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Process Simulation
Using PRO/II with
PROVISION
Dr. Jungho Cho, Professor
Department of Chemical Engineering
Dong Yang University
Introduction
Ê PRO/II Electrolytes has the full capabilities of
SimSci's Conventional PRO/II.
Ê Electrolyte code from OLI Systems, Inc.,
y Electrolyte Thermodynamic Methods (Rigorous)
y Electrolyte Models (Fixed set of components)
y Chemical and Phase Equilibrium Algorithm
y Pure Component + Species Interaction Data Banks
Slide 2
Introduction
Ê SIMSCI’s ELDIST algorithm for modeling
distillation columns with electrolytes,
Ê ELECTROLYTE UTILITY PACKAGE
y User-added Electrolyte Model Generation Program
y Data Bank Management Program
Slide 3
Implementation
SimSci SimSci/OLI OLI Systems SimSci/OLI
PRO/II Interface Electrolytes Utility Package
Set Up
P Models
R
O
II Built-In
OLILIB
w Thermo Model
P Equations Data Bank
R (DBSFILE)
Perform
Models
O Flash
V ÊEquilibri Model
I um Generation
S Set Up ÊSolver
I ELDIST
O
OLI
N
Component
Data Banks
Slide 4
Unit Opeations
Ê Unit Operation Modules built in PRO/II
y Flash
y Calculator
y Pump
y Controller
y Valve, Mixer, Splitter
y Optimizer
y Pipe
y ELDIST Column
y HEX, LNG HEX
y Conversion Reactor
y Stream Calculator
y Equilibrium Reactor
y HCURVE
y Batch Reactor
Slide 5
Thermodynamic Models ( I )
Ê Pregenerated models for 40 systems:
y Amine systems
y Caustic systems
y Acid systems
y Benfield systems
y Mixed salt systems
y Scrubber systems
y Sour water systems
y LLE and Hydrate systems
Slide 6
Thermodynamic Models ( II )
Ê User added model can be generated using
Electrolyte Utility Package(EUP):
y Maximum of 60 built-in models allowed
y Maximum of 50 model components allowed, but 30
component maximum is recommended.
Slide 7
Application Range
Ê Aqueous Elelctrolyte
y Temperature: 0 ~ 200 C
y Pressure: 0 ~ 200 atm
y Dissolved Gases: 0 ~ 30 mole%
y Ionic Solutes: 0 ~ 30 ionic strength
Ê Amine System
y Pressure: 0 ~ 30 atm
Ê LLE System
y Organic Solutes: Max wt% = 10
Slide 8
PRO/II Electrolyte & Conventional PROII
Ê PRO/II Electrolyte Module takes the followings into
account:
y Chemical and Phase Equilibria
y Charge Balance
y Material Balance
Ê All Thermodynamic Method in Conventional
PRO/II tank into account only Phase Equilibria
except:
y SOUR
y GPSWATER
y AMINE
Slide 9
Component Reconstitution
Ê Phase and chemical equilibrium are solved for
unknown concentrations of the true species (ionic,
neutral) in the aqueous phase.
Ê A reconstitution procedure is used to calculate
apparent concentrations of the model’s neutral
components that are consistent with the true
species concentrations.
Slide 10
Component Reconstitution
Ê Example:
y Models components: H2O, NAOH, HCL, NACL
y Feed components: 50mol H2O + 1mol NAOH + 1mol
HCL
y Product as True Chemical Species:
51mol H2O+1mol NA+1+1mol CL-1+10-7 mol OH-1+10-7 mol H+1
Ê Product as Reconsitituted Components: 51mol
H2O + 1mol NACL
Ê Reconstitution is automatic.
Ê Output gives true and reconstituted values.
Slide 11
Slide 12
Simulation Steps: Predefined Modes
4. Component Databank: OLILIB and SIMSCI Bank
5. Build PFD with Unit Operations and Streams
6. Run
7. Generate Output
Slide 13
Slide 14
Problem #1: HCL & H2O Solution
Slide 15
x=y
Equilibrium curve
Vapor Composition, Mole Fraction HCL
0.8
0.6
0.4
0.2
0
0 0.2 0.4 0.6 0.8 1.0
Slide 16
Problem #2: Na2CO3 Solubility in Water
Ê Employ a Flash Solid model to determine the
solubility of Na2CO3 in water.
FWS1 TEMP = 25 C
PRES = 1.0332 KG/CM2
CA1
LIQUID
Stream Name FEED
Fluid Rates KG-MOL/HR
H2O 55.51
NA2CO3 5.00
Temperature 25.00 C
Pressure 1.0197 KG/CM2
SOLID
ELECTROLYTE SYSTEM = LLE AND HYDRATE
ELECTROLYTE MODEL = TWL1
Slide 17
5.0
Molality
4.0
3.0
Molality
2.0
1.0
0
0 20.0 40.0 60.0 80.0 100.0
TEMP, C
Slide 18
Problem #3: Sodium Chloride Solution
VAPOR
55.1 kg-mol/sec H 2O
6.5 kg-mol/sec NaCl
0.1 kg-mol/sec CO 2 Isothermal
Flash
25 C
FEED 1 bar
LIQUID
Solids
Separator
LIQUID &
SOLID
SOLID
Slide 19
Slide 20
Problem #4: Acid Gas Absorber
Sweet Gas
HCl Solution
1
650 kg/h
15 wt. % HCl
2
T=30 C
P=1.01 bar
Acid Gas 4
Slide 21
Slide 22
Electrolyte Distillation (ELDIST)
Ê Electrolyte distillation column equations for
component balance and energy balance are
solved by Newton-Raphson algorithm in the Outer
Loop while liquid phase speciation along the k-
value computation are handled by the Inner Loop.
Slide 23
Slide 24
Electrolyte Distillation (ELDIST)
Ê OUTER LOOP:
y Outer loop is solved by the Newton-Raphson algorithm.
Slide 25
Slide 26
Problem #5: Benfield Process
CO2_RECOVERY
ABS_OFF_GAS 1
SWEET_GAS
MAKEUP_CALC
1
OFFGAS_FLASH
2
REGEN_BOTTOM
LIQUID1 2
REGEN_FEED
3
MIXED_STREAM
HEATER
MIXER
ABSORBER FLASH_GAS
4
GAS_FEED LIQUID2 REGENERATOR 3
ABS_BOTTOMS 4
WATER_MAKEUP
RECYCLE1
BOTTOM_FLASH
M1
RECYCLE2
PUMP
K2CO3_SOL
Slide 27
Slide 28
Problem #5: Benfield Process
Ê You need to answer to followings:
y What are the flowrate and compositions of the sweet
gas, CO2 recovery, and K2CO3/KHCO3 solution
stream?
y What is the make-up water flowrate?
y What is the weight percentages of CO2 in the feed gas
and sweet gas stream?
Slide 29
Slide 30
Electrolyte Utility Package (EUP)
Ê Use the electrolyte utility package (EUP) to
generate model’s FORTRAN routines.
Ê Equations for Mass and Charge Balance
Ê Equations for Chemical and Phase Equilibria and
to generate model’s data block.
Ê Data on Pure Species and Species Interactions
Slide 31
Slide 32
Run PROVISION
y From “File” Select “New”
y From “View” Select “Thermodynamic Data”
y Select Electrolytes
y Select User Models
y Select desired model
Slide 33
Slide 34
Problem #6: Acid Gas Absorber using
EUP
Sweet Gas
Make-up
1
HCl Solution
650 kg/h
Mixer
2
15 wt. % HCl
T=30 C
P=1.01 bar
3 Recycle
Stream
Acid Gas 4
Slide 35
Slide 36
Equilibrium of HCL-H2O System
Ê Components:
y H2O, HCL
Ê Ionic Species:
y OH-1, H+1, CL-1
Ê Ionic Equilibria: H 2 O ( l ) ⇔ H + ( a q ) + O H − ( a q )
H C l(a q ) ⇔ H + (a q ) + C l− (a q )
Ê Phase Equilibria: H 2 O ( l ) ⇔ H 2 O ( v )
H C l(a q ) ⇔ H C l(v )
Slide 37
Thermodynamic: Equilibrium
Expression
Ê Thermodynamic Equilibrium Constant K:
∏ [(γ iP ) ni P ( miP ) ni P ]
K=
∏ [(γ ]
iP
iR ) ni R ( miR ) ni R
iR
Slide 38
Equilibrium of H2O-CO2-NACL
Ê Ionic Equilibrium:
H O (l ) ⇔ H + ( aq ) + OH − ( aq )
2
CO ( aq ) + H O (l ) ⇔ H + ( aq ) + HCO − ( aq )
2 2 3
HCO − ( aq ) ⇔ H + ( aq ) + CO 2 − ( aq )
3 3
NaCl ( s ) ⇔ Na + ( aq ) + Cl − ( aq )
Slide 39
Equilibrium of H2O-CO2-NACL
Ê Vapor-Liquid Equilibrium:
H O (vap ) ⇔ H O (l )
2 2
CO (vap ) ⇔ CO ( aq )
2 2
Slide 40
Equilibrium of H2O-CO2-NACL
Ê Ionic Equilibrium Constant Expression:
γ m γ m
K = H + H + OH − OH −
H O ( aq ) a
2 H O
2
γ m γ m
H + H + HCO − HCO −
K = 3 3
CO
2
( aq ) γ m a
COCO H O
2 ( aq ) 2 ( aq ) 2
γ m γ m
H + H + CO 2 − CO 2 −
K = 3 3
HCO − ( aq ) γ m
3 HCO − HCO −
3 3
γ m γ m
+ Na + Cl − Cl −
K = Na
NaCl ( s ) a
NaCl ( s )
Slide 41
Equilibrium of H2O-CO2-NACL
Ê Vapor-Liquid Equilibrium Constant Expression:
a
H O
K 2=
H O φ y P
2 H O H O
2 2
γ m
CO CO
2( aq ) 2( aq )
KCO =
2 φ y P
CO CO
2 2
Slide 42
Thermodynamic: Equilibrium
Expression
Ê Assuming a constant heat capacity of reaction, the
equilibrium constant are determined by the
following:
∆G 0 ∆H 0 1 1 ∆Cp 0 Tr Tr
ln K (T ) = − − − − ln T − T + 1
RTr R T Tr R
Slide 43
Thermodynamic Framework
Ê Ionic Strength is defined by the following equation:
1 nI 2
I = ∑ zi mi
2 i =1
( )
Slide 44
Thermodynamic Framework
Ê For example, a 1.0 molal solution of CaCl2 has 1.0
moles of Ca+2 ion and 2.0 moles of Cl-1 ion per Kg
of H2O.
I=
1
(
2 Ca
)
(Z +2 )2 (mCa +2 ) + (Z Cl −1 )2 (mCl −1 )
I=
1
2
(
(2 )2 (1.0 ) + (− 1)2 (2.0 ) = 3.0)
Slide 45
Thermodynamic Framework
Ê Aqueous Phase:
Ê The key to successful simulation of aqueous
systems I sto accurately predict:
y Activity coefficients of ions in solution
y Activity coefficients of molecules in solution
y Activity of water
Slide 46
Thermodynamic Framework
Ê Aqueous Phase:
Ê For activity coefficients of ions in solution the
formulation is made up of 3 terms:
y The Debye-Huckel term for long-range, ion-ion
interactions
y The Bromley-Zemaitis term for short-range, ion-ion
interactions
y The Pitzer term for short-range, ion-molecular
interactions
Thermodynamic Framework
Ê Aqueous Phase:
Ê For activity coefficients for molecules other than
water in solution, the Setschenow equation is
used.
Ê For activity of water in a multicomponent system
the Meissner and Kusik mixing rule equation is
used.
Slide 48
Thermodynamic Framework
Ê Vapor Phase:
Ê To calculate vapor liquid equilibrium, vapor phase
fugacity coefficient methods are used which are
strong functions of temperature, pressure and
composition, particularly at elevated pressures.
The methods are:
y Ideal, all fugacity coefficients are assumed to be 1.0
y Nothnagel method, valid up to 20 atmospheres
y Nothnagel method, valid up to 200 atmospheres
y SRK method, valid for wider range of conditions and for
vapor-phase nonideality
Slide 49
Thermodynamic Framework
Ê Vapor Phase:
Ê To calculate vapor liquid equilibrium, vapor phase
fugacity coefficient methods are used which are
strong functions of temperature, pressure and
composition, particularly at elevated pressures.
The methods are:
y Ideal, all fugacity coefficients are assumed to be 1.0
y Nothnagel method, valid up to 20 atmospheres
y Nothnagel method, valid up to 200 atmospheres
y SRK method, valid for wider range of conditions and for
vapor-phase nonideality
Slide 50
Thermodynamic Framework
Ê Non-Aqueous Phase:
Ê Normally strong functions of temperature and
composition and weaker function of pressure.
Slide 51
Thermodynamic Framework
Ê Bulk Phase Properties:
Ê Old vs. New Framework:
y Old: Equilibrium constant, K, is temperature dependent
(retirived from PUBLIC databank).
y New: Equilibrium constant is temperature and pressure
dependent (retrieved from PUBNEW databank) Tanger
and Helgeson equation used fro K calculation.
Slide 52
The End….
Slide 53
Slide 54