Examples and Exercises

Process simulation
 Ammonia production: Haber Bosh
process
S6

S7
SPLITTER

S4

S2
S3
S5
FEED S1 MIXER

REACTOR FLASH

R1
F1

Process and product design

 Example: Ammonia production
Haber Process: N2 + 3 H2 2 NH3
Reaction conditions: T= 930 F, P= 7350 psi
Feed composition: 74% H2, 24.5% N2, 1.2% CH4,
0.3% Ar; T= 300F; P = 500 psi
Feed flow rate: 100 lb-mole/hr
Conversion per pass: 65% of N2
Thermodynamic model: Equation of state (Peng
Robinson)
Reaction products are refrigerated to separate 75%
mole of NH3 product per pass (no pressure drop).
The product is pure NH3 at -20 F (i.e. all other
compositions in bottom product is zero).
The remaining product is recycled back after purge
(10%) i.e. no gases in the product stream.
Process and product design
 Example: Ammonia production
Goal 1: adjust the purge flow rate so that the stream to
the reactor contains 0.11 CH4(mole fraction)
Goal 2: calculate all streams for two values of initial molar
flow rate of methane (2 and 3 lbmole/hr). Prepare a graph
with % CH4 in carica spurgo con vincolo 1
Goal 3: maximize the value of the product:
Equal to the difference between the flow rate of NH3 in S-5 and S-7.
Subject to constraint: total flow rate to the reactor less than 240
lbmol/hr

S-3

S-2 S-6
MX RXTR SEPA SPL
S-1 S-7

S-5
S-4

Process and product design

 Example: Ammonia production
Run base case with the stream manipulator
Run the base case with the flash
Flash is substituted to SM (T= -20F; P=500 psi)
Perform sensitivity analysis on the methane concentration vs recycle
ratio (purge from .92 to .98)
Set a design specification to keep methane mole frac. = 0.11 at the
inlet of the reaction (take a suggestion from sensitivity)
Save a final flowsheet with the desired value of purge and without
any design spec or sensitivity
Optimize the problem with the following Objective function
FOB = Flow rate of NH3 in product Flow rate NH3 in purge
Constraint: the total flow rate to the reactor be less than 240 lb mol/hr
Suggestions:
Reinitialize the simulation, particularly after sensitivity analysis
If needed modify tolerances for convergence
If convergence is slow, increase the number of iterations for Wegstein
method
Force the tear stream to be S-3
Process and product design
 Ammonia: the real process
S2
STAGE1
FEED-MIX
S1 S5
INTCOOL
S3 REACTMIX
STAGE2

S6
S14 S11
BLEED RECOMPR
SPLIT PREHTR

S7

S12

S10

CONDNSER QUENCH

REACT
S9 S9A S8
HPFLASH

LPFLASH

S13

PRODUCT

Process and product design

 Optimizing steam
consumption for solvent recovery
Typical example of organic aqueous stream
separation
The final goal is to comply the emission
specification ( in this case 150 ppm) by reducing
the amount of steam injections to a minimum
reducing the operation cost
addressing the environmental restrictions.
Goal
recovery of methylene chloride from waste
Use of a liq-liq decanter for separating organic rich phase
Lower organic content to less than 150 ppm in water
stream

Process and product design

 The process
Simulation details
calculation of the steam consumption
identification of the optimum conditions (sensitivity
analysis)
Process Input
Feed stream containing an aqueous stream of Methylene
chloride (S1): total flow rate of 100,000 lb/hr, Temperature
at 100 0F, pressure of 24.7 psia and components in the feed
stream are 0.0140 of CH2Cl2 and 0.986 of H2O in mass
fraction
Steam Streams injected to the two towers ( S2 & S4)
Steam saturate vapor at 200 psi flow rate of 10.000 lb/hr is
fed to the primary tower of.
Steam (S2) at a flow rate of 5000 lb/hr at the secondary
tower.
The top product of both towers (primary & secondary) or
vapor overheads are collected in the mixer and condensed
at a Temperature of 75 0F and pressure of 14.7 psi.
The remaining stream of the process is carried off to a
decanter to separate the condensate into a methylene
Process and product design chloride-rich stream and a water-rich stream.
 Methylene chloride recovery
VENT

DECANT
MIXER COND

CONDIN CONDOUT MECL

TOP2
WATER

TOWER2
TOP1
STEAM2

BOT2
BOT1

TOWER1

STEAM1

FEED

Process and product design

 Process Simulation goal
Recovery of methylene chloride in waste water;
Sensitivity analysis 1 to obtain methylene chloride
concentration of 150 ppm in the bottom of the
secondary tower (Stream 7 in Figure 2) by
regulating the flowrate of the steam inlet to the
primary tower;
Simulate sensitivity analysis 2 to obtain a
methylene chloride concentration of 150 ppm in
the bottom of the second tower in (Stream 7) by
regulating the flow rate of the steam inlet to the
secondary tower;
Optimize the total stream injections in the process.

Process and product design

 Input specifications

STREAM ID S1 S2 S4
NAME
PHASE LIQUID VAPOR VAPOR
FLUID WEIGHT
FRACTIONS
1 CH2CL2 0.014 0 0
2 H2O 0.986 1 1

TOTAL RATE, LB/HR 100000.1767 10000.00 5000.002

TEMPERATURE, F 99.9999 381.8395 381.8395
PRESSURE, PSIA 24.7 200 200
ENTHALPY, MM BTU/HR 6.7263 15.1648 2.5956
MOLECULAR WEIGHT 18.2159 18.015 18.015
WEIGHT FRAC VAPOR 0 1 1
WEIGHT FRAC LIQUID 1 1 1

Process and product design

 Thermodynamic validation
Pure component properties
0 0
Components Tc F Pc PSIA TNB F

A+ PRO II Lit. A+ PRO II Lit. A+ PRO II Lit.

CH2Cl2 458.33 458.6 445.58 881.8295 881.757 881.83 103.55 103.64 103.59
H2O 705.64 705.56 705.65 3198.81 3208.12 3208.13 212 212 212

Components
0 0
Tc F Pc PSIA TNB F

CH2Cl2
ASPEN -12.75 0 0.04
PRO II -13.02 0.073 0.05
H2O
ASPEN 0.01 9.32 0
PRO II 0.09 0.01 0

Process and product design

 Thermodynamic validation
Binary LLE

Literature Aspen+ PRO II

Solubility of 1 in 2 0.420 0.419 0.443
(mole %)
Solubility of 2 in 1 0.760 0.812 0.991
(mole %)

Process and product design

 Sensitivity analysis 1
Independent Variable: Steam flow rate injected to
the primary tower
Dependent Variable : Methylene Chloride
concentration in Bottom 2
Fixed Parameters: Steam flow rate injected to the
secondary tower fixed at 5000 lb/hr and Feed
conditions

Process and product design

 Sensitivity analysis 1

Process and product design

 Sensitivity analysis 2
Independent Variable: Steam feed rate inlet to the
secondary tower

Dependent Variable: Methylene chloride

concentration in Bottom 2
Fixed Parameters: Steam feed rate inlet to the
primary tower fixed at 10,000 lb/hr, feed conditions

Process and product design

 Sensitivity analysis 2

Process and product design

 Design specification
Controller
set design specification on the concentration of methylene
chloride in stream 7 is equal to 150 ppm
the variable is the flow rate (lb/hr) of steam injected to the
primary and secondary tower (S2 & S4).
Optimizer
The sensitivity studies show that several solutions exist to
give a methylene chloride concentration of 150 ppm at the
bottom of the secondary tower.
The optimizer is introduced to determine among them the
solution with the minimum consumption of energy.
The optimization procedure followed is to couple the
controller with an optimizer to minimize the total steam
consumption and the variable is the steam flow rate
injected to the first and second tower.

Process and product design

 Optimization results
Results
savings in steam usage realized without any major process
or equipment changes
Steam saving of 30000 $ per year (assuming $ 2.5/ 1000 lb
steam)
STEAM lb/hr
Tower I Tower II TOTAL
Sensitivity I 10,650 5,000 15,650 lb/hr
Sensitivity II 10,000 6,200 16,200 lb/hr
Optimizer 12,659.71 2163.97 14,823.7 lb/hr

Process and product design

 Cyclohexane production
Reaction section
Benzene + 3 Hydrogen = Cyclo hexane
Separation section
Recovery of cyclohexane
S8
S1 S11
FEEDPUMP
TANK2

S23
COMPRESS S10

SPLIT1

MULT2 S5 S12
S18
S4
S9
S3
M ULT
REACTOR
MIXER
S7 COLUMN
FLASH

PREHTR
S2 S17
M ULT
S21
TANK
MULT1 PUMP S19
S13
S20
TANK1
SPLITREC

S16
S15
S14

RECPUMP

Process and product design

 Cyclo hexane production process
The production process

The objectives of the case study are the following:

Verification of the thermodynamic data and models
Simulate the base case of the reaction section
Simulate the base case of the entire process with a simple
model for the distillation column
Simulate the base case of the separation section such that
the bottom liquid product from the distillation column is
equal to 135 kgmol/hr
Modify the process condition to obtain high recovery of
cyclohexane (99.5 %) at the bottom product stream (S5)
Maintain a flow rate of 5.3 kmol/hr in the distillate stream
(S4)
Simulate the complete process with a distillation column

Process and product design

 Thermodynamic and data bank
0 0
Components Tc F Pc PSIA TNB F

A+ PRO II Lit. A+ PRO II Lit. A+ PRO II Lit.

CYCLOHEX 537.17 536.5 536.88 591.75 590.78 591.02 177.29 177.33 177.30

BENZENE 552.02 553.0 552.22 709.96 714.22 710.39 176.16 176.8 176.62

METHANE -116.7 -116.7 -116.7 667.03 667.19 666.88 -258.68 -258.68 -258.74

0 0
Components Tc F Pc PSIA T NB F

PRO II ASPEN PRO II ASPEN PRO II ASPEN

CYCLOHEX 0.34 0.29 0.247 0.73 0.034 0

BENZENE 0.21 0.2 0.383 0.435 0.18 0.46

METHANE 0.02 0 0.145 0.145 -0.06 .06

Process and product design

 Vapor pressure of cyclohexane
VAPOR PRESSURE CYCLOHEXANE

Literature PRO II

100
VAPOR PRESSURE,mmHg

95

90

85

80

75

70
0.00332 0.00333 0.00334 0.00335 0.00336 0.00337 0.00338
TEM PERATURE,1/K

Process and product design

 Binary VLE cyclo hexane - benzene
Thermodynamic model: RKS (or GE )

Process and product design

 Reaction section
Reaction is a catalytic hydrogenation with total
conversion = 0.998
Feed 1 Gas: T= 48C - P= 22 atm Rate 523
kgmol/hr
H2= 465 N2= 15 CH4= 43
Feed 2 Benzene: T=40C - P= 20.4 atm Rate
144.4
S1
S3 S4 S5
S2
M1 E1
R1

Stream Name S5

Results
Stream Description
Phase Vapor
Temperature C 200.0000
Pressure ATM 15.0000
Enthalpy M*KJ/HR 9.3944
Molecular Weight 56.6959
Mole Fraction Vapor 1.0000
Mole Fraction Liquid 0.0000
Rate KG-MOL/HR 235.066

Fluid Rates KG-MOL/HR

BENZENE 0.2888
CH 144.1112
H2 32.6664
N2 15.0000
METHANE 43.0000

Process and product design

 Cyclohexane production
S8

C1

S7
S9
SP1

S15
S6

S14

S1
S3 S4 S5
S2 SC1
M1 S11 P2
E1 F1
R1
S16

S13

S10
S12

SP2
P1

Stream Name S14 S15 S16 S5 S6 S10 S12 S8

Stream Description

Phase Liquid Liquid Vapor Vapor Vapor Liquid Liquid Vapor

Temperature F 120.646 -200.000 386.000 400.000 120.000 120.000 120.000 120.000

Pressure PSIA 200.000 200.000 200.000 15.000 20.000 20.000 20.000 20.000

Flowrate LB-MOL/HR 236.221 235.002 1.218 1289.377 951.918 337.458 101.237 875.765

Composition
BENZENE 0.001 0.000 0.141 0.000 0.000 0.001 0.001 0.000
METHANE 0.001 0.001 0.038 0.163 0.221 0.001 0.001 0.221
N2 0.000 0.000 0.000 0.045 0.061 0.000 0.000 0.061
H2 0.000 0.000 0.000 0.335 0.454 0.000 0.000 0.454
CH 0.998 0.999 0.821 0.457 0.265 0.998 0.998 0.265

Process and product design

 Separation section
The initial feed flow rate is 232 kg-mol/hr at a
temperature of 200 C and pressure of 15 atm
Inlet to a flash separator, operated at a Pressure of
15 atm and Temperature of 50 C.
The vapor out of the flash is an output of the
process,
The liquid product is fed in the middle tray of a
distillation column with a reboiler and partial
condenser.
The internal design specification of the process is
the reflux ratio is equal to 1.2.
Thermodynamic: RKS or GE

Process and product design

 Separation section

S4
1

CN1 2

5
N stages= 15
6
(feed at 8)
S3
7
P= 13.33 atm
T= 200 C T= 50 C
8
Ref R= 1.2
P= 15 atm
9

P= 15 atm 10
Vapor dist (1: vap; 15:
S1 F1 11 liq)
H2 = 30.0 kmol/hr S2 12

N2 = 15.0 13

CH4 = 43.0 14

CYC6 = 144.2 T1 15

Bz = 0.2 S5
Rate initial = 135
Process and product design
kmol/hr
 Base case: results
Stream Name S1 S3 S2 S4 S5

Stream Description

Phase Vapor Vapor Liquid Vapor Liquid

Temperature, C 200 50 50 169.2375183 199.5368652

Pressure,ATM 15 15 15 13.32999992 13.32999992

Flowrate,kg-mol/hr 232.3999939 86.66875458 145.7312469 10.73137283 134.9998779

FLUID RATES, Kg-

mol/hr

HYDROGEN 30 0.3855 29.6145 0.3855 1.27E-11

NITROGEN 15 0.3108 14.6892 0.3108 2.37E-11

METHANE 43 3.0901 39.9099 3.0901 2.53E-08

CYCLOHEX 144.2 141.7496 2.4504 6.9231 134.8266

COMPOSITION

HYDROGEN 0.129087776 0.341697156 0.002645517 0.035925929 9.40E-14

NITROGEN 0.064543888 0.169486165 0.002133012 0.028966138 1.76E-13

METHANE 0.185025826 0.460488141 0.021203889 0.287947208 1.87E-10

CYCLOHEX 0.620481908 0.028272673 0.972678483 0.645144701 0.998714685

BENZENE 0.000860585 5.59E-05 0.001339122 0.002016034 0.001285313

Process and product design

 Base Case results
Only 90 % of cyclohexane is recovered.
Concentrations of cyclohexane and benzene
emitted in the vapor stream of the flash (S3) are
within the TLV standard of NIOSH.
The third goal to maintain a minimum flow rate of
5.3 k-mol/hr in Stream 4 is not reached.

Process and product design

 Internal design specification
To obtain a high recovery of cyclohexane at the
bottom product stream (S5) an additional design
specification is established
Adjustment of the flow rate of cyclohexane at the bottom
product stream (S5) with reference to the bottom of the
flash (S2) be 0.995
The variable is the duty of heater in the condenser.
The other design specification is the reflux ratio be equal
to 1:2
The variable is the duty of the heater in the reboiler.
The total flowrate in Stream 5 is equal to 141.04
kg-mol/hr which indicates that 99.5 % of
cyclohexane is recovered.
The second goal to attain high recovery of
cyclohexane is reached.

Process and product design

 Internal design specification
STREAM ID S1 S2 S3 S4 S5
NAME
PHASE VAPOR LIQUID VAPOR VAPOR LIQUID

FLUID RATES, KG-MOL/HR

1 HYDROGEN 30 0.3855 29.6145 0.3855 3.35E-11

2 NITROGEN 15 0.3108 14.6892 0.3108 6.40E-11

3 METHANE 43 3.0901 39.9099 3.0901 7.24E-08

4 CYCLOHEX 144.2 141.7496 2.4504 0.7088 141.0409

5 BENZENE 0.2 0.1952 4.85E-03 4.20E-03 0.1909

TOTAL RATE, KG-MOL/HR 232.4 145.7312 86.6688 4.4994 141.2318

TEMPERATURE, C 200 50 50 102.2286 199.5356

PRESSURE, ATM 15 15 15 13.33 13.33
ENTHALPY, M*KCAL/HR 2.2402 0.2559 0.0917 0.0131 1.2584
MOLECULAR WEIGHT 57.3255 82.3734 15.2082 26.4565 84.1548
MOLE FRAC VAPOR 1 0 1 1 0
MOLE FRAC LIQUID 0 1 0 0 1

Process and product design

 Sensitivity Analysis 1
The independent variable for this parametric study
is the variation of the temperature in the flash.

Independent Variable: Flash T 10.C to 50 C

Fixed Parameters: Feed Conditions & Column
Conditions

Dependent Variable: Flow rate of all components

in the Vapor Stream (S4) In kg-mol/hr

Process and product design

 Sensitivity analysis 1

Process and product design

 Sensitivity Analysis 2
The independent variable for this parametric study
is the variation of the pressure in the flash.

Independent Variable: Flash P 10 to 35 atm

Fixed Parameters: Feed Conditions & Column
Conditions

Dependent Variable: Flow rate of all components

in the Vapor Stream (S4) In kg-mol/hr

Process and product design

 Sensitivity analysis 2
SENSITIVTY FLASH PRESSURE
Kg-mol/H
10
FLOWRATE, Kg-mol/H

2
10 15 20 25 30 35

PRESSURE, ATM

Process and product design

 External design specification
Sensitivity analysis gave indications and feasibility
of process modification (T is the best variable)
The target of of 5.3 kg-mol/hr in the distillate or
Stream 4 of the process is reachable
An external design specification is established to
this aim.
The flow rate of 5.3 kg-mol/hr in the distillate is
reached with out affecting the product quality
( purity of cyclohexane recovered at the bottom
product stream).

Process and product design

 Design specification
Stream Name S1 S3 S2 S4 S5

Stream Description

Phase Vapor Vapor Liquid Vapor Liquid

Temperature, C 200 2.957733154 2.957733154 25.61639404 199.5356445

Pressure, ATM 15 15 15 0.99999994 13.32999992

Flowrate,kg-mol/hr 232.3999939 83.74118805 148.6588135 5.300059795 143.3587494

Composition

HYDROGEN 0.129087776 0.354866177 0.001904261 0.053411685 6.42E-14

NITROGEN 0.064543888 0.175634116 0.001965511 0.055129658 1.56E-13

METHANE 0.185025826 0.465723932 0.02690541 0.754656792 2.39E-10

CYCLOHEX 0.620481908 0.003767717 0.967884004 0.135731429 0.99864918

BENZENE 0.000860585 8.07E-06 0.001340818 0.001070414 0.001350815

Process and product design

 The complete process
Stream manipulator distillation column

S8

C1

S7
S9
SP1
S15

S6
1

S1
S3 S4 S5 2

S2
3
M1 S11 P2
E1 F1
R1 4
S14
5
S13

S10 6
S12
7

9
SP2
P1 10

11

12

Stream Name S14 S15 S16 S5 S6 S10 S12 S8 13

Stream Description
14
Phase Liquid Vapor Liquid Vapor Vapor Liquid Liquid Vapor

Temperature F 120.646 380.376 392.346 400.000 120.000 120.000 120.000 120.000 T1 15

Pressure PSIA 200.000 195.456 195.456 15.000 20.000 20.000 20.000 20.000 S16
Flowrate LB-MOL/HR 236.220 4.000 232.220 1289.011 951.554 337.457 101.237 875.430

Composition
BENZENE 0.001 0.002 0.001 0.000 0.000 0.001 0.001 0.000
METHANE 0.001 0.058 0.000 0.163 0.220 0.001 0.001 0.220
N2 0.000 0.005 0.000 0.044 0.060 0.000 0.000 0.060
H2 0.000 0.016 0.000 0.336 0.455 0.000 0.000 0.455
CH 0.998 0.919 0.999 0.457 0.265 0.998 0.998 0.265

Process and product design

Cyclohexane production process
 Cyclohexane production
S8

C1

S7
S9
SP1

S15
S6

S14

S1
S3 S4 S5
S2 SC1
M1 S11 P2
E1 F1
R1
S16

S13

S10
S12

SP2
P1

Stream Name S14 S15 S16 S5 S6 S10 S12 S8

Stream Description

Phase Liquid Liquid Vapor Vapor Vapor Liquid Liquid Vapor

Temperature F 120.646 -200.000 386.000 400.000 120.000 120.000 120.000 120.000

Pressure PSIA 200.000 200.000 200.000 15.000 20.000 20.000 20.000 20.000

Flowrate LB-MOL/HR 236.221 235.002 1.218 1289.377 951.918 337.458 101.237 875.765

Composition
BENZENE 0.001 0.000 0.141 0.000 0.000 0.001 0.001 0.000
METHANE 0.001 0.001 0.038 0.163 0.221 0.001 0.001 0.221
N2 0.000 0.000 0.000 0.045 0.061 0.000 0.000 0.061
H2 0.000 0.000 0.000 0.335 0.454 0.000 0.000 0.454
CH 0.998 0.999 0.821 0.457 0.265 0.998 0.998 0.265

Process and product design

 Process data
Components: Hydrogen, Nitrogen, methane,
Cyclohexane, benzene
Thermodynamics: Equation of State (Peng Robinson)
Reaction: Hydrogenation of benzene to cyclohexane
with conversion 0.998 at T= 400F
C6 H 6 3H 2 C6 H12

Process and product design

 Reaction section
Reaction hydrogenation with total conversion = 0.998; T=
400F
Feed 1 Gas: T=120C - P= 335 psi Rate 823.43 lbmol/hr
H2= 802.73 N2= 4.15 CH4= 16.55 lbmol/hr
Feed 2 Benzene: T=104.1F - P= 300 psi Rate 256
lbmol/hr pure benzene
Mixer: no specifications
Heater: process stream exit temperature = 300 F

Process and product design

 Separation and recycle
Flash: temperature 120F, pressure drop 5 psi
Vapor recycle:
Splitter: purge ratio (purged stream/feed to the splitter) =
0.08
Compressor: outlet pressure 382 psi
Liquid recycle:
Splitter: recycle ratio (recycle stream/feed to the splitter) =
0.30
pump: pressure rise 5 psi
Separation section
Pump: outlet pressure 200 psi
Separator (stream calculator): Overhead temperature =
120F - Bottom temperature = 120 F
Specifications recovery in overhead: H2=1, N2=1, CH4=0.8
Specifications recovery in bottom: Benzene=1, CyC6=1
Process and product design
 Excercise
Setup the Units, Description of the flowsheet,
autosave off
Flowsheet
Name streams and units
Components
Thermodynamic specification
SRK and UNIFAC
Data retrieval
Vapor pressure Enthalpy of vaporization
Verification of VLE for benzene cyclo hexane
Reaction specification
Base case calculation
Include a stream property table
Verify:
Total flow rate in overhead product S15 = 5.1 lb mol /hr
Composition of Bottom product S16 of CyC6 = 0.996
Recovery of cyclo hexane in the separation section =
Process and product design