OLI Mixed Solvent Electrolyte With Aspen Plus

Opening new doors with Chemistry
THINK SIMULATION!
OLIs Mixed Solvent
Electrolyte with Aspen
PLUS
OLI Systems, Inc.
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SIMULATION
2
Agenda
OLIs basic history
OLIs history with Aspen Technologies
Advantages/disadvantages of Aspen PLUS OLI
Architecture of the Aspen PLUS OLI interface
Introduction to MSE
Overview of Aspen PLUS OLI (with MSE)
Demonstration
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SIMULATION
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OLIs basic history
Company founded in 1971 by Marshall Rafal
First electrolyte simulator (ECES) 1973
Developed for OLIN Chemical
First commercial sale of ECES 1975
Dupont
The Environmental Simulation Program developed in
1991
Linkage to simulators in 1995
Windows program (Analyzers) became commercial in
2000
Mixed-Solvent Electrolytes commercially available 2005
Windows based process simulator (OLI Pro) to be
available in 2007
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SIMULATION
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OLIs history with Aspen Technologies

That Other chemical company that has a D in its name.
25 years of process simulation experience with electrolyte
1995 switched to Aspen PLUS as their process simulator
Wanted OLIs electrolytes in Aspen PLUS
1996 first Aspen PLUS OLI interface created
No model manager, version 8.2
1997 Aspen PLUS OLI linked to model manager
Version 9.0
2006 Aspen PLUS OLI updated for Aspen ONE 2006
Included change in concentration basis
Included MSE
2007 Aspen PLUS OLI updated for Aspen ONE 2006.5
General release of MSE for all Aspen PLUS OLI clients
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SIMULATION
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Advantages of Aspen PLUS OLI

User Interface
Learn one flow sheeting system
Multiple Property Options in same flowsheet
Different Non-electrolyte capability
Sizing
Costing
Two Software Venders

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SIMULATION
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Disadvantages of Aspen PLUS OLI

No Corrosion
No advanced OLI technology
No Ion-exchange
No Surface Complexation
No Bio-kinetics
No Scaling Tendencies
Two Software Venders

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SIMULATION
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OLI Chemistry
Generator
OLI
Databases
OLI/A+
XREF
OLI Numerical
Solver/Engine
.BKP
.ASP/.INP
.DBS
A+
Model Manager
A+
Simulation Engine
Electrolyte Flash or Property
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SIMULATION
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Aspen Unit Operations available with the OLI Property Set
MIXERS
FSPLIT
SEP
SEP2
HEATER
FLASH2
FLASH3
HEATX
MHEATX
RADFRAC
RSTOIC
RYIELD
RCSTR
RPLUG
PUMP
COMPR

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SIMULATION
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Thermodynamic Properties from OLI used by Aspen
PLUS (OLI propset)
PHIVMX DLMX KL DGL
PHILMX SIGLMX DV PHILPC
HVMX PHIV DL DSV
HLMX PHIL SIGL KVPC
GVMX HV HSMX
GLMX HL PHIL
SVMX GV VV
SLMX GL MUVMXL
VVMX SV MUVLP
VLMX SL KVMXLP
MUVMX VV KVLP
MULMX VL DHV
KVMX MUV DHL
KLMX MUL DHLPC
DVMX KV DGV
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SIMULATION
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The OLI-Aspen Plus Cross Reference File (partial listing)
Full listing is available on your computer:
C:\Program Files\OLI Systems\Alliance Suites\Aspen OLI
2006\Databanks\OLIAspenPlusCompXRef.lis
ESP-NAME DB 8-CHAR ASP-ALIAS ASP-NAME
================ = ====== ========= =====================================
AR P AR AR ARGON 7440-37-1 Ar
ABIETICAC P ABIETICA C20H30O2 ABIETIC-ACID 514-10-3 C20H30O2
ACENAPHTHN P ACENAPHT C12H10-D0 ACENAPHTHENE 83-32-9 C12H10
ACENITRILE P ACENTL C2H3N ACETONITRILE 75-05-8 C2H3N
ACET2 P ACET2 ........... C4H8O4
ACETACID P ACETACID C2H4O2-1 ACETIC-ACID 64-19-7 C2H4O2
ACETAL P ACETAL C6H14O2-D1 ACETAL 105-57-7 C6H14O2
ACETALDEHD P ACEALD C2H4O-1 ACETALDEHYDE 75-07-0 C2H4O
ACETAMIDEPPT P ACETAM-S 60-35-5 C2H5NO
ACETAMIDE P ACETAMD C2H5NO-D1 ACETAMIDE 60-35-5 C2H5NO
ACETANHYD P ACETAHYD C4H6O3 ACETIC-ANHYDRIDE 108-24-7 C4H6O3
ACETANILID P ACEANILD C8H9NO ACETANILIDE
ACETATEION P ACET- CH3COO- CH3COO- ........... C2H3O2-1
ACETBR P ACETBR 506-96-7 C2H3BrO
ACETCL P ACETCL C2H3CLO ACETYL-CHLORIDE 75-36-5 C2H3ClO
ACETONE P ACETONE C3H6O-1 ACETONE 67-64-1 C3H6O
ACETPHENON P ACEPHEN C8H8O METHYL-PHENYL-KETONE 98-86-2 C8H8O
ACETYLENE P ACETYLN C2H2 ACETYLENE 74-86-2 C2H2
ACRIDINE P ACRIDINE 260-94-6 C13H9N
ACROLEIN2 P ACROLIN2 C3H4O ACROLEIN 107-02-8 C3H4O
ACRYLAMIDEPPT P ACRAMI-S 79-06-1 C3H5NO
ACRYLAMIDE P ACRYAMID C3H5NO-D1 ACRYLAMIDE 79-06-1 C3H5NO
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SIMULATION
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OLI added user blocks to Aspen PLUS
EFRACH
EFLASH
Available during Aspen PLUS Installation
Must be enabled at run-time
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SIMULATION
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EFLASH
Organic (3)
Solid (4)
EFLASH

(Four outlet material streams)
Feeds
Heat
Heat
Vapor (1)
Aqueous (2)
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SIMULATION
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EFRACH
DECANTER
Vapor or Liquid
Organic
Heat Heat
1
2

3
N
Feeds Products
Heat Heat
Heat Heat
Bottoms
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SIMULATION
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Introduction to MSE

Why develop a new thermodynamic model?
The Bromley-Zemaitis model (a/k/a Aqueous Model-AE)
had limitations
Water was required as a solvent
Mole fraction of all solutes was limited to approximately 0.35
Limited in temperature (Approximately 300
o
C)
LLE predictions exclude critical solution points (limited to
strongly dissimilar phases)
A Mixed Solvent Electrolyte model (MSE) has advantages
Water is not required
Mole fraction of solute can approach and be equal to 1.0
Temperature can be up to 0.9 T
c
of solution
Full range of LLE calculations including electrolytes in both
phases

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SIMULATION
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Introduction to MSE
Advantages and disadvantages between AE and MSE

MSE model
Model advantages:
No composition limitations
Reliable predictions for
multicomponent concentrated
solutions
Full range of LLE calculations
including electrolytes in both
phases
Methodological advantages
Multi-property regressions
Consistent use of
thermochemical properties
(no shortcuts like KFITs)
Rigorous quality assurance
Disadvantages:
A smaller in-place databank
but it is continuously
extended

AE Model
Advantages:
Larger existing databank
The only model available for
rates of corrosion
Disadvantages:
Limitations with respect to
composition (30 m with
respect to electrolytes,
x=0.3 with respect to
nonelectrolytes
LLE predictions exclude
critical solution points
(limited to strongly dissimilar
phases)

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Introduction to MSE

Overview of species coverage between AE and MSE models.

C
o
m
p
o
n
e
n
t
s

Solute Mole Fraction
0
2000
4000
6000
8000
0.0
1.0
AE
MSE
Build 7.0.54
Growing with each build
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SIMULATION
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Structure of the thermodynamic model
Definition of species that may exist in the liquid,
vapor, and solid phases
Excess Gibbs energy model for solution
nonideality
Calculation of standard-state properties
Helgeson-Kirkham-Flowers equation for ionic and
neutral aqueous species
Standard thermochemistry for solid and gas
species
Algorithm for solving phase and chemical
equilibria
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SIMULATION
Outline of the model:
Solution nonideality

RT
G
RT
G
RT
G
RT
G
ex
II
ex
LC
ex
LR
ex
+ + =
LR Debye-Hckel theory for long-range electrostatic
interactions
LC Local composition model (UNIQUAC) for neutral
molecule interactions
II Ionic interaction term for specific ion-ion and ion-
molecule interactions

Excess Gibbs energy
( )

|
|
.
|
\
|
=
i j
x ij j i
i
i
ex
II
I B x x n
RT
G
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SIMULATION
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Chemical equilibrium calculations
For a chemical reaction:

At equilibrium

with

dD cC bB aA + = +
|
|
.
|
\
|
=
b
B
a
A
d
D
c
C
b
B
a
A
d
D
c
C
0
x x
x x
ln
RT
G

A
=
i
0
i i
0
v G A
Standard-state
chemical
potential of i
Infinite-dilution properties
Thermochemical databases for aqueous systems
Helgeson-Kirkham-Flowers model for T and P dependence

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SIMULATION
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Constraints
Activity coefficients are converted to unsymmetrical normalization to
work with infinite-dilution properties
Constraining the parameters of the G
E
model to reproduce the Gibbs
energy of transfer

R O
2
H x
i
, ,
S , O
2
H , x
i
Activity coefficient of ion i in solvents R and

S in unsymmetrical, mole-fraction based
convention
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SIMULATION
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Mixed-solvent electrolyte model:
Applicability

Simultaneous representation of multiple properties
Vapor-liquid equilibria
Osmotic coefficient/water activity and activity coefficients
Solid-liquid equilibria
Properties of electrolytes at infinite dilution, such as acid-
base dissociation and complexation constants
Properties that reflect ionic equilibria, e.g., solution pH and
species distribution
Enthalpy (AHdil or AHmix)
Heat capacity
Density

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Validity range
Concentrations from infinite dilution to
saturation or fused salt or pure solute limit
Temperatures up to 0.9Tc of mixtures
This translates into 300 C for H2O dominated
systems
For concentrated inorganic systems, substantially
higher temperatures can be reached
Solvents: water, various organics or solvent
mixtures
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SIMULATION
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Representative applications of the MSE
thermodynamic model
Strong acid systems
Simultaneous representation of phase equilibria
and speciation
Salt systems
Prediction of properties of multicomponent
systems
Organic salt water systems
Salt effects on VLE, LLE and SLE
Acid-base equilibria
pH of mixed-solvent systems

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SIMULATION
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VLE for H2SO4 + SO3 + H2O

1.0E-08
1.0E-07
1.0E-06
1.0E-05
1.0E-04
1.0E-03
1.0E-02
1.0E-01
1.0E+00
1.0E+01
1.0E+02
1.0E+03
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
x SO
3
P
,

a
t
m
0C
200C
100C
50C
25C
500C 400C
300C

Phase
equilibria are
accurately
reproduced
from 0 C to
500 C

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SIMULATION
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Speciation for H
2
SO
4
+ SO
3
+ H
2
O:

0
10
20
30
40
50
60
70
80
90
100
0.0 0.2 0.4 0.6 0.8 1.0
(x SO3)
1/2
m
o
l
e

p
e
r
c
e
n
t
1957HR
1959YMS
1994CRP&1995CB
2000WYCH
SO
4
-2
H
2
SO
4
0
SO
3
0
x (SO
3
)=0.5
HSO
4
-

Predicted
speciation in
concentrated
solutions agrees
with
spectroscopic
data

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SIMULATION
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Partial pressures in the H
2
SO
4
+ SO
3
+ H
2
O system

Partial pressures
of H
2
SO
4
, SO
3

and H
2
O are
also correctly
reproduced

1.E-15
1.E-14
1.E-13
1.E-12
1.E-11
1.E-10
1.E-09
1.E-08
1.E-07
50 55 60 65 70 75 80
H
2
SO
4
, Wt%
H
2
S
O
4
,

a
t
m
25C
30C
35C
25C
30C
35C
Perry 30C
Partial pressures of H
2
SO
4

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SIMULATION
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Salt systems:
Na K Mg Ca Cl NO
3
Step 1: Binary systems
solubility of solids
The model is valid for
systems ranging from
dilute solutions to the
fused salt limit

0
10
20
30
40
50
60
70
80
90
100
-20 0 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 320
Temperature, C
N
a
N
O
3
,

w
e
i
g
h
t

%
NaNO3
H2O(s)
Cal, NaNO3
Cal, H2O(s)

0
10
20
30
40
50
60
70
80
90
100
-40 -20 0 20 40 60 80 100 120 140 160 180 200
Temperature, C
M
g
(
N
O
3
)
2
,

w
e
i
g
h
t

%
H2O(s)
Mg(NO3)2.9H2O
Mg(NO3)2.6H2O
Mg(NO3)2.2H2O
Mg(NO3)2
Cal, H2O(s)
Cal, Mg(NO3)2.9H2O
Cal, Mg(NO3)2.6H2O
Cal, Mg(NO3)2.2H2O
Cal, Mg(NO3)2
NaNO
3
H
2
O
Mg(NO
3
)
2
H
2
O
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SIMULATION
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Modeling salt systems:
Na K Mg Ca Cl NO
3

Step 1: Binary
systems solubility
of solids
Water activity
decreases with salt
concentration until
the solution becomes
saturated with a
solid phase

0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45 0.5 0.55 0.6 0.65
Total apparent salt, mole fraction
W
a
t
e
r

a
c
t
i
v
i
t
y
1 - NaCl
6 - LiCl
11 - CaCl2
3 - Mg(NO3)2
12 - Ca(NO3)2
Ca(NO
3
)
2
LiCl
Mg(NO
3
)
2
CaCl
2
.2H
2
O
NaCl
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SIMULATION
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Step 2: Ternary systems
Solubility in the system
NaNO
3
KNO
3
H
2
O
at various
temperatures

Activity of water over
saturated NaNO
3

KNO
3
solutions at 90 C:
Strong depression at
the eutectic point

0.35
0.4
0.45
0.5
0.55
0.6
0.65
0.7
0.75
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
NaNO
3
, mole fraction (water free)
W
a
t
e
r

A
c
t
i
v
i
t
y
KNO
3
NaNO
3
+KNO
3
NaNO
3

0
10
20
30
40
50
60
70
80
90
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95
KNO
3
, weight %
N
a
N
O
3
,

w
e
i
g
h
t

%
0C 10C
20C 25C
30C 40C
50C 75C
100C 125C
150C 175C
200C
NaNO
3
(s)
KNO
3
(s)
NaNO
3
.KNO
3
(s)
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SIMULATION
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Step 3: Verification of predictions for multicomponent systems
Deliquescence data
simultaneously
reflect solid
solubilities and
water activities

0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Total apparent salt, mole fraction
W
a
t
e
r

a
c
t
i
v
i
t
y
10 - NaNO3+KNO3
4 - NaNO3+KNO3+Ca(NO3)2+Mg(NO3)2
NaNO
3
NaNO
3
+NaNO
3
.KNO
3
NaNO
3
NaNO
3
+Ca(NO
3
)
2
Mixed nitrate systems at 140 C
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SIMULATION
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Electrolyte + organic systems:
Examples

Effect of electrolytes on phase equilibria in nonelectrolyte water
systems
Salting out(in) effects
Liquid-liquid equilibria in aqueous systems containing water-
soluble polymers and salts
Liquid immiscibility is induced by the presence of a salt

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SIMULATION
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LLE results salt effect

0.00000
0.00005
0.00010
0.00015
0.00020
0.00025
0.00030
0.00035
0.00040
0.00045
0 100 200 300 400
g salt/kg H
2
O
S
o
l
u
b
i
l
i
t
y

o
f

b
e
n
z
e
n
e

(
x
)

i
n

a
q
u
e
o
u
s

s
a
l
t

s
o
l
u
t
i
o
n
s
NaCl
25 C
(NH
4
)
2
SO
4
Solubility of
benzene in
aqueous
(NH
4
)
2
SO
4
and
NaCl solutions
at 25C
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SIMULATION
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VLE: salting-out effect
60
70
80
90
100
110
0.0 0.2 0.4 0.6 0.8 1.0
x, y (methanol)
t
/
C
P=1 bar
---- Salt-free
Saturated NaCl
0.0
1.0
2.0
3.0
4.0
5.0
6.0
7.0
0.0 0.2 0.4 0.6 0.8 1.0
x-methanol
m
o
l

N
a
C
l
/
k
g

s
o
l
v
e
n
t
Solubility
25C
Simultaneous representation of
thermodynamic properties:
NaCl-methanol-water

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SIMULATION
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LLE in aqueous polymer
salt systems

PEG (MW=1000) + NaH
2
PO
4
+ H
2
O at
25 C

PEG (MW=4000) + (NH
4
)
2
SO
4
+ H
2
O
at 25 C

0.00
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
0.000 0.005 0.010 0.015 0.020 0.025
x - PEG1000
X

-

N
a
H
2
P
O
4
0.000
0.005
0.010
0.015
0.020
0.025
0.030
0.0000 0.0005 0.0010 0.0015 0.0020 0.0025
x - PEG 4000
x

-

(
N
H
4
)
2
S
O
4
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SIMULATION
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Acid-base and phase equilibria:
Treatment of pH in mixed solvents
Classical treatment
pH scale can be defined separately for each, pure or mixed,
solvent
pH scales can be converted using the Gibbs energy of transfer
of the proton

Such a conversion is inconvenient (availability of Gibbs energy of
transfer, extrathermodynamic assumptions)
However, it opens the possibility of a uniform calculation of pH
using an activity coefficient model as long as the model
accurately reproduces activity coefficients of individual species
and the Gibbs energy of transfer
10 ln
,
RT
G
pH pH
A w t
H
w A
+
A
+ =
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SIMULATION
36
Treatment of pH in mixed-solvents

Uniform treatment of apparent pH
Starting point: Aqueous definition of pH

Conversion to mole fraction scale and solvated proton basis

Activity coefficients are obtained directly from the model
Values can be compared with measurements using glass
electrode
Does not require the presence of water equivalent
expressions can be obtained for other solvents
|
|
.
|
\
|
= =
+ +
+
0
log log
m
m
a pH
H H
H
O H O H
O H
O H O H
x
M
x pH
2 2
2
3 3
log log
1000
log log log + +
|
|
.
|
\
|
=
+ +
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SIMULATION
37
Speciation Effects
Acetic Acid in EtOH-H
2
O Acetic Acid in MeOH-H
2
O
Apparent (Mixed Solvent-Based) Ionization Constants
4
6
8
10
12
0.0 0.2 0.4 0.6 0.8 1.0
x-Methanol
p
K
a
cal
exp
4
6
8
10
12
0.0 0.2 0.4 0.6 0.8 1.0
x-Ethanol
p
K
a
cal
Sen et al.
Woolley
Equilibrium constant
obtained from aqueous
solutions
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SIMULATION
38
Parameters in the MSE Databank (1)
Binary and principal ternary systems composed of the following primary ions
and their hydrolyzed forms
Cations: Na
+
, K
+
, Mg
2+
, Ca
2+
, Al
3+
, NH
4
+

Anions: Cl
-
, F
-
, NO
3
-
, CO
3
2-
, SO
4
2-
, PO
4
3-
, OH
-

Aqueous acids, associated acid oxides and acid-dominated mixtures
H
2
SO
4
SO
3

HNO
3
N
2
O
5

H
3
PO
4
H
4
P
2
O
7
H
5
P
3
O
10
P
2
O
5

H
3
PO
2

H
3
PO
3

HF
HCl
HBr
HI

H
3
BO
3

CH
3
SO
3
H
NH
2
SO
3
H
HFSO
3
HF H
2
SO
4

HI I
2
H
2
SO
4

HNO
3
H
2
SO
4
SO
3

H
3
PO
4
with calcium phosphates
H Na Cl NO
3

H Na Cl F

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SIMULATION
39
Inorganic gases in aqueous systems
CO
2
+ NH
3

H
2
S + NH
3

SO
2
+ H
2
SO
4

N
2

O
2

H
2

Transition metal aqueous systems
Fe(III) H O SO
4
, NO
3

Fe(II) H O SO
4
, Br
Sn(II, IV) H O CH
3
SO
3

Zn(II) H SO
4
, NO
3
, Cl
Zn(II) Li - Cl

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SIMULATION
40
Transition metal aqueous systems - continued
Cu(II) H SO
4
, NO
3

Ni(II) H SO
4
, NO
3
, Cl
Mo(VI, IV) H O Cl, SO
4
, NO
3

W(VI) H - O - Na Cl, NO
3

Most elements from the periodic table in their elemental form
Base ions and hydrolyzed forms for the majority of elements from the
periodic table
Hydrogen peroxide chemistry
H
2
O
2
H
2
O H - Na OH SO
4
NO
3

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SIMULATION
41
Miscellaneous inorganic systems in water
NH
2
OH
NH
4
HS + H
2
S + NH
3

LiCl KCl
LiCl CaCl
2

Na
2
S
2
O
3
LiOH H
3
BO
3
H
2
O
Organic acids in water, methanol and ethanol and their Na salts
Formic
Acetic (also K salt)
Citric
Adipic
Nicotinic
Terephthalic
Isophthalic
Trimellitic

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SIMULATION
42
Organic components and their mixtures with water
Hydrocarbons
Straight chain alkanes: C1 through C30
Isomeric alkanes: isobutane, isopentane, neopentane
Alkenes: ethene, propene, 1-butene, 2-butene, 2-methylpropene
Aromatics: benzene, toluene, o-, m-, p-xylenes, ethylbenzene, cumene,
naphthalene, anthracene, phenantrene
Alcohols
Methanol, ethanol, 1-propanol, 2-propanol, cyclohexanol
Glycols
Mono, di- and triethylene glycols, propylene glycol, polyethylene glycols
Phenols
Phenol, catechol
Ketones
Acetone, methylisobutyl ketone
Aldehydes
Butylaldehyde
THINK
SIMULATION
43
Organic solvents and their mixtures with water
Carbonates
Diethylcarbonate, propylene carbonate
Amines
Tri-N-octylamine, triethylamine, methyldiethanolamine
Nitriles
Acetonitrile
Amides
Dimethylacetamide, dimethylformamide
Halogen derivatives
Chloroform
Aminoacids
Methionine
Heterocyclic components
N-methylpyrrolidone, 2,6-dimethylmorpholine
THINK
SIMULATION
44
Polyelectrolytes
Polyacrylic acid
Complexes with Cu, Zn, Ca
Mixed-solvent organic systems
HAc tri-N-octylamine toluene H
2
O
HAc tri-N-octylamine methylisobutylketone H
2
O
HAc MeOH EtOH H
2
O
HAc MeOH CO
2
H
2
O
Dimethylformamide HFo H
2
O

THINK
SIMULATION
45
Mixed-solvent inorganic/organic system
Hydrocarbon water salt (Na, K, Ca, Mg, NH
4
, H, Cl, SO
4
, NO
3
) systems
Mono, di- and triethylene glycols - H Na Ca Cl CO
3
HCO
3
- CO
2

H
2
S H
2
O
Phenol - acetone - SO
2
- HFo - HCl H
2
O
Benzene NaCl and (NH
4
)
2
SO
4
- H
2
O
Cyclohexane NaCl - H
2
O
n-Butylaldehyde NaCl - H
2
O
LiPF
6
diethylcarbonate propylene carbonate
Ethanol LiCl - H
2
O
Methanol - H
2
O + NaCl, HCl

THINK
SIMULATION
46
Predictive character of the model
Levels of predictivity
Prediction of the properties of multicomponent
systems based on parameters determined from
simpler (especially binary) subsystems
Extensively validated for salts and organics
Prediction of certain properties based on
parameters determined from other properties
Extensively validated (e.g., speciation or caloric
property predictions)

THINK
SIMULATION
47
What does it mean for the
model to be predictive?

Parameters were determined
using only binary salt + H
2
O
data
SLE for the ternary system
was predicted without making
any ternary fits
MSE is clearly superior even
in the applicability range of
the aqueous model
This can work only when the
ternary system does not
introduce a chemistry change
(e.g., double salts)
0
5
10
15
20
25
30
35
40
45
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
NaH
2
PO
4
, weight %
K
H
2
P
O
4
,

w
e
i
g
h
t

%
0C 5C
10C 15C
20C 25C
30C 35C
40C 45C
50C 55C
60C 65C
70C 75C
0
5
10
15
20
25
30
35
40
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
NaH
2
PO
4
, weight %
K
H
2
P
O
4
,

w
e
i
g
h
t

%
0C 5C
10C 15C
20C 25C
30C 35C
40C 45C
50C 55C
60C 65C
70C 75C
MSE (no ternary fits)
Aqueous model
(no ternary fits)
THINK
SIMULATION
48
Predictive character of the model
Levels of predictivity - continued
Prediction of properties without any knowledge of
properties of binary systems
Standard-state properties: Correlations to predict the
parameters of the HKF equation
Ensures predictivity for dilute solutions
Properties of solids: Correlations based on family analysis
Parameters for nonelectrolyte subsystems
Group contributions: UNIFAC estimation
Quantum chemistry + solvation: CosmoTherm
estimation
Also has limited applicability to electrolytes as long
as dissociation/chemical equilibria can be
independently calculated

THINK
SIMULATION
49
Transport properties in the OLI
software
Available transport properties:
Diffusivity
Viscosity
Electrical conductivity
OLI was the first to develop transport property
models for concentrated, multicomponent
aqueous solutions
More recently, the models have been extended
to mixed-solvent systems
THINK
SIMULATION
50
Modeling diffusivity in electrolyte systems
Limiting diffusivity
Long-range electrostatic interactions
Relaxation effect:

Short-range interactions
Hard-sphere contribution:

Combination of the two effects:
|
|
.
|
\
|
+
i
i
k
k
1
o
0
i
HS
i
D
D
|
|
.
|
\
|
|
|
.
|
\
|
+ =
0
i
HS
i
i
i
0
i i
D
D
k
k
1 D D
o
Enskog theory:
Significant for
concentrated
solutions
MSA theory:
Important in
relatively dilute
solutions
0
i
D
THINK
SIMULATION
51
Calculation of diffusivity in MSE solutions
0.0
0.5
1.0
1.5
2.0
2.5
0.0 0.2 0.4 0.6 0.8 1.0
x'
methanol
D
m
e
t
h
a
n
o
l
*
1
0
9
,

m
2
/
s
x
LiCl
=0.005
x
LiCl
=0.01
x
LiCl
=0.02
x
LiCl
=0
D
methanol
in methanol-water-LiCl
system at 25C at various LiCl
concentrations
x
NaCl
=0.005
0.0
0.5
1.0
1.5
2.0
2.5
0.0 0.2 0.4 0.6 0.8 1.0
x'
methanol
D
m
e
t
h
a
n
o
l
*
1
0
9
,

m
2
/
s
x
NaCl
=0.01
x
NaCl
=0.02
salt-free
D
methanol
in methanol-water-NaCl system
at 25C at various NaCl concentrations
THINK
SIMULATION
52
Computation of diffusion coefficients:
Species in NiCl
2
solutions
For complexed species,
measured diffusion
coefficients are
weighted averages of
diffusion coefficients of
individual complexes:
0.0
0.5
1.0
1.5
2.0
2.5
0 1 2 3 4 5
m NiCl
2
D

1
0
9

(
m
2

s
-
1
)
Ni species - Stokes et
al. (1979)
Ni species - Salmon et
al. (1987)
Cl species - Stokes et
al. (1979)
D iD
c
c
X Q X
Q X
X i
T i i
i i
T
=

c
c
THINK
SIMULATION
53
Modeling electrical conductivity
|
.
|
\
|
+
|
|
.
|
\
|
+ =
X
X
v
v
i
el
i
i i
o o
1 1
0
0
Limiting
conductivity
Dependence of
i
on
electrolyte concentration
relaxation
effect
electrophoretic
correction
The model includes the computation of
1. Limiting conductivities of ions as a function of temperature and
solvent composition
2. Dependence of electrical conductivity on electrolyte concentration
(the mean spherical approximation theory)
THINK
SIMULATION
54
Electrical conductivity model:
H
2
O H
2
SO
4
SO
3

0.0001
0.001
0.01
0.1
1
10
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
x-SO3
s
p
e
c
i
f
i
c

c
o
n
d
u
c
t
i
v
i
t
y

(
S
.
c
m
-
1
)
THINK
SIMULATION
55
Electrolytes in mixed solvents:
MgCl
2
+ ethanol + water
1.0E-05
1.0E-04
1.0E-03
1.0E-02
1.0E-01
1.0E+00
0.0001 0.001 0.01 0.1 1 10
mol MgCl
2
/kg solvent
80%
60%
40%
100% EtOH (------)
20%
0% EtOH
s
p
e
c
i
f
i
c

c
o
n
d
u
c
t
i
v
i
t
y
,

S

c
m
-
1

THINK
SIMULATION
56
Viscosity model
s s s LR
mix
A + A + A = q q q q q
0
viscosity of the
MSE solution
viscosity of the
solvent mixture
long-range
electrostatic
contribution
individual ion
contributions
interactions
between species
Dependence of q
on electrolyte
concentration
In MSE solutions, q-q
0
is found to show regularities with respect to
both electrolyte concentrations and solvent composition, and is the
most convenient quantity to define the model
THINK
SIMULATION
57
Viscosities of solvent mixtures, q
0
mix

0.0
0.5
1.0
1.5
2.0
0.0 0.2 0.4 0.6 0.8 1.0
x-acetone
V
i
s
c
o
s
i
t
y

(
c
P
)
20C
25C
50C
acetone + water
Mixing rule
( )
ij j i ij
k + + = 1
2
1
0 0
q q q
=
l
l l
i i
i
v x
v x
Y
*
*
il l
i l
l i i
g v x v v
0 4 1 0 *
+ =
=
Modified volume fractions
=
i j
ij j i mix
Y Y q q
0
THINK
SIMULATION
58
Effects of electrolyte concentration
Aq
LR
From the analytical
model by Onsager and Fuoss
(1932)

Aq
s
defined for multiple
solvents

Aq
s-s
defined for solvent
combinations
(
(
|
|
.
|
\
|
|
.
|
\
|
= A

=0
0
2 1
4
2
n
n
n
N
i
i
i i LR
s c r
z
T
I
a
i
c
q
= A
j i
j i i j j
s
B c x
,
0
q q
= A

j l i k
ik,jl k i jl l j
s s
I D f f x x
2 0 ' '
q q
calculated using c and
i
0
in
the mixed solvent
j = solvent; i = ion or neutral
j,l = solvent; i,k = ion or neutral
B
i,j
evaluated
based on
viscosities of
electrolyte in
pure solvent
D
ik,jl
(I,T) adjusted based on
experimental data
THINK
SIMULATION
59
Viscosity of H
2
O H
2
SO
4
SO
3

0.1
1
10
100
1000
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
x-SO3
q
,

c
P
THINK
SIMULATION
60
Viscosity of salt organic - water systems:
LiNO
3
-ethanol-H
2
O
Viscosities of the ternary solutions
of LiNO
3
-ethanol-H
2
O as a function
of the molarity of LiNO
3
at 25C and
at various ethanol weight percent.
0
2
4
6
8
10
12
14
16
0 5 10 15
c-LiNO
3
, mol/L
q
,

c
P
100 wt%
70 wt%
30 wt%
EtOH=0 wt%
THINK
SIMULATION
61
Sublimation / salt point
calculations

Solid-gas equilibrium
computations for pure
NH
4
Cl and NH
4
HS

0.001
0.01
0.1
1
10
150 200 250 300 350
t/C
s
u
b
l
i
m
a
t
i
o
n

p
r
e
s
s
u
r
e
Stull-1947
OLI
0.001
0.01
0.1
1
10
-60 -30 0 30 60 90
t/C
s
u
b
l
i
m
a
t
i
o
n

p
r
e
s
s
u
r
e
,

a
t
m
Stull-1947
P, atm (cal)
NH
4
Cl
NH
4
HS
THINK
SIMULATION
62
HI - I2 - H2O

H2O/HI/I2 full range of concentration, T
The heart of the IS Process
Challenge: presence of more than one LLE
region together with regions of VLE and SLE
THINK
SIMULATION
63
MSE Challenge
For systems within the AQ model limits, yes
Binary systems give reasonable results
when water remains the dominant solvent
When the 2
nd
solvent, or different solvent
predominates
All major components must be studied with
respect to all solvents
e.g., for MEG systems, MEG Ca and MEG Na
must be regressed, along with
Will MSE work out-of-the-box?
THINK
SIMULATION
64
Overview of Aspen PLUS OLI
(with MSE)
Using the Aspen PLUS OLI Chemistry Generator
THINK
SIMULATION
65
Aspen OLI Chemistry Generator
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SIMULATION
66
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67
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Aspen OLI Chemistry Wizard
THINK
SIMULATION
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Aspen Plus 2006
THINK
SIMULATION
99
Aspen Plus 2006
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SIMULATION
100
Aspen Plus 2006
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Aspen Plus 2006
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Aspen Plus 2006
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Aspen Plus 2006
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SIMULATION
104
Aspen Plus 2006
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SIMULATION
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Aspen Plus 2006
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Aspen Plus 2006
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Aspen Plus 2006
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Aspen Plus 2006
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Aspen Plus 2006
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Aspen Plus OLI with EFRACH
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Aspen OLI
More examples?
Live cases?
Questions?
THINK
SIMULATION
122
Conclusion
Using MSE in Aspen Plus is very similar to using
any property set.
The OLI property sets can be used with
standard Aspen PLUS unit operations or with OLI
unit operations

OLI Mixed Solvent Electrolyte With Aspen Plus

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