen ADSIM 5-11

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.

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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

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Estimation with Aspen ADSIM 5-13

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.

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6 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 11.1
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

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Cyclic Operation 6-1

Cyclic Operations in Aspen ADSIM

11.1
In Aspen ADSIM 11.1, 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).

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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.

Adsorption Reference Manual

Cyclic Operation 6-3

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
Adding or Deleting
(available only if you
variables
selected Manipulated from
the Step menu)

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.

6-4 Cyclic Operation

Adsorption Reference Manual

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 Event-driven step controls are implicit events, for which the time
of occurrence is unknown. For example, "the step will terminate
Step
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

Adsorption Reference Manual

Cyclic Operation 6-5

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.

6-6 Cyclic Operation

Adsorption Reference Manual

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

Adsorption Reference Manual

Cyclic Operation 6-7

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.

6-8 Cyclic Operation

Adsorption Reference Manual

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.

Adsorption Reference Manual

Cyclic Operation 6-9

Adding Step
Variables

To add a new manipulated step variable:

1. Click the Variable button on the toolbar; or from its dropdown 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.

6-10 Cyclic Operation

Adsorption Reference Manual

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.

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Cyclic Operation 6-11

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

6-12 Cyclic Operation

To delete an interaction:
From the drop-down list, click None.

Adsorption Reference Manual

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 1 3 and 5 4; interaction unit D2 has a single
interaction 2 4; interaction unit D3 has a single interaction, 3 5.

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.
Adsorption Reference Manual

Cyclic Operation 6-13

Additional Cycle Controls

To access additional cycle controls:
Click the Cycle toolbar button, or from the buttons dropdown 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

6-14 Cyclic Operation

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.

Adsorption Reference Manual

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 reduce 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.

Adsorption Reference Manual

Cyclic Operation 6-15

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.

6-16 Cyclic Operation

Adsorption Reference Manual

Take Snapshot at End To automatically take a snapshot at the end of step for every cycle
(or cycles based on your settings for Record Initial and Record
of Step Box
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.

Adsorption Reference Manual

Cyclic Operation 6-17

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:

when the cyclic task has been

You see
successfully generated (should there be any errors, these will be
given in the simulation messages window)

You see

when there is another activate cycle.

Note the following points:

If any variable in a step is ramped, additional task 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).

6-18 Cyclic Operation

Adsorption Reference Manual

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 on the task in the Flowsheet section of
Simulation Explorer.
To activate a cycle:

With the cycle currently inactive

Cycle drop-down menu, click Activate Cycle.

, from the

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

Adsorption Reference Manual

Cyclic Operation 6-19

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).

6-20 Cyclic Operation

Adsorption Reference Manual

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.

Adsorption Reference Manual

Cyclic Operation 6-21

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

6-22 Cyclic Operation

Adsorption Reference Manual

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.

Adsorption Reference Manual

Cyclic Operation 6-23

7 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

Adsorption Reference Manual

Flowsheeting 7-1

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:

7-2 Flowsheeting

Adsorption Reference Manual

General Model Types

The general model types available in Aspen ASDIM are:
Model Type

Used In

Description

Typical Models

Non-Reversible

Gas
Assumes that there is no flow reversal in All models (except
for adsorbent/resin
Ion-Exchange the model. Material flow is from
Process_In to Process_Out.
beds) can be
Liquid
configured in this
way.

Reversible Flow
Setter

Gas

Reversible Pressure
Setter

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.

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_interac
tion, gas_feed,
gas_product.

Non-Reversible
Delay

Gas

Used as part of an interaction train.

Stores stream information or pass
downstream/upstream pressure
information.

gas_valve,
gas_ramp,
gas_interaction.

Reversible

Ion-Exchange Feed or product train to allow for

reversible flow.
Liquid

Adsorption Reference Manual

feeds, products,
valves, tanks,
distributors.

Flowsheeting 7-3

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).

Tank1

Y1
T1
P1
H1

Ys1,in = Ys1,out
Ts1,in = Ts1,out
Ps1,in = Ps1,out
Hs1,in = Hs1,out

Valve

Ys2,in = Ys2,out
Ts2,in = Ts2,out
Ps2,in = Ps2,out
Hs2,in = Hs2,out

S1

Ys1,in = Y1
Ts1,in = T1
Ps1,in = P1
Hs1,in = H1

S2

F = (Ps1,out,Ps2,in)
Ys1,out = Ys2,in
Ts1,out = Ts2,in
Hs1,out = Hs2,in

Tank2

Y2
T2
P2
H2

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.

7-4 Flowsheeting

Adsorption Reference Manual

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.

Tank1

Y1
T1
P1
H1

Ys1,in = Ys1,out
Ys1,in,r = Ys1,out,r
Ts1,in = Ts1,out
Ts1,in,r = Ts1,out,r
Ps1,in = Ps1,out
Hs1,in = Hs1,out
Hs1,in,r = Hs1,out,r

Valve

Ys2,in = Ys2,out
Ys2,in,r = Ys2,out,r
Ts2,in = Ts2,out
Ts2,in,r = Ts2,out,r
Ps2,in = Ps2,out
Hs2,in = Hs2,out
Hs2,in,r = Hs2,out,r

S1

Ys1,in,r = Y1
Ts1,in,r = T1
Ps1,in = P1
Hs1,in,r = H1

Tank2

S2

F = (Ps1,out,Ps2,in)
Ys1,out = Ys2,in
Ts1,out = Ts2,in
Hs1,out = Hs2,in

Ys2,out,r = Y2
Ts2,out,r = T2
Ps2,out = P2
Hs2,out,r = H2

Y2
T2
P2
H2

If Ps1,out >= Ps2,in Then Ys1,out = Ys1,out,r Else Ys2,in = Ys2,in,r

If Ps1,out >= Ps2,in Then Ts1,out = Ts1,out,r Else Ts2,in = Ts2,in,r
If Ps1,out >= Ps2,in Then Hs1,out = Hs1,out,r Else Hs2,in = Hs2,in,r
By using an alternating sequence of pressure and flow setters, you
can model process trains where reversibility may occur, without
causing singularities.

Adsorption Reference Manual

Flowsheeting 7-5

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.
Forward Direction

Process In

Inlet
Boundaries

n-1

n-1

Discretization
Nodes

Process In

Outlet
Boundaries

Process Out

n-1

Outlet
Boundaries

Inlet
Boundaries

n-1

n-1

Process Out

Reverse Direction

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.

7-6 Flowsheeting

Adsorption Reference Manual

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
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

Adsorption Reference Manual

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

Flowsheeting 7-7

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
Controllers are not connected using material connections; 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.

7-8 Flowsheeting

Adsorption Reference Manual

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.

Adsorption Reference Manual

Flowsheeting 7-9

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.
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.

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Adsorption Reference Manual

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:
Feed boundary unit
Adsorbent/resin bed (can contain any number of layers)
Product boundary unit

Product Boundary

Adsorbent or
Resin Bed

Feed Boundary

Adsorption Reference Manual

Flowsheeting 7-11

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.
Product Valve
Product Boundary
Top
Deadspace
(Tank)

Adsorbent
Bed

Bottom
Deadspace
(Tank)

Feed Boundary
Feed Valve

Use the intermediate flowsheet to simulate:

Co-current or counter-current adsorption
Repressurization and depressurization.
Purge using streams of different compositions

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Adsorption Reference Manual

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:
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)

Adsorption Reference Manual

Flowsheeting 7-13

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 countercurrently 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:

Bed 1

Bed 2

Bed 3

60

7-14 Flowsheeting

120

180

Adsorption Reference Manual

If the single bed approach is applied, using Bed 1 as the real bed,
the interactions would look like this:

Flowsheet Scope
Record

Replay

Bed 1

Bed 2

Bed 3

60

Adsorption Reference Manual

120

180

Flowsheeting 7-15

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:

Bed 1

60

120

180

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:

Bed 1

60

120

180

The three, 60 second duration steps were:

Step 1 0 through 60 seconds there is production with
some material used to repressurize another bed
Step 2 60 through 120 seconds there is counter-current
evacuation to waste
Step 3 120 through 180 seconds there is 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
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Adsorption Reference Manual

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
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.

Valve Present
In Scope
Real Bed
Scope

Store Profile

Adsorption Reference Manual

Store

Valve Not Present

In Scope

Replay

Real Bed
Scope

Replay Profile

Flowsheeting 7-17

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.

Valve

To product

Tank

Interaction

From bed

Notes:
The interaction units use the Delay function.
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.
If the simulation is closed or a snapshot re-used, the delay
buffer is emptied and all historical profile information is lost.
The snapshot does not store delay information.

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Adsorption Reference Manual

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:
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

The recommended solver options are:

Adsorption Reference Manual

Option

Value

Integrator

Variable Step Implicit Euler

Initial Integration Step

Minimum Integration Step

Maximum Integration Step

Step Reduction Factor

0.5

Maximum Step Increment Factor

1.5

Absolute Integration Error Tolerance

1e-5

Tear Integration Tolerance

Maximum Corrector Iterations

500

Show Highest Integration Errors

Use Interpolation

Enabled

Reconverge Torn Variables

Disbaled

Flowsheeting 7-19

Note When running rapid cycles, the integration steps may need
reducing.
Linear Solver Tab: Solver Options
The recommended solver options are:
Option

Value

Name

MA48

Drop Tolerance

Pivot Tolerance

Re-analyse Threshold

Re-analyze FLOPS Window 0

Size
Re-pivot every

Solver searches

Non-Linear Solver Tab: Solver Options

The recommended solver options are:

7-20 Flowsheeting

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

Dogleg Method

Disabled

Adsorption Reference Manual

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

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.

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.

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Flowsheeting 7-21

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 rightclicking on 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.

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Adsorption Reference Manual

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

Adsorption Reference Manual

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.

Flowsheeting 7-23

7-24 Flowsheeting

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 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.

Adsorption Reference Manual

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:
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 converted it to a component set (to do this, right-click on
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.

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Flowsheeting 7-25

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) are 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.

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 a 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

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Adsorption Reference Manual

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 on
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 on the ComponentLists object in Explorer and
browse for a previously created .appdf file.)
2. Select the currently active component list.
3. Right-click on the list and select Convert.
The component list switchers 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.

Adsorption Reference Manual

Flowsheeting 7-27

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 11.1 installation.
3. Place the required Aspen Dynamics model onto the Aspen
ADSIM flowsheet.

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Adsorption Reference Manual

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.
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.

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Flowsheeting 7-29

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.
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.

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Adsorption Reference Manual

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

Adsorption Reference Manual

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

Flowsheeting 7-31

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

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.

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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.

Adsorption Reference Manual

Flowsheeting 7-33

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.
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.

Continued overleaf

7-34 Flowsheeting

Adsorption Reference Manual

GlobalTimeScaler

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.

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.
Flowrate

Cycle
time
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

Adsorption Reference Manual

Flowsheeting 7-35

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.
Flowrate
Delayed Profiles
4 x DT
3 x DT
2 x DT
DT
Cycle
time

-5
7-36 Flowsheeting

B1.Toggle
1 2 3 4 5 6 7 8 9 10

B1.DelayTime
10 15 20 25 30

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 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

10 20 30 40 50 60 70 80 90 100
Time Seconds

Adsorption Reference Manual

B1.RealOutput
0
0.5

B1.CalcOutput
1
1.5
0.5

-1

-0.5

The result of this procedure is a continuously variable delay time

that produces a profile with a repeating pattern.

Output_Values

10 20 30 40 50 60 70 80 90 100
Time Seconds

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.

Adsorption Reference Manual

Flowsheeting 7-37

8 Reference List for Adsorption

Processes

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.

Adsorption Reference Manual

References 8-1

Tien, Chi, Adsorption Calculations and Modeling, ButterworthHeinemann, 1994.

Wakoo, N., Chem Eng Sci, 31, pp 1115, 1976.
Yang, R.T., Gas Separation by Adsorption Processes,
Butterworth, 1987.

8-2 References

Adsorption Reference Manual

Index

Activating cyclic tasks 6-19

Adsorbed solution theory (gas) 1-55
Adsorption isotherms (gas)
about 1-41
choosing 1-42
list 1-45
multicomponent mixture isotherms 1-42
Aspen Custom Modeler 5-2
Aspen Properties 7-26
Axial dispersion (gas) 1-10
Axial dispersion (ionx) 2-7
Axial dispersion (use for differencing
schemes) 4-7

B.E.T isotherm (gas) 1-48

B.E.T. Multilayer isotherm (gas) 1-49
Bed model assumptions (gas) 1-3
Bed model assumptions (ionx) 2-3
Bed model assumptions (liq) 3-3
Bed model ports (gas) 1-4
Bed models (gas) 1-4
Biased Upwind Differencing Scheme 4-13
Brunaur, Emmet and Teller See B.E.T
Burke-Plummer equation (gas) 1-15

Central differencing schemes 4-7, 4-8

Complex expression step control 6-8
Compressiblity (gas) 1-9

Adsorption Reference Manual

Conduction (gas) 1-56

Conduction (liq) 3-19, 3-23
Configure form (gas)
about 1-4
bed types 1-5
internal heat exchanger 1-7
spatial dimensions of beds 1-7
Configure form (ionx) 2-3
Configure form (liq) 3-3
Configure form tabs (gas)
Energy Balance 1-56
General 1-9
Isotherm 1-41
Kinetic Model 1-20
Material/Momentum Balance 1-10
Procedures 1-68
Reaction 1-65
Configure form tabs (ionx)
General 2-4
Isotherm 2-11
Kinetic Model 2-8
Material/Momentum Balance 2-5
Configure form tabs (liq)
Energy Balance 3-19
General 3-4
Isotherm 3-12
Kinetic Model 3-8
Material/Momentum Balance 3-5
Procedures 3-26
Configure Layer form (gas) 1-8
Configure Layer form (ionx) 2-4
Configure Layer form (liq) 3-4
Connecting controllers 7-8

Index 1

Connectivity in flowsheets 7-7

Consistency checks for flowsheets 7-23
Constant variables (specifying) 7-22
Controllers 7-8
ControlSignal stream 7-8
Convection (gas) 1-12
Convection (ionx) 2-5
Convection (liq) 3-5
Convert_EstMod script 5-14
Cycle controls 6-14
Cycle Organizer
about 6-2
cycle controls 6-14
Cycle Organizer window 6-3
cyclic reports 6-19
cyclic tasks 6-18, 6-19
interaction control 6-12
opening 6-3
step controls 6-4, 6-16
step variables 6-9
Cycle Organizer block 6-3
Cycle Organizer window 6-3
cycle controls 6-14
cyclic reports 6-19
cyclic tasks 6-18, 6-19
E
interaction controls 6-12
step controls 6-16
step variables 6-9
Cycle snapshots 6-15
Cyclic corrections (gas) 1-39
Cyclic operations 6-1
Cyclic Recovery report 6-23
Cyclic reports 6-19
Cyclic Recovery reports 6-23
Cyclic Stream reports 6-21
preparing 6-20
Cyclic Stream report 6-21
Cyclic tasks 6-18

Darcy's Law (gas) 1-14

Darcy's law (liq) 3-7
Deactivating cyclic tasks 6-19
Demonstration Organizer 7-10
Demonstrations 7-10
2 Index

Density (liq) 3-8

Discretization methods
about 4-2
choosing 4-3
list 4-4
recommended 4-3
Discretization methods (gas) 1-9
Discretization methods (ionx) 2-4
Discretization methods (liq) 3-4
Dispersion (gas) 1-12
Dispersion (ionx) 2-5, 2-7
Dispersion (liq) 3-5
Dispersion coefficient (ionx) 2-5
Dispersion coefficient (liq) 3-5
Dispersive properties (gas) 1-16
Dual Layer B.E.T isotherm (gas) 1-53
Dual-Site Langmuir isotherm (gas) 1-52
Dual-Site Langmuir isotherms (liq) 3-13
Dubinin-Astakov isotherm (gas) 1-49
Dynamic estimation
about 5-9
entering data manually 5-9
importing data from clipboard 5-11

Effective diffusivity (gas) 1-26, 1-29, 1-40

Energy balance assumption (gas) 1-56
Energy balance assumption (liq) 3-19
Energy balance equations (gas)
factors affecting equations 1-72
gas phase 1-69, 1-72
solid phase 1-69, 1-75
wall 1-70, 1-77
Energy balance equations (liq) 3-26
Energy Balance tab (gas) 1-56
Energy Balance tab (liq) 3-19
Enthalpy (gas) 1-57
Enthalpy (liq) 3-20
Equation symbols (gas) 1-79
Equation symbols (ionx) 2-14
Equation symbols (liq) 3-28
Ergun equation (gas) 1-15
Estimated mass transfer coefficient (gas) 140
Estimated Variables tab 5-4

Adsorption Reference Manual

Estimation
converting Estimation Module data 5-14
dynamic 5-9
estimated variables 5-4
Estimation Module 5-2
methods available 5-2
performing using Estimation Module 5-13
recommendations 5-14
steady-state 5-5
Estimation methods 5-14
Estimation Module
about 5-2
converting to Aspen Custom Modeler
methods 5-14
defining estimated variables 5-4
dynamic estimation 5-9
recommendations 5-14
steady-state estimation 5-5
using 5-13
Estimation Module block 5-3
Estimation Module form 5-3
Event-driven step controls 6-5
Experimental Data tab 5-5, 5-9
Expression Builder dialog
G box 6-8
Extended Langmuir isotherm (ionx) 2-12
Extended Langmuir isotherms (gas) 1-51
Extended Langmuir isotherms (liq) 3-14
Extended Langmuir-Freundlich isotherm
(gas) 1-52
Extended Langmuir-Freundlich isotherm
(ionx) 2-13
Extended Langmuir-Freundlich isotherms
(liq) 3-15

Film model assumption (gas) 1-20

Film model assumption (ionx) 2-8
Film model assumption (liq) 3-9
Flow reversibility 7-4
Flowsheet specifications See Specifying
flowsheets
Flowsheet types 7-11
full 7-13
intermediate 7-12
simple 7-11

Adsorption Reference Manual

Flowsheets
about 7-7
Connectivity 7-7
Cycle Organizer block 6-3
demonstrations 7-10
interactions 7-16
model types 7-3
physical property calculations 7-25
Pressure Interaction diagram 7-14
reversibility of flow 7-4
single bed approach 7-13
specifications 7-19
templates 7-9
types 7-11
Fluid phase energy balance (liq) 3-27
Fluid thermal conductivity (liq) 3-23
Flux Limited Differencing Scheme 4-14
Flux Limiter method? (gas) 1-9
Freundlich isotherms (gas) 1-47
Freundlich isotherms (liq) 3-14
Fromm's Scheme 4-14
Full flowsheet 7-13

g_Material_Port 7-8
Gas adsorption processes (overview) 1-2
Gas model assumption (gas) 1-9
Gas thermal conductivity (gas) 1-61
gas_Material_connection 7-8
Gas-Wall heat transfer coefficient (gas) 1-64
General tab (gas) 1-9
General tab (ionx) 2-4
General tab (liq) 3-4
Generating cyclic tasks 6-18
Glueckauf approximation (gas) 1-39
gUserCompressibility submodel 1-10
gUserCpa submodel 1-58
gUserDH submodel 1-59
gUserDispersion submodel 1-13
gUserEffDiff submodel 1-27, 1-31, 1-40
gUserGibbs submodel 1-54
gUserHTC submodel 1-60
gUserIsothermC submodel 1-54
gUserIsothermPoi submodel 1-54
gUserIsothermPp submodel 1-54
Index 3

gUserKg submodel 1-61

gUserKinetic submodel 1-25
gUserKineticModel submodel 1-33
gUserMTC submodel 1-39

Heat capacity (gas) 1-58

Heat capacity (liq) 3-20
Heat exchanger (gas) 1-7
Heat of adsorbed phase (gas) 1-57
Heat of adsorbed phase (liq) 3-20
Heat of adsorption (gas) 1-58
Heat of adsorption (liq) 3-21
Heat transfer coefficient (gas) 1-59
Heat transfer coefficient (liq) 3-22
Heat transfer to environment (gas) 1-62
Heat transfer to environment (liq) 3-24
Henry isotherms (gas) 1-47
Henry's coefficient (gas) 1-36
Heterogeneous rate dependency (gas) 1-67
Heterogeneous reactions (gas) 1-66
Homogeneous rate dependency (gas) 1-66
Homogeneous reactions (gas) 1-66
Horizontal beds (gas) 1-6

i_Material_Port 7-8
IAS (gas) 1-43, 1-55
IAS (liq)
about 3-11
IAS Freundlich isotherms 3-17
IAS Langmuir isotherms 3-16
IAS Langmuir-Freundlich isotherms 3-17
Purecomponent procedure with IAS
isotherm 3-18
K
Purecomponent submodel with IAS
isotherm 3-19
IAS Freundlich isotherms (liq) 3-17
IAS isotherm (gas) 1-55
IAS Langmuir isotherms (liq) 3-16
IAS Langmuir-Freundlich isotherms (liq) 317
Ideal Adsorbed Solution theory See IAS
Ideal gas (gas) 1-9

4 Index

Importing data from Microsoft Excel

dynamic 5-12
steady-state 5-8
Initialization for models 7-22
Interaction control 6-12
Interactions 6-12
Interactions between steps 7-16
Interactions example 7-16
Intermediate flowsheet 7-12
Internal heat exchanger (gas) 1-7
Ion-exchange adsorption processes
(overview) 2-2
Ion-exchange equilibria 2-11
Ion-exchange resins 2-2
ionx_Material_connection 7-8
Isotherm assumed for layer (gas) 1-45
Isotherm assumed for layer (ionx) 2-11
Isotherm assumed for layer (liq) 3-12
Isotherm dependency (gas) 1-55
Isotherm list (gas) 1-45
Isotherm list (ionx) 2-11
Isotherm list (liq) 3-12
Isotherm tab (gas) 1-41
Isotherm tab (ionx) 2-11
Isotherm tab (liq) 3-12
Isothermal conditions (gas) 1-56
Isothermal conditions (liq) 3-19
Isotherms (gas) 1-45
Isotherms (ionx) 2-11
Isotherms (liq) 3-11
iUserDispersion submodel 2-6
iUserIsotherm submodel 2-13
iUserKinetic submodel 2-9
iUserMTC submodel 2-10

Karman-Kozeny equation (gas) 1-15

Karman-Kozeny equation (liq) 3-7
Kinetic model assumption (gas) 1-20
Kinetic model assumption (ionx) 2-9
Kinetic model assumption (liq) 3-9
Kinetic Model tab (gas) 1-20
Kinetic Model tab (ionx) 2-8
Kinetic Model tab (liq) 3-8
Knudson diffusion coefficient (gas) 1-37

Adsorption Reference Manual

Langmuir isotherms (gas) 1-46

Langmuir isotherms (liq) 3-13
Langmuir-Freundlich isotherm (gas) 1-47
Langmuir-Freundlich isotherms (liq) 3-15
Leonard Differencing Scheme 4-8
Linear isotherm (gas) 1-50
liq_Material_connection 7-8
liq_Material_Port 7-8
Liquid adsorption processes (overview) 3-2
Lumped resistance (gas) 1-21, 1-34, 1-36
Lumped resistance (ionx) 2-9
Lumped resistance (liq) 3-9
lUserDH submodel 3-22
lUserDispersion submodel 3-6
lUserGibbs submodel 3-19
lUserHTC submodel 3-23
lUserIsotherm submodel 3-18, 3-19
lUserKinetic submodel 3-10
lUserKl submodel 3-24
lUserMTC submodel 3-10

Mass action equilibrium isotherm (ionx) 212

Mass balance equations (gas)
additional solid phase 1-69, 1-72
factors affecting equations 1-70
gas phase 1-68
Mass balance equations (ionx) 2-13
Mass balance equations (liq) 3-26
Mass transfer (gas)
N
about 1-20
lumped resistance 1-21, 1-34
micro and macropore effects 1-21
molecular diffusivities 1-34
particle material balance 1-26, 1-29
procedures 1-33
submodels 1-33
Mass transfer (ionx) 2-8
Mass transfer (liq) 3-8
Mass transfer coefficient (gas) 1-36, 1-40
Mass transfer coefficient (ionx) 2-10
Mass transfer coefficient (liq) 3-10

Adsorption Reference Manual

Mass transfer driving force (gas) 1-20

Mass transfer driving force (ionx) 2-8
Mass transfer driving force (liq) 3-9
Material balance assumption (gas) 1-12
Material balance assumption (ionx) 2-5
Material balance assumption (liq) 3-5
Material/Momentum Balance tab (gas) 1-10
Material/Momentum Balance tab (ionx) 2-5
Material/Momentum Balance tab (liq) 3-5
Maximum number of cycles 6-14
Micro and macropore effects (gas) 1-21, 124, 1-36
Micro and macropore effects (liq) 3-10
Microsoft Excel 5-8, 5-12
Mixed Differencing Scheme 4-11
Model configuration (defining) 7-22
Model specifications 7-21
Model types 7-2
Models
list of types 7-3
reversibility 7-4
types 7-2
Molecular diffusivities (gas) 1-34
Molecular diffusivity (ionx) 2-7
Momentum balance assumption (gas)
about 1-13
constant pressure options 1-14
pressure driven options 1-14
Multicomponent mixture isotherms (gas) 142
Myers isotherm (gas) 1-50

New Experiment dialog box

dynamic 5-9
steady-state 5-5
Nodes (gas) 1-9
Non-ideal gas (gas) 1-9
Non-isothermal conditions (gas) 1-56
Non-isothermal conditions (liq) 3-22, 3-23
Non-Isothermal conditions (liq) 3-19
Nonlinearity and numerical methods 4-2
Non-Reversible Delay models 7-3
Non-Reversible models 7-3

Index 5

Number of heterogeneous reactions (gas) 167

Number of homogeneous reactions (gas) 167
Number of nodes (gas) 1-9
Number of nodes (ionx) 2-4
Number of nodes (liq) 3-4
Numerical methods
about 4-2
Biased Upwind Differencing Scheme 4-13
Central Differencing Schemes 4-7, 4-8
Flux Limited Differencing Scheme 4-14
Fromm's Scheme 4-14
Leonard Differencing Scheme 4-8
Mixed Differencing Scheme 4-11
Quadratic Upwind Differencing Scheme
4-9
recommended 4-3
selecting 4-3
Upwind differencing schemes 4-5
Upwind Differencing Schemes 4-6

Obtain Dynamic Measurements for

Experiment DynExpt From Clipboard
dialog box 5-11
Obtain Steady State Experiments From
Clipboard dialog box 5-7
Overall material balance assumption (liq) 38

Particle material balance See Particle MB

options
Particle MB 2 option (gas) 1-29, 1-40
Particle MB option (gas) 1-26, 1-40
Particle resistance coefficients (gas) 1-24
PDE differencing schemes
Biased Upwind 4-13
Central 4-7, 4-8
Flux Limited 4-14
Fromm's 4-14
Leonard 4-8
Mixed 4-11

6 Index

Quadratic Upwind 4-9

Upwind 4-5, 4-6
Peclet number (gas) 1-11
Peclet number (ionx) 2-7
Physical property calculations
about 7-25
external applications 7-26
switching between methods 7-27
user Fortran 7-26
Port types 7-8
Prandl number (gas) 1-60
Prandl number (liq) 3-22
Presets for models 7-22
Pressure (gas) 1-13
Pressure (liq) 3-6
Pressure drop assumption (liq) 3-6
Pressure drop options (gas) 1-16
Pressure Interaction diagram 7-14
Pressure Interaction diagram example 7-14
Problem definition checks for flowsheets 723
Procedures (used in)
effective diffusivity 1-40
fluid thermal conductivity 3-24
gas thermal conductivity 1-61
heat of adsorbed phase 1-58
heat of adsorption 1-59, 3-21
heat transfer coefficient 1-60, 3-23
isotherms 1-53, 2-13, 3-18
kinetic model 1-33, 2-9, 3-10
mass transfer coefficient 1-39, 2-10, 3-10
material balance 1-13, 2-6, 3-6
molecular diffusivities 1-35
purecomponent isotherms 3-18
Procedures tab (gas) 1-68
Procedures tab (liq) 3-26
Properties Plus 7-26
pUser_Act_Coeff procedure 1-55
pUser_g_Cat_Rx_Heat procedure 1-75
pUser_g_Cat_Rx_Rate_C procedure 1-67,
1-75
pUser_g_Cat_Rx_Rate_C_Sol procedure 167, 1-75
pUser_g_Cat_Rx_Rate_Pp procedure 1-67,
1-68, 1-75

Adsorption Reference Manual

pUser_g_Cat_Rx_Rate_Pp_Sol procedure 167, 1-68, 1-72, 1-75

pUser_g_Compressibility procedure 1-10
pUser_g_Cpa procedure 1-58
pUser_g_De procedure 1-27, 1-31, 1-40
pUser_g_DH procedure 1-59
pUser_g_Diffusivity procedure 1-35
pUser_g_Dispersion procedure 1-13
pUser_g_Gas_Rx_Heat procedure 1-75
pUser_g_Gas_Rx_Rate_C procedure 1-66,
1-75
pUser_g_Gas_Rx_Rate_Pp procedure 1-66,
1-75
pUser_g_Gibbs procedure 1-54
pUser_g_HTC procedure 1-60
pUser_g_Isotherm_C procedure 1-53
pUser_g_Isotherm_P procedure 1-53
pUser_g_Isotherm_PoiSprocedure 1-54
pUser_g_Kg procedure 1-61
pUser_g_Kinetic procedure 1-25, 1-33
pUser_g_MTC procedure 1-39
pUser_i_Dispersion procedure 2-6
pUser_i_Isotherm_C procedure 2-13
pUser_i_Isotherm_W procedure 2-13
pUser_i_Kinetic procedure 2-9
pUser_i_MTC procedure 2-10
pUser_l_DH procedure 3-21
pUser_l_Dispersion procedure 3-6
pUser_l_Gibbs procedure 3-18
pUser_l_HTC procedure 3-23
pUser_l_Isotherm_C procedure 3-18
pUser_l_Isotherm_W procedure 3-18
pUser_l_Kinetic procedure 3-10
pUser_l_Kl procedure 3-24
pUser_l_MTC procedure 3-10

Quadratic Upwind Differencing Scheme 4-9

Radial beds (gas) 1-7

Radial nodes (gas) 1-9
Rate dependency (gas) 1-66, 1-67
Reaction processes (gas) 1-65

Adsorption Reference Manual

Reaction tab (gas) 1-65

Reactions present? (gas) 1-66
Reactions type (gas) 1-66
Real Adsorbed Solution theory (gas) 1-55
Real Adsorbed Solution Theory (gas) 1-45
Recommended numerical methods 4-3
Recording cycle information 6-14
Reference list 8-1
Reversibility example 7-4
Reversibility of flow 7-4
Reversible Flow Setter models 7-3
Reversible models 7-3
Reversible Pressure Setter models 7-3
Rigorous multiple bed approach 7-13
Run time options (specifying) 7-21
Running end-of-step scripts 6-16

Sherwood number (gas) 1-37

Simple flowsheet 7-11
Simulation Messages window 6-14, 6-15
Single bed approach 6-12, 7-13
Single Layer B.E.T isotherm (gas) 1-52
Snapshots 6-15, 6-17
Solid phase energy balance (liq) 3-27
Solid reactant list (gas) 1-68
Solid reactants present? (gas) 1-67
Solver options (specifying) 7-19
Spatial dimensions of beds (gas) 1-7
Specifying flowsheets
checks 7-23
list of options 7-19
model specification 7-21
run time options 7-21
solver options 7-19
Static_isotherm model 5-5
Steady state testing (cyclic) 6-15
Steady-state estimation
about 5-5
entering data manually 5-5
importing data from clipboard 5-7
Step controls 6-16
Step dependent step control 6-9
Step interaction control 6-12
Step interactions 6-12, 7-16
Index 7

W
Step variables 6-9
Stoichiometric Equilibrium isotherms (liq)
3-16
Submodels (used in)
component isotherms 3-19
effective diffusivity 1-40
fluid thermal conductivity 3-24
gas thermal conductivity 1-61
heat of adsorbed phase 1-58
heat of adsorption 1-59, 3-22
heat transfer coefficient 1-60, 3-23
isotherms 1-54, 2-13, 3-18
kinetic model 1-33, 2-9, 3-10
mass transfer coefficient 1-39, 2-10, 3-10
material balance 1-13, 2-6, 3-6

Wall energy balance (liq) 3-27

Water softening and purification (ionx) 2-2

Task Language 6-18

Template Organizer 7-9
Templates 7-9
Time controls (reason for) 6-13
Time-driven step controls 6-5
Toth isotherm (gas) 1-48

Upwind differencing schemes 4-5, 4-6

User Multicomponent Procedure isotherm
(liq) 3-18
User Multicomponent Submodel isotherm
(liq) 3-18
User Purecomponent Procedure with IAS
isotherm (liq) 3-18
User Purecomponent Submodel with IAS
isotherm (liq) 3-19

Variable fields 6-11

Variable Selector dialog box 6-10
Velocity (gas) 1-13
Velocity assumption (liq) 3-7
Vertical beds (gas) 1-5, 1-7, 1-16
Volmer isotherm (gas) 1-50

8 Index

Adsorption Reference Manual