Advanced Distillation with Aspen Plus

Reactive Distillation

Reactive Distillation
Advanced Distillation with Aspen Plus

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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.

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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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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.

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Kinetic Reactions (2)

Aspen Plus allows flexible concentration terms when using the Power Law expression:

R = kT n e E / RT (Ci )i
Mole fraction Mass fraction Molarity Molality

Concentration (Ci) can be:

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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:

ln K eq = A +

B + C ln(T ) + DT T

with Temperature (T) in Kelvin

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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
Mole gamma Molal gamma Mole fraction

Expression

Description
(Liquid only)(Default) (Electrolytes, Liquid only)

.... .. i .... .. m i .... .. i .... .. m i

K = ( X i i ) K = (C i i ) K = ( xi ) K = ( X i)

Mass fraction Molarity

.... ..

K = ( C )i Molality (Electrolytes, Liquid only) K = (C m i )i .... .. i K = ( fi ) Fugacity

i .... ..
.... ..

Partial pressure
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K = ( Pi )i

(Vapor only)

Conversion Reactions (1)

Aspen Plus uses the following built-in conversion expression:

Conv = A +

B + C ln(T ) + DT T

with Temperature (T) in Kelvin

The key component for conversion reactions must be specified.

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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.

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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 conversion MEG + DEG -> TEG + H2O conversion 1% of MEG 1% of DEG

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

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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 reactions 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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Reactive Distillation

Example: Kinetic Reactions (5)

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

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Example: Kinetic Reactions (6)

Esterification Column
Distillate rate = 30 kmol/hr

DIST COL
Stage 1 Pressure 1 bar Stage 15 Pressure 1 bar

FEED
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 MX + TBB TBMX + BZ

(1)

(2)

K1 = K1 =

X TBMX X TBB ; ln K1 = 0.51 X MX X DTBB X TBMX X TBZ ; ln K 2 = 1.83 X MX X TBB

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Example: Equilibrium Reactions (2)

Enter a reactions associated equilibrium data on the Reactions Reactions Equilibrium sheet.

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Reactive Distillation

Example: Equilibrium Reactions (3)

Para/Meta Xylenes Separation Column
Saturated liquid P = 44 torr DTBB 0.6552 lb/hr TBB 0.1248 lb/hr SOLVENT 2 COL no reactions in condenser Distillate rate = 0.44 lb/hr DIST 15 stages Molar reflux ratio = 2

FEED Saturated liquid P = 54 torr MX 0.5734 lb/hr PX 0.6466 lb/hr

11 BOTTOMS

FILENAME: EX4B -EQUIL-PMXYLENE.BKP

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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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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.

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User Kinetic Subroutine Template (3)

C C C C SUBROUTINE USRKNT (N, 2 3 4 5 6 7 8 T, F, KDIAG, NCOMP, TLIQ, X, STOIC, NR, TVAP, Y, NRL, P, IDX, NRV, PHFRA C, NBOPS T, TIMLI Q, INT, RATEV , NIWOR K, User Kinetics Subroutine for RADFRAC, BATCHFRAC, RATEFRAC (REAC -DIST type Reactions)

IHLBAS, HLDLIQ, TIMVAP, NINT, RATES, RATEL,

IHVBAS, HLDVAP, NREAL, NINTB, IWORK, REAL, INTB, NWORK,

NREALB, REALB, WORK)

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Reactive Distillation

User Kinetic Subroutine Template (4)

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

NRV T TLIQ TVAP P PHFRAC

I I I I I I

I R R R R R

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User Kinetic Subroutine Template (5)

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

TIMLIQ IHVBAS HLDVAP

I I I

R I R

TIMVAP NINT INT

I I I/O

R I I

NINT

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Reactive Distillation

User Kinetic Subroutine Template (6)

C C C C C C C C C C C C C C C C C C C C C C C C C C C C C NREAL REAL RATES RATEL I I/O O O I R R R NREAL NCOMP NRLT LENGTH OF REAL VECTOR REAL VECTOR COMPONENT REACTION RATES (KMOL/SEC) INDIVIDUAL REACTIO N RATES IN THE LIQUID PHAS E (KMOL/SEC) WHAT IS NRLT? NRLT = NRL(1)+NRL( 2)+NRL(3 NRLT IS NOT INCLUD ED IN TH ARGUMENT LIST. * USED ONLY BY RAT EFRAC * INDIVIDUAL REACTIO N RATES IN THE VAPOR PHASE (KMOL/SEC) * USED ONLY BY RAT EFRAC * LENGTH OF INTEGER VECTOR (FROM UOS BLOCK) INTEGER VECTOR (FROM UOS BLOCK) LENGTH OF REAL VECTOR (FROM UOS BLOCK) REAL VECTOR (FROM UOS BLOCK) LENGTH OF INTEGER WORK VECTOR INTEGER WORK VECTO R LENGTH OF REAL WORK VECTOR REAL WORK VECTOR

RATEV

NRV

NINTB INTB NREALB REALB NIWORK IWORK NWORK WORK

I I/O I I/O I I/O I I/O

I I I R I I I R

NINTB NREALB NIWORK NWORK

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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)

R1 and R2 are in kg-moles/sec-m3

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2 P P R1 = 66500e 15200 / T * PBZ DP H 2 0.312 P P R2 = 38400e 15200 / T * PBZ PDP TP H 2 0.48

FILENAME: EX4C-USER-DP.BKP

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 ISOBUTYLENE + METHANOL <==> MTBE 95 psia Temperature = 70 F Pressure = 400 psia METHANOL C4RAFF 15 30 stages Catalyst on stages 15-19 Molar reflux ratio = 8 Top tray pressure = 100 psia Use the UNIFAC property method

540 lbmol/hr

MEOHFEED MBTECOL C4FEED Temperature = 110 F Pressure = 400 psia PROPANE ISOBUTANE ISOBUTYLENE N-BUTANE 1-BUTENE CIS-2-BUTENE TRANS-2-BUTENE MTBE METHANOL

20

7 lbmol/hr 670 lbmol/hr 530 lbmol/hr 20 lbmol/hr 5 lbmol/hr 5 lbmol/hr 5 lbmol/hr 0 lbmol/hr 0 lbmol/hr

MTBEPROD 115 psia

520 lbmol/hr

Vary bottoms rate from 500 to 550 lbmol/hr to achieve a mole fraction of 0.998 for MTBE in the bottoms.

Start with: WS4-REACDIST-MBTE-START.BKP FILENAME: WS4-REACDIST-MBTE.BKP

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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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