Introduction to Electrolyte

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

Simulation Steps: Predefined Modes

1. Description of the simulation
2. Input Unit of Measurement
3. Select Electrolyte Thermodynamic

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

Problem #1: HCL & H2O Solution

Ê Run a simple Flash model for H2O-HCL system
using:
y NRTL Method
y HCL Electrolyte Method
Ê And then compare the results.

Slide 14
Problem #1: HCL & H2O Solution

Stream Name HCL

Stream Description VAPOR
Phase Vapor
Temperature 20.000 C
Pressure 1.033 KG/CM2
Flowrate 50.000 KG-MOL/HR
Composition
H2O 0.000 FLASH
HCL 1.000

Stream Name H2O DP=0.0, Duty=0.0

Stream Description
Phase Liquid
Temperature 20.000 C
Pressure 1.033 KG/CM2
Flowrate 100.000 KG-MOL/HR
Composition
H2O 1.000 AQUEOUS
HCL 0.000

Slide 15

Problem #1: HCL & H2O Solution

VLE LIQUID INTERACTION PARAMETERS FOR H2O-HCL PAIR
NRTL BINARY COEFFICIENTS

I J A(I,J) B(I,J) C(I,J) ALPHAC UNITS FROM

A(J,I) B(J,I) C(J,I) ALPHAT
--- --- -------- ---------- ----------- ------- --------- ----
1 2 0.000000 2222.9199 0.00 0.2007 DEG K SIMSCI VLEBANK
0.000000 -2037.3400 0.00 0.0000

X-Y Plot for HCL and H2O

1.0

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

Liquid Composition, Mole Fraction HCL

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

Problem #2: Na2CO3 Solubility in Water

Ê Employ Case Study option for the followings:
- Temperature from 5 C to 100 C with step size = 5 C

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

Problem #3: Sodium Chloride Solution

Ê Part 1:
y Is the CO2 absorbed in the solution and to what
extent?
y Is the solution saturated with NaCl?
y Is there an excess of salt, and does it form a solid
phase?
y What is the pH of the solution?
Ê Part 2:
y How does increasing the temperature of the flash
change the pH and NaCl concentration of the outlet
streams?

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

T=75 C 190 kg/h SO2

P=1.06 bar 105 kg/h HCl Bottoms
50 kg/h N2

Slide 21

Problem #4: Acid Gas Absorber

Ê Part 1:
y How effective is the absorber?
y What is the weight fraction of HCl in the bottoms
stream?
y What is the pH of the bottoms stream and the HCl
solution stream?
y What is the temperature of the absorber?
Ê Part 2:
y What flowrate of HCl wash solution in necessary to
reduce the OVHD weight fraction of HCl to 0.1%?
y What is the weight fraction of HCl in the bottoms stream
with the new wash solution flowrate?

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

Electrolyte Distillation (ELDIST)

Ê INNER LOOP:
y Input to the Inner Loop model are T, P, x and y. T, P
and x are needed for speciation calcualations
(equations that include equilibrium constants,
electroneutrality and independent atom balance
equations) and for computation of liquid phase
fugacities.
y Once the true model fraction of aqueous components
are determined, they are then translated to
reconsitituted species.
y Once the speciation equations are solved, VLE k-
values and its derivatives are computed as a function of
T, P, x and y.

Slide 24
Electrolyte Distillation (ELDIST)
Ê OUTER LOOP:
y Outer loop is solved by the Newton-Raphson algorithm.

Ê The equation to be solved on each tray are:

y Component balance
y Vapor liquid equilibrium
y Energy balance
y Overall mass balance

Slide 25

Initial Estimate Generator (IEG)

Ê Given the initial estimates for the column
overhead and bottoms flowrate, the top tray
temperature, the condenser temperature, and the
column pressure, along with the column
specifications, the IEG=ELECTROLYTE will then
calculate initial estimates for all other column
parameters.
Ê These column parameters are then used by
ELDIST to solve the column.

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

Problem #5: Benfield Process

Ê Reactions produce potassium bicarbonate and
potassium bisulfide:

K 2CO3 ( aq ) + H 2O + CO2 ⇔ 2 KHCO3 ( aq )

K 2CO3 (aq) + H 2 S ⇔ KHCO3 (aq) + KHS (aq)

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

User-added Electrolyte Model

Ê Look up the component name for EUP using
PRO/II Component Utility Program.

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

Created Files from EUP

Ê The following files are generated from EUP:
y DBS Model database file
y MDL Inflow file
y MOU Inflow log file
y MOD Model definition file
y EQN Equation file
y OUT Summary of Generated model
y ERR Log/Error File

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

Select “Input” & “Thermodynamic Data”

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

190 kg/h SO2

105 kg/h HCl Splitter
50 kg/h N2
5 kg/h CH3CH 2Cl
Bottoms
T=75 C Product
P=1.06 bar Cooler

Slide 35

Problem #6: Acid Gas Absorber using

EUP
Ê Part 1:
y Use the EUP to generate a new model that combines
SO2, N2, HCl, H2O and CH3CH2Cl.
Ê Part 2:
y How does the ethyl chloride distribute in the system?
y Is it absorbed by the HCl solution or does it remain in
the gas stream?

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

Note: Long-range is for moderately dilute solutions, short-

range is for increased concentractions
Slide 47

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.

Ê Activities of components in the organic liquid

phase are determined from SRK Kabadi-Danner
equation of state.

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