Dr. Jungho Cho, Professor Department of Chemical Engineering Dong Yang University
Introduction
PRO/II Electrolytes has the full capabilities of SimSci's Conventional PRO/II. Electrolyte code from OLI Systems, Inc.,
Electrolyte Thermodynamic Methods (Rigorous) Electrolyte Models (Fixed set of components) Chemical and Phase Equilibrium Algorithm Pure Component + Species Interaction Data Banks
Slide 2
Introduction
SIMSCIs ELDIST algorithm for modeling distillation columns with electrolytes, ELECTROLYTE UTILITY PACKAGE
User-added Electrolyte Model Generation Program Data Bank Management Program
Slide 3
Implementation
SimSci PRO/II SimSci/OLI Interface Set Up Models OLI Systems Electrolytes SimSci/OLI Utility Package
P R O II w P R O V I S I O N
OLILIB
Perform Flash
Set Up ELDIST
Equilibri um Solver
Model Generation
Unit Opeations
Unit Operation Modules built in PRO/II
Flash Calculator Pump Controller Valve, Mixer, Splitter Optimizer Pipe ELDIST Column HEX, LNG HEX Conversion Reactor Stream Calculator Equilibrium Reactor HCURVE Batch Reactor
Slide 5
Thermodynamic Models ( I )
Pregenerated models for 40 systems:
Amine systems Caustic systems Acid systems Benfield systems Mixed salt systems Scrubber systems Sour water systems LLE and Hydrate systems
Slide 6
Thermodynamic Models ( II )
User added model can be generated using Electrolyte Utility Package(EUP):
Maximum of 60 built-in models allowed Maximum of 50 model components allowed, but 30 component maximum is recommended.
Slide 7
Application Range
Aqueous Elelctrolyte
Temperature: Pressure: Dissolved Gases: Ionic Solutes: 0 ~ 200 C 0 ~ 200 atm 0 ~ 30 mole% 0 ~ 30 ionic strength 0 ~ 30 atm Max wt% = 10
Amine System
Pressure:
LLE System
Organic Solutes:
Slide 8
All Thermodynamic Method in Conventional PRO/II tank into account only Phase Equilibria except:
SOUR GPSWATER AMINE
Slide 9
Component Reconstitution
Phase and chemical equilibrium are solved for unknown concentrations of the true species (ionic, neutral) in the aqueous phase. A reconstitution procedure is used to calculate apparent concentrations of the models neutral components that are consistent with the true species concentrations.
Slide 10
Component Reconstitution
Example:
Models components: H2O, NAOH, HCL, NACL Feed components: 50mol H2O + 1mol NAOH + 1mol HCL Product as True Chemical Species:
51mol H2O+1mol NA+1+1mol CL-1+10-7 mol OH-1+10-7 mol H+1
Product as Reconsitituted Components: 51mol H2O + 1mol NACL Reconstitution is automatic. Output gives true and reconstituted values.
Slide 11
Slide 12
Slide 13
Slide 14
Stream Name Stream Description Phase Temperature Pressure Flowrate Composition H2O HCL
H2O Liquid 20.000 1.033 100.000 1.000 0.000 C KG/CM2 KG-MOL/HR AQUEOUS
DP=0.0, Duty=0.0
Slide 15
0.8
0.6
0.4
0.2
Slide 16
SOLID
ELECTROLYTE SYSTEM = LLE AND HYDRATE ELECTROLYTE MODEL = TWL1
Slide 17
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
FEED
Solids Separator
LIQUID
Slide 19
Part 2:
How does increasing the temperature of the flash change the pH and NaCl concentration of the outlet streams?
Slide 20
Acid Gas
190 kg/h SO2 T=75 C P=1.06 bar 105 kg/h HCl 50 kg/h N2
Bottoms
Slide 21
Part 2:
What flowrate of HCl wash solution in necessary to reduce the OVHD weight fraction of HCl to 0.1%? What is the weight fraction of HCl in the bottoms stream with the new wash solution flowrate?
Slide 22
Slide 23
Slide 25
Slide 26
MAKEUP_CALC
OFFGAS_FLASH
2 LIQUID1 2
REGEN_BOTTOM
REGEN_FEED MIXED_STREAM
FLASH_GAS
MIXER
HEATER
LIQUID2
REGENERATOR
3 4
PUMP K2CO3_SOL
Slide 27
Slide 28
Slide 29
Slide 30
Slide 31
Slide 32
Run PROVISION
From File Select New From View Select Thermodynamic Data Select Electrolytes Select User Models Select desired model
Slide 33
Slide 34
HCl Solution
2
650 kg/h 15 wt. % HCl T=30 C P=1.01 bar
Mixer
Recycle Stream
Acid Gas
190 kg/h SO2 105 kg/h HCl 50 kg/h N2 5 kg/h CH3CH 2Cl T=75 C P=1.06 bar
Product
Part 2:
How does the ethyl chloride distribute in the system? Is it absorbed by the HCl solution or does it remain in the gas stream?
Slide 36
Ionic Species:
OH-1, H+1, CL-1
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 )
Phase Equilibria: H 2 O ( l ) H 2 O ( v )
Slide 37
H C l(a q ) H C l(v )
[( K= [(
iP iR
iP
) ni P ( miP ) ni P ) ni R ( miR ) ni R
iR
] ]
Slide 38
Equilibrium of H2O-CO2-NACL
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
Vapor-Liquid Equilibrium:
H O (vap ) H O (l ) 2 2 CO (vap ) CO ( aq ) 2 2
Slide 40
Equilibrium of H2O-CO2-NACL
Ionic Equilibrium Constant Expression:
K H 2 O ( aq ) = H + m H + a H +
OH 2 O
OH
K CO 2 ( aq ) =
H + CO
HCO
m HCO
Slide 41
Equilibrium of H2O-CO2-NACL
Vapor-Liquid Equilibrium Constant Expression:
H O 2 H O y P 2 H O H O 2 2 m CO CO 2( aq ) 2( aq ) KCO = 2 y P CO CO 2 2 = a
Slide 42
Slide 43
Thermodynamic Framework
Ionic Strength is defined by the following equation:
1 nI 2 I = zi mi 2 i =1
Slide 44
Thermodynamic Framework
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 (Z Ca +2 )2 (mCa +2 ) + (Z Cl 1 )2 (mCl 1 ) 2
I=
Slide 45
Thermodynamic Framework
Aqueous Phase: The key to successful simulation of aqueous systems I sto accurately predict:
Activity coefficients of ions in solution Activity coefficients of molecules in solution Activity of water
Slide 46
Thermodynamic Framework
Aqueous Phase: For activity coefficients of ions in solution the formulation is made up of 3 terms:
The Debye-Huckel term for long-range, ion-ion interactions The Bromley-Zemaitis term for short-range, ion-ion interactions The Pitzer term for short-range, ion-molecular interactions Note: Long-range is for moderately dilute solutions, shortrange is for increased concentractions
Slide 47
Thermodynamic Framework
Aqueous Phase: For activity coefficients for molecules other than water in solution, the Setschenow equation is used. For activity of water in a multicomponent system the Meissner and Kusik mixing rule equation is used.
Slide 48
Thermodynamic Framework
Vapor Phase: 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:
Ideal, all fugacity coefficients are assumed to be 1.0 Nothnagel method, valid up to 20 atmospheres Nothnagel method, valid up to 200 atmospheres SRK method, valid for wider range of conditions and for vapor-phase nonideality
Slide 49
Thermodynamic Framework
Vapor Phase: 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:
Ideal, all fugacity coefficients are assumed to be 1.0 Nothnagel method, valid up to 20 atmospheres Nothnagel method, valid up to 200 atmospheres SRK method, valid for wider range of conditions and for vapor-phase nonideality
Slide 50
Thermodynamic Framework
Non-Aqueous Phase: Normally strong functions of temperature and composition and weaker function of pressure. Activities of components in the organic liquid phase are determined from SRK Kabadi-Danner equation of state.
Slide 51
Thermodynamic Framework
Bulk Phase Properties: Old vs. New Framework:
Old: Equilibrium constant, K, is temperature dependent (retirived from PUBLIC databank). 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