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WS-4-03 Prediction of the carbon deposition in steam reforming unit (Equilibrium reaction calculation in Gibbs Reactor)
Problem Steam reformer is often used in refineries or chemical plants. Design and operation of steam reformer need to avoid deposition of solid carbon that can plug the reactor. Some authors reported that reactions in steam reformer are well described by equilibrium assumption. We predict the deposition of carbon using Gibbs reactor under the following condition. The following reactions are involved. CH4+H2O=3H2+CO 2H2O=2H2+O2 2CO+O2=2CO2 2CO=2C(solid)+O2 So, the following components are involved.

CH4,H2O,CO2,H2,CO,O2,C(solid) Feed Composition

CH4 : 1 kg-molh H2O : 1 kg-molh Temperature: 600 degC Pressure: 2 kg/cm2 Q-1 Do we expect carbon deposit in the reactor under the above conditions?

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1. Preparation 1UOM: Metric

2Components Select the following components.

CH4 H2O CO2 H2 CO O2 C

Select SIMSCI as the databank.

3) Thermo set Select SRK.

2. Flow sheet setting 1) Addition of unit operation Add a Gibbs reactor. Invensys Systems Japan, Inc. Thermo Workbook 109

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S1

S2

R1

2) Setting the feed stream

3) Setting the Gibbs Reactor At first select SET1 and click OK.

After that open the Gibbs reactor again and select None.

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3.Run the simulation Add stream property list (Material balance list). Carbon appears in the outlet stream.

S1

S2

R1 Stream Name Stream Description Phase Temperature Pressure Flowrate Composition CH4 H2O CO2 H2 CO O2 C C KG/CM2 KG-MOL/HR S1 Vapor 600.000 2.000 2.000 0.500 0.500 0.000 0.000 0.000 0.000 0.000 S2 Mixed 600.000 2.000 2.749 0.228 0.182 0.062 0.454 0.058 0.000 0.016

4.Results Q-1:Carbon deposition is expected. Needs some measure to avoid the deposition. -Increase in H2O/CH4 ratio -Increase in Temperature

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WS-5-01 Production of Methyl Acetate

Problem Reaction kinetics for synthesis of methyl acetate from methanol and acetic acid is described as follows. (Song et al.)
CH 3 COOH + CH 3 OH CH 3 COOCH 3 + H 2 O
HOAC MeOH MeOAc

C C r = k f C HOAC C MeOH MeOAc H 2O K eq 12493 .6 k f = 9.732 10 8 exp RT

1555.78 K eq = 2.32 exp RT The above equitation is supposed to be derived from the following equations for forward and back reactions.
r f = k f C HOAC C MeOH

rb = k b C MeOAc C H 2O kb = kf K eq 14049.4 = 4.195 10 8 exp RT

Equilibrium constant Keq becomes as follows;

ln K eq = 0.84156 +

( )

where C:[kg-mol/m3],R: 1.987[kcal/kg-mol K],r:[kg-mol/m3 h] Q-1. Calculate the conversion of methanol at a Plug Flow Reactor under the following conditions. FEED Temp.:77deg C, Press.:1kg/cm2acetic acid: 280kg-mol/h, methanol:280kg-mol/h Reactor ID: 1000mm, length:20m, Temp.:77deg C Reaction Operation Phase;Liquid Reaction Kinetics Power low Procedure Q-2. Calculate the conversion of methanol at a Equilibrium Reactor under the same condition (Reaction Operation Phase;Liquid) Q-3. Calculate the conversion of methanol at a Gibbs Reactor under the same condition (Reaction Operation Phase;Liquid)
[reference] Song,W.,G. Venimadhavan,J.M.Manning,M.F.Malone, and M.F.Doherty Measurement of Residue Curve Map and Heterogeneous Kinetics in Methyl Acetate Synthesis, Ind.Eng.Chem.Research,37,1917-1928(1998)

782.98 T

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2. Preparation 1UOM: Metric

2Components Select the following components in exactly the same order. HOAC MEOH MEAC H2O Select SIMSCI as the databank.

Set component phases as vapor-liquid for all the components.

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3) Property estimation method Select NRTL (single phase). Push Modify. Vapor fugacity: Hyden- OConnel Vapor enthalpy: SRK-Modified- Panag. Check calculate transport property.

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4Reaction Stoichiometric Data input Make reaction sets SET1 and SET2. SET1 includes reactions R1(forward reaction) and R2(back reaction). Stoichiometric data for R1 is set as HOAC+MEOH ->MEAC+H2O.

Stoichiometric data for R2 is set as MEAC+H2O ->HOAC+MEOH. So that the GUI appearance finally becomes as follows.

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5)Input power law constants for reaction kinetics The following equation is set for R1 and R2. 12493.6 R1: k f = 9.732 10 8 exp RT kf 14049.4 R2: k b = = 4.195 10 8 exp K eq RT

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6)Reaction equilibrium data For reaction set SET, only R1HOAC+MEOH The following equation is set for R1.
ln K eq = 0.84156 +

->MEAC+H2O is set.

( )

782.98 T

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7)Input Procedure for the reaction kinetics Procedure set PSET1 is declared. The code is input as follows; (copy and paste from attached MethylAcetate.txt)

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2.Process flow diagram Make a flow diagram that consists of two PFRs, an Equilibrium Reactor and a Gibbs Reactor. Appropriately name each stream.
FEED3 CONR-OUT FEED PFR1-POWER PFR1-OUT

FEED2 PFR2-PROCE

PFR2-OUT

CON-RX

FEED4

GIBBS-OUT

GIBBS-RX

Set the contents of PFR-1 This reactor uses power-law as the kinetics.
FEED P FR1-OUT

Temp.:77Cdeg Press.:1Kg/cm2 HOAC:280kg -mol/h M EOH:280kg -mol/h

P FR1-P OWER

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Set the contents of the PFR-2 This reactor uses Procedure for the kinetics.

FEED2

PFR2 -OUT

Define to FEED

PFR2 -POWER

3) Set the contents of the Equilibrium Reactor

FEED3

CONR-OUT

CON-RX

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4)Set the contents of Gibbs Reactor

FEED4 GIBBS-OUT

GIBBS-RX

3.RUN the simulation

PFR1-OUT FEED PFR1-POWER Stream Name Stream Description Phase Fluid Rates HOAC MEOH MEAC H2O CONR-OUT Rate Temperature Pressure Enthalpy Molecular Weight Mole Fraction Vapor Mole Fraction Liquid KG-MOL/HR 50.2355 50.2355 229.7645 229.7645 KG-MOL/HR C KG/CM2 M*KCAL/HR 560.000 77.0000 1.0000 4.4535 46.0474 0.7386 0.2614 50.2355 50.2355 229.7645 229.7645 560.000 77.0000 1.0000 4.4535 46.0474 0.7386 0.2614 49.4770 49.4770 230.5230 230.5230 560.000 77.0000 1.0000 4.4648 46.0474 0.7409 0.2591 57.4798 57.4798 222.5202 222.5202 560.000 77.0000 1.0000 4.3444 46.0474 0.7163 0.2837 PFR1-OUT Mixed PFR2-OUT Mixed CONR-OUT Mixed GIBBS-OUT Mixed

FEED2

PFR2-OUT

PFR2-PROCE

FEED3

CON-RX

FEED4

GIBBS-OUT

GIBBS-RX

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4.Results Q-1. PFR Conversion of methanol at PFR with Power-law Recovery =( 1-49.4452/280)x100 =82.341 % Conversion of methanol at PFR with Procedure Recovery =( 1-49.4452/280)x100 =82.341 % Because the exactly the same equations are used, the result must be exactly the same. Q-2. Equilibrium Reactor Recovery =( 1-49.477/280)x100 =82.329 % Since the result of PFR is closed to that of Equilibrium Reactor, it is presumed that increase in the volume of PFR dose not significantly increase the recovery. Q-3.Gibbs Reactor Recovery =( 1-57.48/280)x100 =79.47 % Since the result of Gibbs Reactor is closed to that of Equilibrium Reactor, the literature value for equilibrium equation is in accord with thermodynamic requirements. 5.Discussion All the problems above regards the reactor is full with liquid. PFR. Users need to select one of vapor or liquid for PFR, Equilibrium Reactor and CSTR. Gibbs reactor can handle phase equilibria simultaneously with reaction equilibria. Conversion of methanol increases to 92.3%, if the Reactor Operation Phase is Calculated at the Gibbs Reactor in Q-3. This increase is caused by the vaporization of MeOAc. So the rate of back reaction decreases.

CH 3 COOH + CH 3 OH CH 3 COOCH 3 + H 2 O
HOAC MeOH MeOAc

Reactive distillation in the next session uses this principle.

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WS-5-02 Production of ethylene oxide

Problem

According to a literature, the reaction kinetics for oxidation of ethylene on catalyst is described as follows;
C2H4 + 1 O2 C2H 4O 2

r1 =
r2 = r3 =

K 1 A1 A2 C1C 2 (1 + A1C1 + A2 C 2 + A3 C 3 ) 2 K 2 A1 A2 C1C 2

(1 + A1C1 + A2 C 2 + A3 C 3 ) 2 K 3 A1 A2 C 2 C 3 (1 + A1C1 + A2 C 2 + A3 C 3 ) 2

C 2 H 4 + 3O 2 2CO 2 + 2H 2 O C2H 4O + 5 O 2 2CO 2 + 2H 2 O 2

4.59 x10 4 K 1 = 1.36 x1015 exp RT 5.27 x10 4 K 2 = 9.59 x1017 exp RT 4.43 x10 4 K 3 = 1.35 x1013 exp RT

4.91x10 3 A1 = 2.92 exp RT

2.65 x10 4 A2 = 3.00 10 11 exp RT 3.37 x10 3 A3 = 1.32 10 2 exp RT

Unit of each variable is;

kg - mol r kg - cat s kg - mol K kg - cat s m3 A kg - mol

kg - mol cal C R mol K 3 m

Q-1: Calculate the conversion of ethylene to ethylene oxide at a Plug Flow Reactor under the following conditions. Reactor Catalytic bulk density: 800kg-cat/m3-bed Reaction temperature: 250 degC(fixed) Pressure 10Kg/cm2 Feed flow rate:10kg-mol/h composition: ethylene 30mol%,O2 7mol%,N2 63mol% Temp.: degC, Press.:10Kg/cm2 ID: 1000mm, Length: 10m Q-2: Calculate the conversion of ethylene to ethylene oxide at a CSTR with the same temperature, pressure ,feed condition and the reaction volume. Q-3: Recent development of catalyst increased the conversion to 80% at the same condition with Q-1. This is mainly due to an increase in the rate of the first reaction (K1). Determine the pre-exponential factor for K1 for the new catalyst. Invensys Systems Japan, Inc. Thermo Workbook 123

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1.Preparation 1)UOM: Metric

2) Components Set the following components just in the same order. ETHYLENE O2 EO CO2 H2O N2

Set component phase as Vapor-Liquid.

3)Thermo system Select NRTL (single liquid). Modify it to calculate transport property.

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4)Reaction stoichiometry Set as follows.

5)Procedure data Declare PSET1. new procedure

Input Procedure Data Code as follows; (The code can be transferred from the file EO.txt in attached disk by copy & paste.)
A1=2.92*EXP(4.91E+3/(RGAS*RTABS)) A2=3.00E-11*EXP(2.65E+4/(RGAS*RTABS)) A3=1.32E+2*EXP(3.73E+3/(RGAS*RTABS)) AK1=1E+15*PREEXP(1)*EXP(-ACTIVE(1)*1000/(RGAS*RTABS)) AK2=1E+17*PREEXP(2)*EXP(-ACTIVE(2)*1000/(RGAS*RTABS)) AK3=1E+13*PREEXP(3)*EXP(-ACTIVE(3)*1000/(RGAS*RTABS)) C1=XVCONC(1) C2=XVCONC(2) C3=XVCONC(3) SS=(1.0+A1*C1+A2*C2+A3*C3)**2 R1=AK1*A1*A2*C1*C2/SS R2=AK2*A1*A2*C1*C2/SS R3=AK3*A2*A3*C2*C3/SS RRATES(1) = R1*3600.0*800. RRATES(2) = R2*3600.0*800. RRATES(3) = R3*3600.0*800. ISOLVE=1 RETURN

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7) Reaction rate constant The values of pre-exponential factors (PREEXP) in the code in procedure are retrieved from Kinetic Reaction Data of which data entry window is accessed by clicking K in the reaction definition window. Since the power part (1E+15,1e+17,1E+13) is multiplied in the procedure, only the figures (1.36,9.56 and 1.35) need to be set. Input

4.59x104 K1 = 1.36x1015 exp RT

5.27x104 K2 = 9.59x1017 exp RT

4.43x104 K3 = 1.35x1013 exp RT

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2.Flow sheet setting 1)Addition of unit operations

PLUG-IN R1 PLUG-OUT

CSTR-IN

CSTR-OUT

R2

2Setting Plug Flow Reactor

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3) Setting CSTR

4) Setting feed stream Feed for Plug Flow Reactor flow rate:10kg-mol/h composition: ethylene 30mol%,O2 7mol%,N2 63mol% Temp.: degC, Press.:10Kg/cm2 Feed for CSTR Reference to the feed stream for the Plug Flow Reactor

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3.RUN the simulation

PLUG-IN R1

PLUG-OUT

CSTR-IN

CSTR-OUT

R2 Stream Name Stream Description Phase Fluid Rates ETHYLENE O2 EO CO2 H2O N2 Rate KG-MOL/HR 3.0000 0.7000 0.0000 0.0000 0.0000 6.3000 KG-MOL/HR 10.000 2.6427 0.0624 0.1737 0.3672 0.3672 6.3000 9.913 250.0000 10.0000 0.0389 28.5525 1.0000 0.0000 3.0000 0.7000 0.0000 0.0000 0.0000 6.3000 10.000 100.0000 10.0000 0.0135 28.3045 1.0000 0.0000 2.7281 0.2111 0.1307 0.2824 0.2824 6.3000 9.935 250.0000 10.0000 0.0380 28.4907 1.0000 0.0000 PLUG-IN PLUG-OUT CSTR-IN CSTR-OUT Vapor Vapor Vapor Vapor

C 100.0000 Temperature KG/CM2 10.0000 Pressure M*KCAL/HR 0.0135 Enthalpy 28.3045 Molecular Weight 1.0000 Mole Fraction Vapor 0.0000 Mole Fraction Liquid

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4.Chage the flow sheet 1) Addition of calculator and optimizer

PLUG-IN R1 PLUG-OUT

CSTR-IN

CSTR-OUT

R2

CA1

OP1

2) Setting the content of calculator

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3) Setting the content of Optimizer

5.RUN the simulation Right click the optimizer and execute RUN RESULT.

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6.RESULT Q-1 Conversion at Plug Flow Reactor Conv.=(0.1737/3.0)x100=5.79% Q-2 Conversion at CSTR Conv.=(0.1307/3.0)x100=4.36% Q-3 Kinetic parameter (pre-exponential factor) 24.35 kg-mol/(kg-catsec)

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WS-5-03 Heat balance of Reactor

Theme

Q-1 Check the heat of reaction at the PFR of WS-5-02 is correctly calculated. Q-2 Check the heat duty of the PFR of WS-5-02 is correctly calculated.

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1.Change of flow sheet Open the file made at WS-5-02. Save with different name using Save as from the file menu. Open the Print option of Plug Flow Reactor. Check to print out enthalpy balance.

2.RUN the simulation

PLUG-IN R1

PLUG-OUT

CSTR-IN

CSTR-OUT

R2 StreamNam e StreamDescription Phase Fluid Rates ETHY LE NE O2 EO CO2 H2O N2 Rate Tem perature Pressure Enthalpy Molecular W eight Mole FractionVapor Mole FractionLiquid KG-MOL/HR 3.0000 0.7000 0.0000 0.0000 0.0000 6.3000 KG-MOL/HR C KG/CM2 M*KCAL/HR 10.000 100.0000 10.0000 0.0135 28.3045 1.0000 0.0000 2.6427 0.0624 0.1737 0.3672 0.3672 6.3000 9.913 250.0000 10.0000 0.0389 28.5525 1.0000 0.0000 3.0000 0.7000 0.0000 0.0000 0.0000 6.3000 10.000 100.0000 10.0000 0.0135 28.3045 1.0000 0.0000 2.7281 0.2111 0.1307 0.2824 0.2824 6.3000 9.935 250.0000 10.0000 0.0380 28.4907 1.0000 0.0000 PLUG-IN Vapor PLUG-OUT Vapor CSTR-IN Vapor CSTR-OUT Vapor

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3.Retrieve data Generate output. From the output file retrieve the data of Heat of Formation (at the last of P-1)

From PLUGFLOW REACTOR SUMMARY (P5) retrieve the data on Duty and Heat of reaction.

From PLUGFLOW REACTOR SUMMARY (P5) retrieve the data on flow rate change for each component.

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From PLUG FLOW HEAT BALANCE retrieve enthalpy of reactant and product both at operating condition and reference condition.

H1

H4

H2 4.Check 1)Heat of formation

H3

Component ETHYLENE O2 EO CO2 H2O N2

A: HEAT FORM. B: Change kcal/kg-mol kg-mol/h 12541.8 -0.3573 0 -0.6376 -12570.46 0.1737 -93988.26 0.3672 -57756.29 0.3672 0 0 Total

AxB kcal/h -4481.18514 0 -2183.488902 -34512.48907 -21208.10969 0 -62385.2728

Agrees with 0.0624 M*Kcal/h in the output file 2) Duty Duty = (H2-H1)+ DH + (H4-H3) = -0.0426 M*Kcal/h Agrees with -0.0426 M*Kcal/h in the output file 5.Results Q-1 Heat of reaction at the PFR of WS-3-02 is correctly calculated. Q-2 Heat duty of the PFR of WS-3-02 is correctly calculated.

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Thermo Workbook 136