Reactor Modeling with Aspen Plus User Kinetics

User Kinetics

Objective:
How to write you own User Kinetics Fortran
routine

Aspen Plus References: User Models Reference Manual , Chapter 11. User Kinetics Subroutines

©2002 AspenTech. All Rights Reserved.

User Kinetic Subroutines

• When your reaction kinetic does not fit the standard Aspen Plus
expressions. The following models allow you to supply a kinetic
subroutine to calculate the reaction rates
Model Name Reaction Type
RPlug USER
RCSTR USER
RBatch USER
Pres Relief USER
RadFrac REAC-DIST or USER
RateFrac REAC-DIST or USER
BatchFrac REAC-DIST
©2002 AspenTech. All Rights Reserved.

©2002 AspenTech. All Rights Reserved. 6– 1 Aspen Technology, Inc.

Reactor Modeling with Aspen Plus User Kinetics

The Goal of the Kinetics Routine

• For reactor models
– Calculate rate of generation for each component in each
substream
– Make sure rates are in mass balance

• For stage separation models

– Calculate the rate of generation for each component on a
given stage
– Make sure rates are in mass balance

©2002 AspenTech. All Rights Reserved.

User Kinetic: Subroutine

• All units are in SI

• Have access to
– Aspen Plus physical property system through the physical
property monitors
– Pure component physical property parameters
– Parameters specific to a reactor

©2002 AspenTech. All Rights Reserved.

©2002 AspenTech. All Rights Reserved. 6– 2 Aspen Technology, Inc.

Reactor Modeling with Aspen Plus User Kinetics

User Kinetic Reactions

• Fortran subroutine
– Name maximum 6 characters in length
– Uses real variables in double precision

• On the Reactions Reactions sheets specify:

– Reaction stoichiometry
– Subroutine name
– Input variables through the INT and REAL vectors

©2002 AspenTech. All Rights Reserved.

Reaction Rates (1)

• Units of reaction rates are different in different blocks:

• For RBatch and RCSTR

– Conventional components:
(kgmole/m3-s)(m3) = kgmole/s

Note:
Rates per unit volume are multiplied by the volume
occupied by the reacting phase

©2002 AspenTech. All Rights Reserved.

©2002 AspenTech. All Rights Reserved. 6– 3 Aspen Technology, Inc.

Reactor Modeling with Aspen Plus User Kinetics

Reaction Rates (2)

• For RPLUG
– Conventional components:
(kgmole/m3-s)(m2) = kgmole/m-s

Note:
Rates per unit volume are multiplied by the cross-
sectional area covered by the reacting phase

©2002 AspenTech. All Rights Reserved.

Points to Remember about Reaction Rates

• We recommend that when calculating the final rates, use
the reaction volume variables, RPROPS_VLIQ and
RPROPS_VVAP from common RXN_RPROPS. This
guarantees:
– That RCSTR behaves the same way with or without the user
kinetics subroutine. (in terms of the behavior of the parameters
VOL and REAC-VOL)
– That the same subroutine can be used for all types of reactor
blocks

©2002 AspenTech. All Rights Reserved.

©2002 AspenTech. All Rights Reserved. 6– 4 Aspen Technology, Inc.

Reactor Modeling with Aspen Plus User Kinetics

User Kinetics: Physical Properties (1)

• Use the ASPEN PLUS monitor routines to access the Aspen Plus
physical property system

• Monitors are available to calculate the following pure component

and mixture thermodynamic properties for either vapor, liquid or
solid
– Fugacity coefficients
– Enthalpies
– Entropies
– Free energies
– Molar volumes
– K-values
– Ideal gas properties

©2002 AspenTech. All Rights Reserved.

User Kinetics: Physical Properties (2)

• Vapor, Liquid and Solids transport properties are also
available

• See the User Models Reference Manual Chapter 3 for

more details

©2002 AspenTech. All Rights Reserved.

©2002 AspenTech. All Rights Reserved. 6– 5 Aspen Technology, Inc.

Reactor Modeling with Aspen Plus User Kinetics

Passing Parameters
• User constants and variables are available to kinetics
routine in the real and integer vectors
• They can be defined in two places
– Reactions Reactions Subroutine sheet
• Global variables
• Vector names in subroutine REALR and INTR
– The User Subroutine Kinetics sheet, for the RCSTR, RBatch
and RPlug reactors
• Local to that reactor
• Vector names in subroutine REAL and INT

©2002 AspenTech. All Rights Reserved.

Useful Argument List Parameters

• SOUT - Vector containing information about the reactor
contents at the time of calling the Fortran routine
– Total and component flow rates
– Temperature and Pressure
– Total mass enthalpy and entropy
– Vapor and liquid molar fractions
– Mass density
– Molecular weight

• Detailed list of contents and units in this array see User

Models reference manual, Appendix C

©2002 AspenTech. All Rights Reserved.

©2002 AspenTech. All Rights Reserved. 6– 6 Aspen Technology, Inc.

Reactor Modeling with Aspen Plus User Kinetics

SOUT: Stream Vector

Array Index Description
1,……,NCC Component mole flows (kmol/s)
NCC+1 Total mole flow (kmol/s)
NCC+2 Temperature (K)
2
NCC+3 Pressure (N/m )
NCC+4 Mass enthalpy (J/kg)
NCC+5 Molar Vapor Fraction
NCC+6 Molar Liquid Fraction
NCC+7 Mass entropy (J/kg-K)
3
NCC+8 Mass Density (kg/m )
NCC+9 Molecular weight (kg/kmol)

©2002 AspenTech. All Rights Reserved.

Useful Argument List Parameters

• Arrays, Y, X, X1 and X2. Vapor, liquid, liquid1 and liquid2
mole fraction arrays
– Mole fraction arrays are packed vectors of length NCOMP
– Contain only components with non zero fractions
– IDX vector defines the order of components with respect to the
Components Specifications Selection sheet
Example. If NCOMP=2 and IDX(1,3)
Then Y(2) is the vapor mole fraction of the third component
on the Components Specifications Selection sheet

©2002 AspenTech. All Rights Reserved.

©2002 AspenTech. All Rights Reserved. 6– 7 Aspen Technology, Inc.

Reactor Modeling with Aspen Plus User Kinetics

Component Mole Fractions

Size = NC
Size = NCOMP Stream Liquid
Order Components.Main Mole Fractions
X IDX 1 Water 0.3
0.3 1 2 Ethanol 0.3
0.3 2 3 Methanol 0
0.4 4 4 Benzene 0.4
5 Nitrogen 0

©2002 AspenTech. All Rights Reserved.

Accessing Universal Constants

• All physical property parameters used in the simulation
are available to a user routine
• Stored in a labeled common call the DMS_PLEX
• Each parameter occupies a continuous area within the
PLEX

• To access a parameter you will need to know:

– The name of the parameter
– The offset of the parameter in the PLEX
– The structure of that area

©2002 AspenTech. All Rights Reserved.

©2002 AspenTech. All Rights Reserved. 6– 8 Aspen Technology, Inc.

Reactor Modeling with Aspen Plus User Kinetics

User Kinetics: Universal Constants (1)

• You can access the following universal constants:
Name Definition

MW Molecular weight(kg/kgmole)

TC Critical Temperature (K)

2
PC Critical Pressure (N/m )
3
VC Critical volume (m /kgmole)

OMEGA Pitzer acentric factor

DHFORM Standard heat of formation of ideal gas at 298.15 K (J/kgmole)

DGFORM Standard energy of formation of ideal gas at 298.15 K (J/kgmole)

TB Normal boiling point (K)

3
VB Liquid molar volume at TB (m /kgmole)

TFP Normal freezing point (K)

3 1/2
DELTA Solubility parameter at 298.15 K (J/m )
©2002 AspenTech. All Rights Reserved.

User Kinetics: Universal Constants (2)

Name Definition
3 1/2
MUP Dipole moment (J*m )

RGYR Radius of gyration (m)

CHI Stiel polar factor

CHARGE Ionic charge number

©2002 AspenTech. All Rights Reserved.

©2002 AspenTech. All Rights Reserved. 6– 9 Aspen Technology, Inc.

Reactor Modeling with Aspen Plus User Kinetics

Practical Steps Required to Get a Value (1)

• Include the labeled common DMS_PLEX in the model
• Find the parameters name
– See page 6-13 of “User Model” Reference Manual for a list of
common parameters

• Determine the offset of the parameter

– Use the functions DMS_IFCMNC or DMS_IFCMN
LMW = DMS_IFCMNC(‘MW’)
– This line must appear before any executable code
– The MW values start from B(LMW + 1) and will be in the same
order as components on Components Specifications sheet

©2002 AspenTech. All Rights Reserved.

Practical Steps Required to Get a Value (2)

• Use statement functions to find the offset of any component:

XMW(I) = LMW + I
– Define XMW as an integer
INTEGER XMW

• Use the parameter in your equation

SUM=0

DO 10 I=1,NC

SUM=SUM+B(XMW(I))
10 CONTINUE

©2002 AspenTech. All Rights Reserved.

©2002 AspenTech. All Rights Reserved. 6 – 10 Aspen Technology, Inc.

Reactor Modeling with Aspen Plus User Kinetics

Reactor Specific Parameters (1)

• Different parameters are available for each reactor unit
operation
• RPlug
COMMON Block Description
RPLG_RPLUGI Integer configuration
parameters, Number of
reactor tubes
RPLG_RPLUGR Reactor length
Reactor diameter

©2002 AspenTech. All Rights Reserved.

Reactor Specific Parameters (2)

• RBatch
COMMON Block Description
RBTC_RBATI Reactor Type

3
RBTC_VOLRB Reactor volume (m )

©2002 AspenTech. All Rights Reserved.

©2002 AspenTech. All Rights Reserved. 6 – 11 Aspen Technology, Inc.

Reactor Modeling with Aspen Plus User Kinetics

Reactor Specific Parameters (3)

• RCSTR
COMMON Block Description
RCST_RCSTRI Reactor Type

3
RXN_RCSTRR Reactor volume (m ),
Reactor volume fraction

©2002 AspenTech. All Rights Reserved.

Reactor Specific Parameters (4)

• General properties
COMMON Block Description
RXN_RPROPS Reactor temperature,
pressure, molar vapor
fraction, BETA, Volume of
vapor, liquid or liquid and
solid

©2002 AspenTech. All Rights Reserved.

©2002 AspenTech. All Rights Reserved. 6 – 12 Aspen Technology, Inc.

Reactor Modeling with Aspen Plus User Kinetics

Using a Fortran Routine

• You must compile on the Aspen Plus server with the
command aspcomp <filename>

• Place the compiled object files in the run directory

• Alternatively
– Write a Dynamic Linking Options (DLOPT) file which specifies
the objects to use

©2002 AspenTech. All Rights Reserved.

Fortran Compiler
• To develop user kinetics routines on the PC you require
a Digital Visual Fortran 5.0 compiler
• End users do not required a compiler, distribute file as as
shared library
– Create shared libraries with the command:
asplink

©2002 AspenTech. All Rights Reserved.

©2002 AspenTech. All Rights Reserved. 6 – 13 Aspen Technology, Inc.

Reactor Modeling with Aspen Plus User Kinetics

User Kinetic References

• See User Models Reference Manual for more detailed
information

• Templates are provided for many user subroutines. By

default they are located in the Program
Files\AspenTech\ap100\user directory

©2002 AspenTech. All Rights Reserved.

User Kinetics: Workshop 7 (1)

Objective: To model a Power Law expression using a User
Kinetics routine
CSTR-PL

DUPL
FEED FEEDPL PRODUCT

FEEDUK

CSTR-UK

PRODUK

Filename: WK7-USERKIN.BKP

©2002 AspenTech. All Rights Reserved.

©2002 AspenTech. All Rights Reserved. 6 – 14 Aspen Technology, Inc.

Reactor Modeling with Aspen Plus User Kinetics

User Kinetics: Workshop 7 (2)

• Setup two RCSTR reactors
– Use the standard Power Law expression
– Use a User kinetic routine of the Power Law expression

• Reaction
Acetone + Allyl Alcohol → N-Propyl Propionate

r = K*EXP(-E/RT)*CACB0.5

Where
CA = Concentration of Allyl-Alcohol, in kmol/m3
CB = Concentration of Acetone, in kmol/m3

©2002 AspenTech. All Rights Reserved.

User Kinetics: Workshop 7 (3)

• Reaction Kinetics
Pre-Exponential Factor= 52860000 m3**0.5/kmol**0.5-Sec
Activation Energy = 62E6 J/ kmol
• Reactor Conditions
Temperature = 25 C
Pressure = 1 Atm
Volume = 300 Liters
• Feed Conditions
Acetone = 75 kg/hr
Allyl Alcohol = 50 kg/hr
Temperature = 25 C
Pressure = 1 Atm

©2002 AspenTech. All Rights Reserved.

©2002 AspenTech. All Rights Reserved. 6 – 15 Aspen Technology, Inc.

Reactor Modeling with Aspen Plus User Kinetics

User Kinetics: Workshop 7 (4)

• Property Method : NRTL-RK
• A template has been supplied for the User kinetic
routine, USRKIN.F
• Calculate the rate of reaction for all the components from
the information given
• Save file as WK7-USERKIN.BKP

©2002 AspenTech. All Rights Reserved.

©2002 AspenTech. All Rights Reserved. 6 – 16 Aspen Technology, Inc.