Advanced Distillation with Aspen Plus Reactive Distillation

Reactive Distillation

Advanced Distillation with Aspen Plus

© 2002 AspenTech. All Rights Reserved.

Lesson Objectives

• Understand how to model a reactive distillation column in

Aspen Plus

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Advanced Distillation with Aspen Plus Reactive Distillation

Distillation with Reactions

• Distillation with reaction is a comprehensive capability

that offers the following features:
– Equilibrium, conversion, electrolytic, and rate-controlled
reactions can occur simultaneously.
– Reactions can occur in vapor and/or liquid phases (liquid, first
liquid, or second liquid phases).
– Reactions can occur on any or all stages, including
thermosyphon reboilers.
– Any number of reactions can occur.

© 2002 AspenTech. All Rights Reserved.

How to Set up Reactive Distillation

1. Create a Reaction ID by clicking on “New” under
Reactions/Reactions in the Data Browser.

2. Select the REAC-DIST type.

3. On the Reactions Stoichiometry sheet create the new reactions.

Define each reaction using the Edit Reaction dialog box.

4. On the Reactions Kinetic, Equilibrium, or Conversion sheet, provide

kinetic, equilibrium, or conversion data.

5. On the Column Reactions Specifications sheet, specify the Reaction

ID and the stages where the reaction occurs.

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Advanced Distillation with Aspen Plus Reactive Distillation

Kinetic Reactions (1)

• Kinetic reactions can be vapor or liquid phase (liquid,

liquid 1, or liquid 2) reactions.
• Kinetic data can be provided using either:
– Built-in Power-Law expression
– User kinetic subroutine

• Kinetic reactions require holdup or residence time data.

– You can provide holdup data in mole, mass, or volume basis.

© 2002 AspenTech. All Rights Reserved.

Kinetic Reactions (2)

• Aspen Plus allows flexible concentration terms when

using the Power Law expression:
R = kT n e − E / RT π (Ci )αi
Concentration (Ci) can be:
- Mole fraction
- Mass fraction
- Molarity
- Molality

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Advanced Distillation with Aspen Plus Reactive Distillation

Equilibrium Reactions (1)

• Aspen Plus can calculate equilibrium constants from

either:
– Reference state free energies
– Built-in expression

• The built-in expression is of the form:

B
ln K eq = A + + C ln(T ) + DT
T
with Temperature (T) in Kelvin

© 2002 AspenTech. All Rights Reserved.

Equilibrium Reactions (2)

• You can specify a temperature approach to equilibrium.

It is added to the stage temperature to determine the
equilibrium constant.
• Equilibrium reactions can occur in the vapor or liquid
phase (liquid, liquid 1, or liquid 2).

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Advanced Distillation with Aspen Plus Reactive Distillation

Equilibrium Reactions (3)

The following table lists the possible bases for built-in equilibrium
constant expressions:
Keq basis Expression Description
……………………………………………………………………………………………………………………………………………………………………...…….
υi
K = π ( X iγ i )
..
Mole gamma (Liquid only)(Default)
……………………………………………………………………………………………………………………………………………………………………...…….
υi
..
Molal gamma
m
K = π (C iγ i ) (Electrolytes, Liquid only)
……………………………………………………………………………………………………………………………………………………………………...…….
υi
K = π ( xi )
..
Mole fraction
……………………………………………………………………………………………………………………………………………………………………...…….
m υi
K = π( X i)
..
Mass fraction
……………………………………………………………………………………………………………………………………………………………………...…….

K = π ( C )υi
..
Molarity
i
……………………………………………………………………………………………………………………………………………………………………...…….

K = π (C m i )υi
..
Molality (Electrolytes, Liquid only)
……………………………………………………………………………………………………………………………………………………………………...…….
υi
K = π ( fi )
..
Fugacity
……………………………………………………………………………………………………………………………………………………………………...…….
..
Partial pressure K = π ( Pi )υi (Vapor only)

© 2002 AspenTech. All Rights Reserved.

Conversion Reactions (1)

• Aspen Plus uses the following built-in conversion

expression:
B
Conv = A + + C ln(T ) + DT
T
with Temperature (T) in Kelvin

• The key component for conversion reactions must be

specified.

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Advanced Distillation with Aspen Plus Reactive Distillation

Conversion Reactions (2)

• For multiple conversion reactions, you must specify one

of the following types:
– Series
– Simultaneous (default)
» All reactions must be of the same type.

• You can provide a conversion profile on the RadFrac

Reactions Conversion sheet.

© 2002 AspenTech. All Rights Reserved.

Conversion Reactions Example (3)

In the MEG Column example, assume ethylene glycol

(MEG) reacts with one another in the reboiler sump to
form diethylene glycol (DEG) and tri-ethylene glycol
(TEG) as follows:
2MEG -> DEG + H2O 1% of MEG
conversion
MEG + DEG -> TEG + H2O 1% of DEG
conversion
Add these reactions to the file ws-meg-col.bkp so that
these reactions are accounted for in the column.

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Advanced Distillation with Aspen Plus Reactive Distillation

Example: Kinetic Reactions (1)

• The following esterification kinetic reactions occur in the distillation

column reactor:

AA + ETOH <--> EA + H2O

Forward Reaction: rf =1.9E8-5.95E7/RT[AA][ETOH]

Reverse Reaction: rr=5.0E7e-5.95E7/RT[EA][H2O]

Where:
Concentration is in kg-mole/m3
Reaction rates are in kg-mole/m3-sec
Activation Energy is in J/kmol

© 2002 AspenTech. All Rights Reserved.

Example: Kinetic Reactions (2)

• Enter reaction stoichiometry on the Reactions Reactions
Stoichiometry sheet.

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Advanced Distillation with Aspen Plus Reactive Distillation

Example: Kinetic Reactions (3)

• Enter a reaction’s associated kinetic data on the
Reactions Reactions Kinetic sheet.

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Example: Kinetic Reactions (4)

• Reactions occur in the liquid phase on all stages except
the condenser.

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Advanced Distillation with Aspen Plus Reactive Distillation

Example: Kinetic Reactions (5)

• The liquid holdup is 1.0 liter for the reboiler and 0.3 liter
for all other stages.

© 2002 AspenTech. All Rights Reserved.

Example: Kinetic Reactions (6)

Esterification Column
Distillate rate = 30 kmol/hr

DIST

COL Stage 1 Pressure 1 bar

FEED Stage 15 Pressure 1 bar

15 stages
Total condenser
Molar reflux ratio = 0.7
FEED enters above stage 7
AA 50 kmol/hr
ETOH 50 kmol/hr BOTTOMS

FILENAME: EX4A-KINETIC-ESTER.BKP

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Advanced Distillation with Aspen Plus Reactive Distillation

Example: Equilibrium Reactions (1)

Para/Meta Xylenes Separation Column

MX + DTBB ↔ TBMX + TBB (1)

MX + TBB ↔ TBMX + BZ (2)

X TBMX X TBB
K1 = ; ln K1 = −0.51
X MX X DTBB

X TBMX X TBZ
K1 = ; ln K 2 = −1.83
X MX X TBB
© 2002 AspenTech. All Rights Reserved.

Example: Equilibrium Reactions (2)

• Enter a reaction’s associated equilibrium data on the

Reactions Reactions Equilibrium sheet.

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Advanced Distillation with Aspen Plus Reactive Distillation

Example: Equilibrium Reactions (3)

Para/Meta Xylenes Separation Column

Saturated liquid
no reactions
P = 44 torr
in condenser
DTBB 0.6552 lb/hr
TBB 0.1248 lb/hr Distillate rate = 0.44 lb/hr
DIST
SOLVENT 2

COL 15 stages
Molar reflux ratio = 2

FEED 11

Saturated liquid BOTTOMS

P = 54 torr
MX 0.5734 lb/hr
PX 0.6466 lb/hr

FILENAME: EX4B-EQUIL-PMXYLENE.BKP
© 2002 AspenTech. All Rights Reserved.

User Kinetic Subroutines (1)

A User-Kinetic Fortran Subroutine:

– Gets called once for each stage specified in the Reactions form
– Has access to reaction stoichiometry, stage temperature,
pressure, composition, holdup, and flows
– Computes and returns rates of conversion (moles/sec) for each
component (positive for products, negative for reactants)
– Uses Sl units
– Uses real variables in double precision

» You need to enter the name of the subroutine on the

Reactions Subroutine sheet. You can enter inputs
through INT and REAL vectors on the same sheet.

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Advanced Distillation with Aspen Plus Reactive Distillation

User Kinetic Subroutine Reference (2)

• 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\ap10x\engine\user directory.

© 2002 AspenTech. All Rights Reserved.

User Kinetic Subroutine Template (3)

C
C User Kinetics Subroutine for RADFRAC, BATCHFRAC, RATEFRAC
C (REAC -DIST type Reactions)
C
SUBROUTINE USRKNT (N, NCOMP, NR, NRL, NRV,
2 T, TLIQ, TVAP, P, PHFRA C,
3 F, X, Y, IDX, NBOPS T,
4 KDIAG, STOIC, IHLBAS, HLDLIQ, TIMLI Q,
5 IHVBAS, HLDVAP, TIMVAP, NINT, INT,
6 NREAL, REAL, RATES, RATEL, RATEV ,
7 NINTB, INTB, NREALB, REALB, NIWOR K,
8 IWORK, NWORK, WORK)

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Advanced Distillation with Aspen Plus Reactive Distillation

User Kinetic Subroutine Template (4)

C VARIABLES IN ARGUMENT LIST
C
C VARIABLE I/O TYPE DIMENSION DESCRIPTION AND RA NGE
C N I I - STAGE NUMBER
C NCOMP I I - NUMBER OF COMPONENTS
C NR I I - TOTAL NUMBER OF KINETIC
C REACTIONS
C NRL I I 3 NUMBER OF LIQUID P HASE
C KINETIC REACTIONS.
C NRL(1): NUMBER OF
C OVERALL LI QUID
C REACTIONS.
C NRL(2): NUMBER OF
C LIQUID1 RE ACTIONS.
C NRL(3): NUMBER OF
C LIQUID2 RE ACTIONS.
C NRV I I - NUMBER OF VAPOR PHASE
C KINETIC REACTIONS
C T I R - STAGE TEMPERATURE (K)
C TLIQ I R - LIQUID TEMPERATURE (K)
C * USED ONLY BY RAT EFRAC **
C TVAP I R - VAPOR TEMPERATURE (K)
C * USED ONLY BY RAT EFRAC **
C P I R - STAGE PRESSURE (N/SQ.M)
C PHFRAC I R 3 PHASE FRACTION
C PHFRAC(1): VAPOR F RACTION
C PHFRAC(2): LIQUID1 FRACTIO
C PHFRAC(3): LIQUID2 FRACTIO
© 2002 AspenTech. All Rights Reserved.

User Kinetic Subroutine Template (5)

C F I R - TOTAL FLOW ON STAGE
C (VAPOR+LIQUID) (KM OL/SEC)
C X I R NCOMP,3 LIQUID MOLE FRACTI ON
C Y I R NCOMP VAPOR MOLE FRACTIO N
C IDX I I NCOMP COMPONENT INDEX VE CTOR
C NBOPST I I 6 OPTION SET BEAD PO INTER
C KDIAG I I - LOCAL DIAGNOSTIC LEVEL
C STOIC I R NCOMP,NR REACTION STOICHIOM ETRY
C IHLBAS I I - BASIS FOR LIQUID
C HOLDUP SPECIFICATI ON
C 1:VOLUME,2:MASS,3: MOLE
C HLDLIQ I R - LIQUID HOLDUP
C IHLBAS UNITS
C 1 CU.M.
C 2 KG
C 3 KMOL
C TIMLIQ I R - LIQUID RESIDENCE TIME
C (SEC)
C IHVBAS I I - BASIS FOR VAPOR
C HOLDUP SPECIFICATI ON
C 1:VOLUME,2:MASS,3: MOLE
C HLDVAP I R - VAPOR HOLDUP
C IHVBAS UNITS
C 1 CU.M.
C 2 KG
C 3 KMOL
C TIMVAP I R - VAPOR RESIDENCE TIME (SEC)
C NINT I I - LENGTH OF INTEGER VECTOR
C INT I/O I NINT INTEGER VECTOR
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Advanced Distillation with Aspen Plus Reactive Distillation

User Kinetic Subroutine Template (6)

C NREAL I I - LENGTH OF REAL VECTOR
C REAL I/O R NREAL REAL VECTOR
C RATES O R NCOMP COMPONENT REACTION RATES
C (KMOL/SEC)
C RATEL O R NRLT INDIVIDUAL REACTIO N RATES
C IN THE LIQUID PHAS E
C (KMOL/SEC)
C WHAT IS NRLT?
C NRLT = NRL(1)+NRL( 2)+NRL(3
C NRLT IS NOT INCLUD ED IN TH
C ARGUMENT LIST.
C * USED ONLY BY RAT EFRAC *
C RATEV O R NRV INDIVIDUAL REACTIO N RATES
C IN THE VAPOR PHASE
C (KMOL/SEC)
C * USED ONLY BY RAT EFRAC *
C NINTB I I - LENGTH OF INTEGER VECTOR
C (FROM UOS BLOCK)
C INTB I/O I NINTB INTEGER VECTOR
C (FROM UOS BLOCK)
C NREALB I I - LENGTH OF REAL VECTOR
C (FROM UOS BLOCK)
C REALB I/O R NREALB REAL VECTOR
C (FROM UOS BLOCK)
C NIWORK I I - LENGTH OF INTEGER WORK
C VECTOR
C IWORK I/O I NIWORK INTEGER WORK VECTO R
C NWORK I I - LENGTH OF REAL WORK VECTOR
C WORK I/O R NWORK REAL WORK VECTOR
© 2002 AspenTech. All Rights Reserved.

User Kinetic Subroutine Template (7)

IMPLICIT NONE
C
C DECLARE VARIABLES USED IN DIMENSIONING
C
INTEGER NCOMP, NR, NRV, NINT, NINTB,
+ NREALB,NIWORK,NWORK
C
#include "ppexec _user.cmn"
EQUIVALENCE (RMISS, USER_RUMISS)
EQUIVALENCE (IMISS, USER_IUMISS)
C
C DECLARE ARGUMENTS
C
INTEGER NRL(3),IDX(NCOMP), NBOPST(6), INT(NINT), INTB(NINT B),
+ IWORK(NIWORK),N, KDIAG, IHLBAS, IHVBAS, NREAL
REAL*8 PHFRAC(3), X(NCOMP,3), Y(NCOMP),
+ STOIC(NCOMP,NR), RATES(NCOMP),
+ RATEL(1), RATEV(NRV),
+ REALB(NREALB),WORK(NWORK), T, TLIQ,
+ TVAP, P, F, HLDLIQ,TIMLIQ
REAL*8 HLDVAP,TIMVAP
C
C DECLARE LOCAL VARIABLES
C
INTEGER IMISS
REAL*8 REAL(NREAL), RMISS
C
C BEGIN EXECUTABLE CODE
C
RETURN
END
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Advanced Distillation with Aspen Plus Reactive Distillation

Example: User Kinetic Subroutine (8)

Suppose the following vapor phase reactions occur in
the reboiler of a distillation column. Write a user kinetic
subroutine to supply the kinetics for the distillation
calculations.
(1) 2 C6 H 6 (BZ ) → C12 H 10 ( DP ) + H 2 ( H 2 )
(2 ) C6 H 6 ( BZ ) + C12 H 10 ( DP ) → C18 H14 (TP ) + H 2 (H 2)
 P P 
R1 = 66500e −15200 / T *  PBZ2 − DP H 2 
 0.312 
 P P 
R2 = 38400e −15200 / T *  PBZ PDP − TP H 2 
 0.48 
R1 and R2 are in kg-moles/sec-m3
FILENAME: EX4C-USER-DP.BKP
© 2002 AspenTech. All Rights Reserved.

Example: User Kinetic Subroutine (9)

REAL*8 PH2, PBZ, PDP, PTP, RATE1, RATE2
C
C EXECUTABLE CODE
C
C COMPUTE PARTIAL PRESSURES
C
PH2 = Y(1)*P
PBZ = Y(2)*P
PDP = Y(3)*P
PTP = Y(4)*P
C
C CALCULATE REACTION RATES
C
RATE1 = HLDAP*6.65D4*DEXP(-1.52D4/T)*PBZ*PBZ -PDP*PH2/0.312D0)
RATE2 = HLDAP*3.86D4*DEXP(-1.52D4/T)*PBZ*PDP -PTP*PH2/0.48D0)
C
C CONVERSION FOR HYDROGEN
RATES(1) = RATE1/2D + RATE2
C
C CONVERSION FOR BENZENE
RATES(2) = - (RATE1 + RATE2)
C
C CONVERSION FOR DI -PHENYL
RATES(3) = RATE1/2D0 - RATE2
C
C CONVERSION FOR TRI-PHENYL
RATES(4) = RATE2
C
RETURN
END
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Advanced Distillation with Aspen Plus Reactive Distillation

Workshop 4: MTBE Reactive Distillation (1)

Equilibrium reaction Use the UNIFAC property method
ISOBUTYLENE + METHANOL <==> MTBE

95 psia
Temperature = 70 F
Pressure = 400 psia C4RAFF
METHANOL 540 lbmol/hr
15 30 stages
MEOHFEED
Catalyst on stages 15-19
MBTECOL Molar reflux ratio = 8
Top tray pressure = 100 psia
20
C4FEED
Temperature = 110 F
Pressure = 400 psia
PROPANE 7 lbmol/hr MTBEPROD 520 lbmol/hr
ISOBUTANE 670 lbmol/hr 115 psia
ISOBUTYLENE 530 lbmol/hr
Vary bottoms rate from 500 to 550 lbmol/hr to achieve
N-BUTANE 20 lbmol/hr
a mole fraction of 0.998 for MTBE in the bottoms.
1-BUTENE 5 lbmol/hr
CIS-2-BUTENE 5 lbmol/hr
TRANS-2-BUTENE 5 lbmol/hr
MTBE 0 lbmol/hr Start with: WS4-REACDIST-MBTE-START.BKP
METHANOL 0 lbmol/hr
FILENAME: WS4-REACDIST-MBTE.BKP
© 2002 AspenTech. All Rights Reserved.

Workshop 4: MTBE Reactive Distillation (2)

• The file WS2-MTBE-START.BKP contains the

components, properties, and inlet stream information
needed for the simulation.
• For better convergence, use Strongly non-ideal liquid
convergence option and input temperature estimates
(130 F).
• For more accurate Keq and enthalpy calculation, input
heat of formation (DHFORM) and free energy of
formation (DGFORM) data for MTBE as the following:
DHFORM: -67686 cal/mol
DGFORM: -28035 cal/mol

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