Electrolyte

ELECTROLYTE MODULE
5.11
ELECTROLYTE
BATCH MODULE
MODULE
Contents
ELECTROLYTES
Chapter 1 Electrolyte Module
Using the Electrolyte Module . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1-1
Thermodynamic Models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1-2
Generating Electrolyte Components. . . . . . . . . . . . . . . . . . . . . . . . .1-3
Electrolytic Column Algorithm (ELDIST). . . . . . . . . . . . . . . . . . . .1-4
Electrolyte Modeling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1-4
General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1-6
Electrolyte General Data. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1-7
Electrolyte Component Data. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1-9
Electrolyte Thermodynamic Data. . . . . . . . . . . . . . . . . . . . . . . . . .1-10
Invalid Calculations for Electrolyte Models . . . . . . . . . . . . . . . . . .1-12
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1-15
Chapter 2 Electrolyte Models

Application Guidelines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-1
Pregenerated Models. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-1
User-Added Models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-2
Electrolyte Model Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-2
Summary of Electrolyte Models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-5
Amine Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-5
Acid Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-6
Mixed Salt Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-9
Sour Water Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-17
Caustic Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-23
Benfield Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-25
Scrubber Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-26
PRO/II 5.11 Add-On Modules User’s Guide iii

LLE and Hydrate Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-27
Alphabetical Component Index of Electrolyte Models. . . . . . . . . . . . . 2-32
A . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-33
B . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-33
C . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-33
D . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-34
E . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-34
F . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-34
H . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-34
K . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-35
L . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-35
M. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-35
ELECTROLYTES
N . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-36
O . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-37
P . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-37
S . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-37
T . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-37
Z . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-37
Chapter 3 Generating a User-Added Electrolyte Model

The Electrolyte Utility Package (EUP) . . . . . . . . . . . . . . . . . . . . . . . . . . 3-1
Generating User-Added Models for PRO/II Electrolytes. . . . . . . . . 3-1
Chapter 4 Electrolytes in PRO/II GUI

General Considerations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-1
Basic Unit Operations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-2
SPEC, DEFINE, VARY . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-2
Flash Drum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-3
Pump, Valve, Mixer, Splitter . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-3
Compressor or Expander . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-3
Pipe . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-4
Heat Exchangers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-4
Distillation Column . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-4
Reactors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-5
Solids Handling Utilities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-6
Calculator . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-7
Flowsheet Control . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-7
Miscellaneous . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-7
HCURVE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-8
iv Contents
BVLE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4-8
Hextables . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4-8
Case Study, Restart, Interactive . . . . . . . . . . . . . . . . . . . . . . . . . . . .4-9
Considerations Regarding Transport Properties . . . . . . . . . . . . . . . . . . .4-9
Output Considerations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4-9
Speed Considerations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4-9
ELECTROLYTES
PRO/II 5.11 Add-On Modules User’s Guide v

ELECTROLYTES
vi
Contents
Chapter 1
Electrolyte Module
ELECTROLYTES
This chapter explains the use of the Electrolyte add-on module
within PRO/II and how to enter general, component, and thermody-
namic data in the form of keywords or through the graphical user
interface.
Using the Electrolyte Module

The Electrolyte add-on module for PRO/II allows you to handle
systems containing electrolytes. The following unit operations can
be used with this Electrolyte add-on:
■ Calculator.
■ Column (Electrolytic Algorithm, see below).
■ Controller.
■ Flash.
■ Heat exchangers (Simple, LNG).
■ Heating/Cooling curve.
■ Mixer.
■ Optimizer.
■ Pipe.
■ Pump.
■ Reactor (Batch, Conversion, Equilibrium).
■ Splitter.
■ Stream calculator.
■ Valve.
PRO/II 5.11 Add-On Modules User’s Guide 1-1

Thermodynamic Models
Eight groups of built-in electrolyte models in PRO/II simulate aque-
ous systems in a wide range of industrial applications. The models
BATCH
apply to fixed component lists with a predefined set of thermody-

namic methods for K-values, enthalpies, and densities. It is not pos-
sible to define individual methods for K-value, enthalpy, or density
when using electrolyte thermodynamic models.
Note: Electrolyte models cannot be used to calculate the follow-

ing properties:
● Non-aqueous electrolyte systems.

● Free water decant.
ELECTROLYTES
● Water dew points.

● Hydrocarbon dew points.
● Entropy and heat capacity.
The following electrolyte models are available in this release:
■ Amine Systems.
■ Acid Systems.
■ Mixed Salt Systems.
■ Sour Water Systems.
■ Caustic Systems.
■ Benfield Systems.
■ Scrubber Systems.
■ LLE and Hydrate Systems.
To select an electrolyte model:
➤ Click the Thermodynamics Data button on the toolbar to dis-
play the Thermodynamics Data dialog box (Figure 1-1).
1-2 Electrolyte Module

Figure 1-1: Thermodynamic Data Dialog Box
➤ Select Electrolyte in the Category list.
ELECTROLYTES
➤ Choose an appropriate electrolyte model.
You may add your own models, specifically suited to your applica-
tion, by using PRO/II and the Electrolyte Utility Package (EUP).
You should be careful when using non-electrolyte and electrolyte

thermodynamic methods in the same application. The PRO/II elec-
trolytic models use a different enthalpy basis from that used for
other thermodynamic systems. When both are used, PRO/II auto-
matically takes care of this difference, but it may appear to be con-
fusing. To avoid this, select the electrolyte enthalpy method for all
non-electrolyte thermodynamic systems in a mixed application. All
systems will then use the electrolyte model basis.
When using Electrolyte thermodynamic methods, the OLILIB com-

ponent databank must be searched first and the SIMSCI databank
second. You can set this hierarchy by clicking the Hierarchy button
in the Component Selection dialog box. See the online help for
more information on setting the databank search order hierarchy.
Generating Electrolyte Components

All electrolyte components resulting from a selected electrolyte
thermodynamic model can be generated automatically when the
thermodynamic method is selected. However, you can also elect to
generate these components via a menu option once the electrolyte
thermodynamic model is selected. Electrolyte components are
always generated automatically before the simulation is run.

To generate the electrolyte components:
➤ Select Generate Electrolyte Components from the Input menu.

BATCH
All electrolyte components for the flowsheet (including compounds

and solid precipitates) are generated automatically.
Electrolytic Column Algorithm (ELDIST)

This column algorithm was designed to solve non-ideal aqueous
electrolytic distillation columns involving ionic species. It uses a
Newton-Raphson method to solve the mass balance, vapor-liquid
equilibrium, and specification equations simultaneously. The
K-values and enthalpies are supplied by the electrolyte thermody-
namic model.
ELECTROLYTES
The Electrolytic Column Algorithm is selected from the Column

Algorithm drop-down list in the Column dialog box.
Note: Electrolytic thermodynamic models support only VLE, and

so total phase draws are not permitted.
Advantages and disadvantages of the Electrolytic Column Algo-
rithm follow:
■ Advantages —
● Rigorously models ionic equilibrium systems.

● Solves highly non-ideal distillation columns.
■ Disadvantages —
● Side columns are not supported.
● Pumparounds and tray hydraulics are not available
● Certain column specifications and variables are not

permitted.
Electrolyte Modeling
The PRO/II Electrolytes module integrates rigorous electrolyte ther-
modynamic algorithms developed by OLI Systems, Inc. (1) with
SIMSCI’s comprehensive flowsheet simulator. The following sec-
tions describe the differences between the electrolyte version and
standard PRO/II.

■ Electrolyte General Data — Description of the GENERAL
DATA keyword input. Overview of the electrolyte-specific out-
put available with the PRINT ION option. Discussion of true
solution species and reconstituted components.
■ Electrolyte Component Data — Description of the COMPO-

NENT DATA keyword input. Discussion of the electrolyte-spe-
cific pure-component databank, OLILIB.
■ Electrolyte Thermodynamic Data — Description of the

THERMODYNAMIC DATA keyword input. Discussions of the
validity range for the electrolyte thermodynamic method,
mixed thermodynamic applications, and special case STREAM
DATA input requirements.
ELECTROLYTES
■ Electrolyte Models — Summaries of the chemical species and
equilibria considered in the 40 built-in ELECTROLYTE MODELS,
including an index, which gives the names of all built-in mod-
els that contain a given component.
■ Generating a User-Added Electrolyte Model — Description

of the use of the Electrolyte Utility Package (EUP) for generat-
ing user-added models, private databanks, and executing stan-
dalone flash drum calculations and sensitivity analyses.
■ Electrolytes in PRO/II Flowsheeting — Overview of the

UNIT OPERATIONS available with PRO/II Electrolytes, includ-
ing description of electrolyte-specific features and PRO/II fea-
tures not available for units using electrolyte thermodynamic
methods. Summaries of keyword input files for the Flash Drum
(as an example of a standard PRO/II unit with a few changes in
functionality) and for the ELDIST Distillation unit (which is spe-
cially designed for PRO/II Electrolytes (2)). Examples of key-
word input files for units using Electrolyte thermodynamic
methods also are provided.
PRO/II Electrolytes is composed of an integrated set of programs

developed by SIMSCI and OLI Systems, Inc. that allows you to
model and simulate aqueous electrolyte solutions. This includes,
under the PRO/II flowsheeting environment, algorithms for the sim-
ulation of single-stage and multistage steady-state processes involv-
ing aqueous electrolytes. These programs calculate both
heterogeneous, multiphase equilibria as well as homogeneous liq-
uid-phase reaction equilibria. The allowed phases at equilibrium
include vapor, aqueous liquid, organic liquid, and solid phases.

With respect to liquid-solid equilibria, saturation of multiple solid
phases can be calculated rigorously.
BATCH
General Information
PRO/II Electrolytes simulates aqueous systems by solving mathe-
matical models that accurately represent these systems. These mod-
els are sets of nonlinear algebraic equations containing appropriate
thermodynamic parameters. Two thermodynamic methods are
available for electrolyte modeling, the OLI method and the NRTL
(Chen) method. The Electrolyte NRTL method can be used for
modeling very concentrated electrolyte solutions with very low
water content (as low as 0.3 wt%) as well as solutions with mixed
solvents ranging in composition from completely aqueous to almost
ELECTROLYTES
completely non-aqueous (again, with water content as low as

0.3 wt%).
PRO/II Electrolytes is built upon a rigorous thermodynamic frame-
work for aqueous electrolyte systems. This framework is an amal-
gam based upon work by Bromley (3), Meissner (4,5), Pitzer (6,7),
Zemaitis (8,9), Nothnagel (10), Nakamura (11), and Tanger (12).
The PRO/II Electrolytes module incorporates electrolyte models
created using standalone software from OLI Systems, Inc. The
PRO/II Electrolytes module has 40 built-in electrolyte models that
can be applied to a wide range of problems of industrial interest,
including, but not limited to the following:
■ Gas scrubbers/purification using carbonate, amine, or caustic

solutions
■ Sour water strippers

■ Amine towers
■ Benfield processes
■ Acid waste stream-neutralization drums
■ Scale formation prediction for wells and pipes (oilfields, geo-

thermal fields)
■ Underground injection well studies
■ Solid salts manufacturing (potash, caustic, carbonates, etc.)
■ Chlor-alkali plant processes.

The integration of electrolytes into PRO/II is, from the user’s point
of view, seamless. In many cases, a keyword input file for an elec-
trolytes problem could be identical (apart from entering the name of
the electrolyte model in the Thermodynamic Data section) to a non-
electrolyte PRO/II input file. The four most important things that
PRO/II Electrolyte users must remember are:
■ PRO/II Electrolytes is designed for use in aqueous electrolyte

systems within the application guidelines given in Electrolyte
Thermodynamic Data. PRO/II Electrolytes cannot currently be
used for mixed-solvent or non-aqueous electrolyte systems,
with the exception of the user-generated models created in the
Electrolyte NRTL framework.
ELECTROLYTES
■ The model chosen in the THERMODYNAMIC DATA keyword input
(see Chapter 2, Electrolyte Models) must contain all of the
components appearing in any stream that is to be treated with
that thermodynamic method.
■ PRO/II Electrolytes has one new unit operation (ELDIST), a

few units are not available, and some other units have reduced
functionality when used with an electrolyte thermodynamic
method. These differences are discussed fully in Chapter 3,
Generating a User-Added Electrolyte Model.
■ The Electrolyte Utility Package (EUP) supplied with PRO/II

Electrolytes allows the user to generate new electrolyte models.
See the discussion in Chapter 3, Generating a User-Added
Electrolyte Model.
If these few differences are kept in mind, users familiar with stan-
dard PRO/II keyword input can quickly make effective use of the
capabilities of the PRO/II Electrolytes module.
Electrolyte General Data

Calculated quantities unique to electrolyte applications can be
printed in the output file using the ION keyword after the PRINT
statement. The ION entry has three options: ION=NONE or PART or
ALL. The default is PART.
NONE No electrolyte-specific output is printed.

PART Adds Liquid Rates table(s) to the Stream Compo-
nent Rates section(s) of the output. This table
gives the flowrates for ionic and/or other true spe-
BATCH
cies in the aqueous solution. Adds, for ELDIST

column only, tables for Tray Compositions for
True Solution Species, Tray Liquid pH and Ionic
Strength, and Tray Component Scaling Indices.
ALL Gives all output given by PART option. Adds Elec-

trolyte Thermo Summary section of the output.
This section gives the equilibrium phases and
phase compositions obtained from the electrolyte
flash calculation. Aqueous solution compositions
ELECTROLYTES
are reported as molalities for the true chemical

species. Also given are values for activity and
fugacity coefficients as well as equilibrium con-
stants. Adds Thermo Notes section to output. This
section gives explanatory notes useful for the
interpretation of the quantities given in the
Electrolyte Thermo Summary.
True Aqueous Solution Species and Reconstituted Components

The true chemical species in the aqueous solution are those aqueous
species that are included in the model’s ionic equilibria and VLE
expressions. Mass and charge balance constraints for the aqueous
phase, together with the model’s aqueous ionic equilibria expres-
sions, are used by PRO/II Electrolytes to calculate apparent concen-
trations of the model’s neutral components in the aqueous phase
automatically from the corresponding concentrations of the true
solution species (ionic and neutral). This calculation is referred to
as the reconstitution of model components. Concentrations and
rates are reported in the output for reconstituted components and, if
ION=PART or ALL is specified on the PRINT statement, they are also
reported for true solution species.
Example:
Calculate the results of an isothermal flash of the feed given below
at 1 bar and 25°C, where the numbers before denote moles.
Model components:
H2O, NaOH, HCl, NaCl

Feed components:
55.51 H2O + 1 NaOH + 1 HCl
Product in terms of True Chemical Species:
56.51 H2O + 1 NA+1 + 1 Cl-1 + 1.0E-7 OH-1 + 1.0E -7 H +1
Product in terms of Reconstituted Components:
56.51 H2O + 1 NaCl
Electrolyte Component Data

Component name lists for the electrolyte models are given in the
Summary of Electrolyte Models. The names in these lists are
printed as they should be entered in the Component Data section on
ELECTROLYTES
the LIBID statement. However, a Pure Component Library name, as
given in the SIMSCI Component and Thermodynamic Data Refer-
ence Manual, Section 1.4, Pure Component Library–Alpha Sort,
and Section 1.5, Pure Component Library–Formula Sort, can be
used instead of a corresponding electrolyte model component name.
For example, you could enter CAHYDROX on the LIBID statement in
place of the name CAOH2 when using the electrolyte model SCRU.
Note: In contrast to conventional PRO/II, the Electrolytes version

does not allow two or more different names for the same compo-
nent to be used at the same time in the Component Data input.
Components can be renamed for printing purposes using the PRO/II

alias approach.
Example:
LIBID
1,NACL,,HALITE
will cause the alias, HALITE, to be printed in the output in place of
the OLI Library name, NACL.
Components in OLI’s databanks that are not covered in the SIMSCI

bank are given in the OLILIB bank. For electrolyte applications, the
recommended bank search order is OLILIB first and SIMSCI sec-
ond. This search order is used as the default whenever an electrolyte
thermodynamic method is used.
Example:
LIBID
1,H2O/2,NACL, BANK=OLILIB,SIMSCI

Electrolyte Thermodynamic Data
The electrolyte models in PRO/II are characterized by a fixed list of
components, a fixed set of chemical equilibria, and a fixed set of
BATCH
thermodynamic methods for K-values, enthalpy, and density. The

components and equilibria considered in the 40 pregenerated elec-
trolyte models in PRO/II are summarized in Chapter 2, Electrolyte
Models.
This section provides a summary of the THERMODYNAMIC DATA
keyword input, and a set of application guidelines.
Note: See the PRO/II Reference Manual for a summary of the

thermodynamic framework and the mathematical model used by
ELECTROLYTES
PRO/II Electrolytes for the calculation of thermodynamic quanti-

ties and chemical equilibrium, respectively.
The name of the selected electrolyte model is treated in the input as

a system of thermodynamic methods.
Example:
METHOD
SYSTEM=SW01
where SW01 represents the name of an electrolyte model.
When multiple thermodynamic methods are needed for an applica-

tion, each of the selected methods should be assigned a method SET
identifier.
Example:
METHOD
SYSTEM=SW01, SET=SET1
where SET1 is the SET identifier.
Four options are available for calculating vapor-phase fugacities

with PRO/II Electrolytes. These options, with their keywords, are:
● Ideal-Gas (IDEA)
● Nothnagel (NOTH)
● Nakamura (NAKA)
● Soave-Redlich-Kwong (SRK).
These options are specified on the METHOD statement with the PHI
entry. If no vapor fugacity option is specified, the calculations
default to ideal-gas.

Examples:
METHOD
SYSTEM=GENX, PHI=SRK
METHOD
SYSTEM=SW01, PHI=NOTH
Note: Only SYSTEM, SET, PHI, TRANSPORT, VISCOSITY, CON-

DUCTIVITY, SURFACE, and DIFFUSIVITY statements (see PRO/II
Keyword Manual, Sec. 20, Thermodynamic Data) are available for
use with electrolyte thermodynamic methods. However, the
PETRO transport property option cannot be used with electrolyte
models, nor can the SIMSCI or API liquid-viscosity options. The
KVALUE, ENTHALPY, and DENSITY methods for electrolytes are
automatically set to the method declared by the SYSTEM entry and
ELECTROLYTES
cannot be modified individually on the METHOD statement.
Application Guidelines
The first step in selecting an electrolyte model as a thermodynamic
method is to determine whether the application of interest falls
within the application guidelines for PRO/II Electrolytes. For exam-
ple, the expected pressures, temperatures, phases, and phase com-
positions for the application should fall within the stated validity
ranges for PRO/II Electrolytes. Next, the user needs to identify one
of the PRO/II Electrolyte models that contains all of the compo-
nents of interest in its component list (see Chapter 2, Electrolyte
Models). However, for applications using electrolyte models
together with non-electrolyte thermodynamic methods, the compo-
nents to be treated by the non-electrolyte methods do not need to be
in the model’s component list if they will not enter any unit using
the electrolyte model.
Pressure, Temperature, and Composition Validity Ranges

The suggested application range for electrolyte thermodynamic
methods is summarized below.
General range
Temperature 32-390°F (0-200°C)
Pressure 0-200 atm
Dissolved gases 0-30 mole%
Ionic solutes 0-30 ionic strength
Amine systems
Pressure 0-30 atm

LLE systems
Organic solutes 10 weight%
where the ionic strength (I) is defined as:
BATCH
1
I = --- ∑ Z ions m ions
2
(1-2)
2
i ons
and Z denotes the ionic charge and m represents the molality of the
aqueous ion. Molality is defined as the moles of solute per 1000
grams of H2O solvent.
Vapor-Phase Fugacity Coefficients

Four alternative methods are provided:
ELECTROLYTES
■ Ideal: all fugacity coefficients are assumed to be 1.0.
■ Nothnagel method: generally valid up to 20 atmospheres, but

not available for some vapor-phase components.
■ Nakamura method: generally valid at higher pressures up to

200 atmospheres, but not available for some vapor-phase com-
ponents.
■ Soave-Redlich Kwong (SRK) method: valid over a wide

range of conditions and generally recommended when vapor-
phase nonideality is important. Also valid for any vapor-phase
chemical species given in OLI’s component databanks distrib-
uted with the Electrolyte Utility Package (EUP).
Invalid Calculations for Electrolyte Models

■ Nonaqueous electrolyte systems.
■ Free water decant.
■ Dew water calculations.
■ Dew hydrocarbon calculations.
■ Entropy and heat capacity calculations.
Use of ENTHALPY = ELEC for Mixed Thermodynamic Applications

The thermodynamic framework for PRO/II Electrolytes uses a dif-
ferent basis, or zero-point, for enthalpies from regular PRO/II.
When both electrolyte and non-electrolyte thermodynamic methods
are used in a flowsheet, PRO/II takes care of this basis change auto-
matically if a stream is changed from one method to another.

However, to avoid the potentially confusing appearance of disconti-
nuities in output values of enthalpy, it is recommended that the
ENTH=ELEC option be used for all non-electrolyte thermodynamic
methods in mixed electrolyte/non-electrolyte thermodynamic appli-
cations. ENTH= ELEC is PRO/II’s IDEAL enthalpy method trans-
lated by a constant to give numbers consistent with the enthalpy
basis for PRO/II Electrolytes.
Example:
METHOD
SYST=SALT, DEFAULT
METHOD
SYST=IDEAL, ENTH=ELEC, SET=SET2
METHOD
ELECTROLYTES
SYST=SRK, ENTH=ELEC, SET=SET3
Note that ENTH=ELEC is used with both non-electrolyte thermody-
namic methods, IDEAL and SRK. For these two methods, the
calculated enthalpy values will be obtained using the IDEAL
enthalpy method followed by a conversion to put these values on the
electrolyte basis.
An example in which this method is useful is when steam is flashed
off from an electrolyte unit (a stage in a multi-effect evaporator, for
example) and then condensed to provide duty for a heat exchanger
(the adjacent stage in the evaporator, for example). OLI’s flash cal-
culation has difficulty with adiabatic (fixed-duty) calculations for
pure water in the two-phase region, with the result that the steam
side of the heat exchanger might fail to solve with electrolyte ther-
modynamic methods. Instead, the user could specify the IDEAL
thermodynamic method with ENTH=ELEC for the steam side of the
exchanger to produce a converged solution with consistent enthalp-
ies for all streams.
Note: Whenever multiple enthalpy methods are used in a flow-

sheet, the safest (and recommended) practice for resetting the
enthalpy basis is to take the stream that is changing methods
through the reset unit that converts to the new enthalpy method.
See the discussion in the PRO/II Keyword Manual, Section 20.5,
Multiple Thermodynamic Sets.
Special Case STREAM DATA Input

Due to the nature of the aqueous electrolyte flash algorithm, elec-
trolyte feed streams with little or no water require special handling
during input; you must specify the phase of the stream in the Stream
Data section. Note that water-free liquid feed streams are not per-

mitted. The algorithm also occasionally has difficulty converging
for vapors or liquids at conditions very near the vapor-liquid phase
boundary. Here again, if the user knows the phase of the stream, it
BATCH
can be entered on the PROPERTY statement; this will assure conver-

gence but should be used with caution because the feed flash will
not be able to correct an incorrect phase designation.
1) Feeds with little or no H2O
Vapor feed Enter PHASE=V on PROPERTY statement
Solid feed Use SOLID card together with PROPERTY statement
Liquid feed Not allowed. H2O must be the predominant component
in the liquid phase.
2) Feeds near saturation

ELECTROLYTES
At pressures and temperatures close to vapor+ liquid saturation

conditions, it is recommended to enter the appropriate PHASE (V or L)
on the PROPERTY statement.
Example:
Set up a pure HCl vapor feed and a pure NaOH solid feed at 25°C
and 1 atm, together with a liquid H2O feed at vapor-liquid satura-
tion conditions of 100°C and 1 atm.
...
COMPONENT DATA
LIBID
1, H2O/2, NAOH/3, HCL
THERMODYNAMIC DATA
METHOD
SYSTEM=GENE
STREAM DATA
PROPERTY
STRM=HCLV, TEMP=25, PRES=1, &
COMP=3, 0.5, PHASE=V
PROPERTY
STRM=SOLD, TEMP=25, PRES=1, &
SOLID STRM=SOLD, COMP=2,0.5
PROPERTY
STRM=WATR, TEMP=100, PRES=1, &
COMP=1, 100, PHASE=L

References
1. OLI Systems, Inc., 1995, Prochem User’s Manuals, Version 12,
Morris Plains, NJ.
2. V.B. Shah, and R.W. Bondy, 1991, “A New Approach to Solv-
ing Electrolyte Distillation Problems”, a paper presented at the
AIChE Annual Meeting in Los Angeles.
3. L. A. Bromley, 1973, “Thermodynamic Properties of Strong
Electrolytes in Aqueous Solutions”, AIChE J, 19:313-320.
4. H. P. Meissner, and C. L. Kusik, 1973, “Aqueous Solutions of
Two or More Strong Electrolytes - Vapor Pressures and Solu-
bilities”, IEC Proc. Des. Dev., 12:205-208.
ELECTROLYTES
5. H. P. Meissner, and N. A. Peppas,1973, “Activity Coefficients -
Aqueous Solutions of Polybasic Acids and their Salts”, AIChE
J., 19:806-809.
6. K. S. Pitzer, 1979, “Theory: Ion Interaction Approach”, Activity
Coefficients in Electrolyte Solutions, 1:157-208, R. M. Pytkow-
icz, ed., CRC Press, Boca Raton, FL.
7. K. S. Pitzer, 1980, “Thermodynamics of Aqueous Electrolytes
at Various Temperatures, Pressures and Compositions”, Ther-
modynamics of Aqueous Systems with Industrial Applications,
451-466, S. A. Newman, ed., ACS Symposium Series 133.
8. J. F. Zemaitis, Jr., 1980, “Predicting Vapor-Liquid-Solid Equi-
libria in Multicomponent Aqueous Solutions of Electrolytes”,
Thermodynamics of Aqueous Systems with Industrial Applica-
tions, 227-246, S. A. Newman, ed., ACS Symposium
Series 133.
9. J. F. Zemaitis, Jr., D. M. Clark, M. Rafal, and N. C. Scrivner,
1986, Handbook of Aqueous Electrolyte Thermodynamics,
AIChE Press.
10. K. H. Nothnagel, D. S. Abrams, and J. M. Prausnitz, 1973,
“Generalized Correlation of Fugacity Coefficients in Mixtures
at Moderate Pressures”, IEC Process Des. Dev., 12:25-35.
11. R. Nakamura, G. J. F. Breedveld, and J. M. Prausnitz, 1976,
“Thermodynamic Properties of Gas Mixtures Containing
Polar and Nonpolar Components”, IEC Process Des. Dev.,
15:557-564.

12. J.C. Tanger, IV, and H.C. Helgeson, 1988, “Calculation of the
Thermodynamic and Transport Properties of Aqueous Species
at High Pressures and Temperatures: Revised Equations of
BATCH
State for the Standard State Partial Molal Properties of Ions and
Electrolytes”, Am. J. Sci, 288:19-98.
ELECTROLYTES

Chapter 2
Electrolyte Models
ELECTROLYTES
This section summarizes the forty pregenerated Electrolyte models
in the PRO/II Electrolyte module. To facilitate application of these
built-in models, the following tables are provided:
Page
Electrolyte Model Index 2-2
■ Component name lists
■ Page index for model summaries
Summary of Electrolyte Models 2-5
■ Component and ion name lists
■ Equilibrium expressions
Component Index for Electrolyte Models 2-32
■ Alphabetical list of component names
■ Name lists of models containing the component of interest
Application Guidelines
Pregenerated Models
The electrolyte model chosen must contain all components appear-
ing in any stream or unit using that method. To reduce CPU time
and eliminate extraneous components from the printout, it is gener-
ally best to use the smallest model encompassing the flowsheet’s
components. Similarly, a model without solids will run faster than a
model with the same components that does allow solid precipita-
tion. Non-solids-forming models should be used only for flowsheets
where the user is certain precipitation will not occur. Models with

solids suppressed are designated by names ending in X; for exam-
ple, CAUX is the CAUS model without solid precipitation.
BATCH
User-Added Models
If none of the 40 pregenerated models is suitable for an application,
user-added, electrolyte models should be investigated. SIMSCI’s
Electrolyte Utility Package (EUP) allows generation of user-added
models that can be used in the PRO/II Electrolytes program. When
model generation is necessary, two possibilities can occur:
■ All desired model components are included in the databanks

used by the EUP. In this case, model generation is relatively
quick and easy.
ELECTROLYTES
■ Some desired model components are not included in the EUP

databanks. In this case, the EUP can be used to add these com-
ponents to its databanks if the appropriate thermodynamic data
are available.
Electrolyte Model Index

Model names (MEA, DEA, etc.) are grouped by systems of general
chemical or application interest.
Models Components Page

Amine Systems 2-5
MEA H2O / CO2 / C2H6 / CH4 / H2S / N2 / C4H10 / C3H8 / 2-5
MEAH
DEA H2O / CO2 / C2H6 / CH4 / H2S / N2 / C4H10 / C3H8 / 2-5
DEAH
TEA H2O / CO2 / C2H6 / CH4 / H2S / N2 / C4H10 / C3H8 / 2-5
TEAH
DGA H2O / CO2 / C2H6 / CH4 / H2S / N2 / C4H10 / C3H8 / 2-5
DGAH
MDEA H2O / CO2 / C2H6 / CH4 / H2S / N2 / C4H10 / C3H8 / 2-5
MDEAH
DIPA H2O / CO2 / C2H6 / CH4 / H2S / N2 / C4H10 / C3H8 / 2-5
DIPAH
2-2 Electrolyte Models

Acid Systems 2-6
ACID H2O / CO / CO2 / H2 / HCN / HCOOH / N2 / NH3 / 2-6
H3PO4
HCL H2O / HCl 2-7
CL2 H2O / HCl / Cl2 / HClO / N2 2-7
CLSF H2O / HCl / Cl2 / HClO / N2 / O2 / SO2 / H2SO3 / 2-7
H2SO4
SULF H2O / SO2 / H2SO3 / H2SO4 2-8
PHOS H2O / H3PO4 2-9
ELECTROLYTES
Mixed Salt Systems 2-9
SALT H2O / NaCl / KCl 2-9
CANA, CANX H2O / HCl / MgSO4 / Na2SO4 / NaCl / H2SO4 / 2-10
CaSO4 / NaOH / CaCl2 / MgCl2 / Ca(OH) 2 /
Mg(OH)2
HOTC, HOTX H2O / CO2 / CO / C2H6 / CH4 / H2S / H2 / N2 / C3H8 / 2-11
NaHCO3 / Na2CO3 / NaOH
GENE, GENX H2O / CO2 / Cl2 / HClO / HCl / N2 / O2 / SO2 / NaOH 2-12
/ NaCl / NaHCO3 / Na2CO3
GEOT H2O / CO2 / NH3 / H2S / HCl / BaCl2 / CaCl2 / CuCl2 2-13
/ FeIICl2 / FeIIICl3 / KCl /LiCl / MgCl2 / MnCl2 /
NaCl / Na2S / Na2SO3 / Na2SO4 / PbCl2 / SrCl2 /
ZnCl2 / Na4EDTA / Ca2EDTA / B(OH)3 / BaCO3 /
BaSO4 / CaCO3 / CaSO4 / Fe3O4 / MgCO3 /
(NH4)2SO4 / SrCO3 / SrSO4
OILF H2O / CO2 / HCl / Na2SO4 / NaHCO3 / Na2CO3 / 2-15
MgCl2 / BaCl2 / CaCl2 / NaCl / NaOH / KCl /
BaSO4 / CaCO3 / CaSO4 / BaCO3 / Ca(OH)2 / K2CO3
/ K2SO4 / KHCO3 / MgCO3 / Mg(OH)2 / BaOH2 /
KOH / MgSO4 / H2SO4
Sour Water Systems 2-17
SW01, SW1X H2O / CO2 / H2S / NH3 / CH4 / C6H5OH / NaOH / 2-17
NaHCO3 / Na2CO3 / C2H6 / C3H8 / N2 / HCl / HCN /
H3PO4 / NaCl / NaHS / HCOOH

NaHCO3 / Na2CO3 / HCl / NaCl / NaHS / HCN /
BATCH
ACETACID
NaHCO3 / Na2CO3 / C2H6 / C3H8 / N2 / HCl / HCN /
C4H10 / NaCl / NaHS / H2 / O2 / CO
NaHCO3 / Na2CO3 / C2H6 / C3H8 / N2 / C4H10
SW05 H2O / CO2 / H2S / NH3 2-22
Caustic Systems 2-23
ELECTROLYTES
CAUS, CAUX H2O / Cl2 / HClO / HCl / SO2 / NaCl / Na2SO3 / 2-23
Na2SO4 / NaOH / H2SO4
CAU2, CA2X H2O / NaOH / KOH 2-24
Benfield Systems 2-25
BENF, BENX H2O / CO2 / CO / C2H6 / C2H4 / CH4 / H2S / H2 / N2 / 2-25
NH3 / C3H8 / K2CO3 / KHCO3 / KHS / H3PO4 /
B(OH)3 / KOH
Scrubber Systems 2-26
SCRU, SCRX H2O / CO2 / HCl / HCN / HCOOH / N2 / O2 / SO2 / 2-26
NaOH / CaCO3 / CaCl2 / NaCl / Na2CO3 / NaHCO3 /
NaCOOH / Ca(OH)2
LLE and Hydrate Systems 2-27
TWL1 H2O / CO2 / H2S / NH3 / CH4 / C6H5OH / Toluene / 2-27
NaOH / NaOH.H 2O / Na2CO3 / Na2CO3·10H2O /
Na2CO3·H2O/ Na2CO3·7H2O / NaHCO3 / NaCl /
NaHS / HCl / CaCl2 / CaCl2·H2O / CaCl2·2H2O /
CaCl2·4H2O / CaCl2·6H2O / Ca(HCO3)2 / CaCO3 /
Ca(OH)2 / NH4Cl / NH4HCO3 / NH4HS
TWL2 H2O / NaCl / NaHSO4 / Na2SO4 / Na2SO4·10H2O / 2-30
NaOH / NaOH·H2O / Ca(HSO4)2 / CaSO4 /
CaSO4·2H2O / Ca(OH)2 / HCl / N2 / CH4 / Methanol
/ Ethanol / M-Xylene / Benzene / Toluene / CaCl2 /
CaCl2·H2O / CaCl2·2H2O / CaCl2·4H2O / CaCl2·6H2O
/ HF / H2SO4 / CaF2 / NaF

Summary of Electrolyte Models
All ionic equilibria given in the model summaries below take place
in aqueous solution. The ppt suffix on a chemical species name
denotes a solid precipitate, and the aq suffix stands for a dissolved
gas or an electrically neutral ion pair. The general form of a vapor-
liquid equilibrium expression is Cvap = Caq, where C denotes a
model component.
Amine Systems
MEA Model
Components:
ELECTROLYTES
H2O / CO2 / C2H6 / CH4 / H2S / N 2 / C3H8 / C4H10 / MEAH
Ions:
-1 -1 +1 -1 -2 -2
OH / HCO3 /H / HS / MEA-1 / MEAH2+1 / CO3 /S
Ionic Equilibria:
+1 -1
CO2aq + H2O = H + HCO3
+1 -1
H2 O = H + OH
H2Saq = H+1 + HS-1
HCO3-1 = H+1 + CO3-2
HS-1 = H+1 + S-2
MEACO2-1 + H2O = MEAHaq + HCO3-1
MEAHaq + H2O = MEAH2+1 + OH-1
Vapor-Liquid Equilibria:
Vapor-liquid equilibrium is considered for all components.
DEA, TEA, DGA, MDEA, and DIPA Models

Component lists for the other amine models differ from the MEA
model only with respect to their amine components; that is, DEAH,
TEAH, DGAH, MDEAH, or DIPAH replaces MEAH. In addition,
these other amine models do not consider vapor-liquid equilibrium
for their amine component. Finally, there is no MDEACO2-1 ion in
the MDEA model.

Acid Systems
ACID Model
BATCH
Components:
H2O / CO / CO2 / H2 / HCN / HCOOH / N2 / NH3 / H 3PO4
Ions:
-1 -2 -1 -2 -1 -1 -1
OH / CO3 / COOH / H2P2O7 / H2PO4 / H 3P2O7 / HCO3 /
+1 -3 -2 -1 +1 -1 -4 -3
H / HP2O7 / HPO4 / NH 2CO2 / NH 4 / CN / P 2 O7 / PO4
Ionic Equilibria:
ELECTROLYTES
-1 +1
CO2aq + H2O = HCO3 +H
H2O = H+1 + OH-1
H2P2O7-2 = H+1 + HP 2O7-3
H2PO4-1 = H+1 + HPO4-2
H3P2O7-1 = H+1 + H 2P2O7-2
HCNaq = H+1 + CN-1
HCO3-1 = H+1 + CO3-2
HCOOHaq = H +1 + COOH-1
HP2O 7-3 = H+1 + P2O7-4
HPO4-2 = H+1 + PO 4-3
NH2CO2-1 + H2O = NH3aq + HCO3-1
NH3aq + H2O = NH4+1 + OH-1
P2O 7-4 + H2O = 2PO 4-3 + 2H+1
Vapor-liquid equilibrium is not considered for H 3PO 4.

HCL Model
Components:
H2O / HCl
Ions:
OH-1 / H+1 / Cl-1
Ionic Equilibria:
H2O = H+1 + OH-1
HClaq = H+1 + Cl-1
ELECTROLYTES
CL2 Model
Components:
H2O / Cl2 / HClO / HCl / N2
Ions:
OH-1 / ClO-1 / H+1 / Cl-1
Ionic Equilibria:
Cl2aq + H2O = H +1 + Cl-1 + HClOaq
H2O = H+1 + OH-1
HClaq = H+1 + Cl-1
HClOaq = H+1 + ClO-1
CLSF Model
Components:
H2O / Cl2 / HClO / HCl / N2 / O2 / SO2 / H2SO3 / H2SO4
Ions:
-1 -1 +1 -1 -1 -1 -2 -2 -2
OH / ClO /H / HSO 3 / HSO4 / Cl / S 2 O5 / SO3 / SO 4

Ionic Equilibria:
BATCH
H2O = H+1 + OH-1
HClaq = H+1 + Cl-1
HClOaq = H+1 + ClO-1
HSO3-1 = H+1 + SO 3-2
HSO4-1 = H+1 + SO 4-2
S2O 5-2 + H2O = 2SO 3-2 + 2H+1

ELECTROLYTES
SO2aq + H2O = HSO3-1 + H+1
Vapor-liquid equilibrium is not considered for H 2SO 3 / H 2SO 4.
SULF Model
Components:
H2O / SO2 / H2SO3 / H2SO4
Ions:
OH-1 / HSO3-1 / HSO4-1 / H +1 / S2O 5-2 /
SO3-2 / SO4-2
Ionic Equilibria:
H2O = H+1 + OH-1
HSO3-1 = H+1 + SO 3-2
HSO4-1 = H+1 + SO 4-2
S2O 5-2 + H2O = 2SO 3-2 + 2H+1
SO2aq + H2O = HSO3-1 + H+1
Vapor-liquid equilibrium is considered for H2O / SO2.

PHOS Model
Components:
H2O / H3PO 4 / PO4
Ions:
OH-1 / H2PO 4-1 / H3P2O7-1 / H+1 / HP 2O7-3 / HPO 4-2 / H2P2O7-2 /
P2O 7-4 / PO4-3
Ionic Equilibria:
H2O = H+1 + OH-1
ELECTROLYTES
H2P2O7-2 = H+1 + HP 2O7-3
H2PO4-1 = H+1 + HPO4-2
H3P2O7-1 = H+1 + H 2P2O7-2
HP2O7-3 = H+1 + P2O7-4
-2 +1 -3
HPO4 =H + PO 4
-4 -3 +1
P2O 7 + H2O = 2PO 4 + 2H
Vapor-liquid equilibrium is considered for H2O only.
Mixed Salt Systems

SALT Model
Components:
H2O / NaCl / KCl
Ions:
OH-1 / H+1 / K+1 / Na+1 / Cl-1
Precipitates and hydrates:

NaCl / KCl
Ionic Equilibria:
+1 -1
H2 O = H + OH

KClppt = K+1 + Cl-1
NaClppt = Na+1 + Cl-1

BATCH
Vapor-liquid equilibrium is considered for H 2O only.
CANA Model
Components:
H2O / HCl / MgSO4 / Na2SO4 / NaCl / H2SO4 / CaSO4 / NaOH /
CaCl2 / MgCl2 / Ca(OH)2 / Mg(OH)2

ELECTROLYTES
Ions:
OH-1 / CaOH+1 / Cl-1 / H+1 / HSO4-1 / MgCl+1 / Mg+2 / Na+1 /
NaSO4-1 / Ca+2 / SO4-2
Precipitates and hydrates:

MgSO4 / Na2SO4 / NaCl / CaSO4 / NaOH / CaCl2 / MgCl2 /
Ca(OH)2 / Mg(OH)2
Ionic Equilibria:
CaCl2ppt = Ca+2 + 2Cl-1
Ca(OH)2ppt = Ca+2 + 2OH-1
CaOH+1 = Ca+2 +OH-1
CaSO4aq = Ca+2 + SO 4-2
CaSO4ppt = Ca+2 + SO4-2
H2O = H+1 + OH-1
HClaq = H+1 + Cl-1
HSO4-1 = H+1 + SO 4-2
MgCl2ppt = Mg+2 + 2Cl-1
MgCl+1 = Mg+2 + Cl-1

Mg(OH)2ppt = Mg+2 + 2OH-1
MgSO4ppt = Mg+2 + SO4-2
Na2SO4ppt = 2Na+1 + SO4-2
NaOHppt = Na+1 + OH -1
NaSO4-1 = Na+1 + SO4-2
Vapor-liquid equilibrium is considered for H 2O / HCl.
ELECTROLYTES
CANX Model
Identical to CANA model except that solid precipitation equilibria
are not considered.
HOTC Model
Components:
H2O / CO2 / CO / C2H6 / CH 4 / H2S / H2 / N2 / C 3H8 / NaHCO3 /
Na2CO 3 / NaOH
Ions:
OH-1 / HCO3-1 / H+1 / HS-1 / Na+1 / CO 3-2 / S-2
Precipitates and Hydrates:

NaHCO3 / Na2CO3 / NaOH
Ionic Equilibria:
-1 +1
+1 -1
H2 O = H + OH
H2Saq = H+1 + HS-1
HCO3-1 = H+1 + CO3-2
HS-1 = H+1 + S-2
Na2CO 3ppt = 2Na+1 + CO3-2

NaHCO3ppt = Na+1 + HCO3-1
BATCH
Vapor-liquid equilibrium is not considered for NaHCO3 / Na2CO3 /
NaOH.
HOTX Model
Identical to HOTC model except that solid precipitation equilibria
are not considered.
GENE Model
ELECTROLYTES
Components:
H2O / CO2 / Cl2 / HClO / HCl / N2 / O2 / SO2 / NaOH / NaCl /
NaHCO3 / Na2CO3
Ions:
OH-1 / ClO-1 / CO3-2 / HCO 3-1 / H+1 / HSO3-1 / Na +1 / Cl-1 /
S2O 5-2 / SO3-2

NaOH / NaCl / NaHCO3 / Na2CO3
Ionic Equilibria:
-1 +1
+1 -1
H2 O = H + OH
+1 -1
HClaq = H + Cl
+1 -1
HClOaq = H + ClO
-1 +1 -2
HCO3 =H + CO3
-1 +1 -2
HSO3 =H + SO 3
+1 -2
Na2CO 3ppt = 2Na + CO3

S2O 5-2 + H2O = 2SO 3-2 + 2H+1
SO2aq + H2O = HSO3-1 + H+1
Vapor-liquid equilibrium is not considered for NaOH / NaCl /
NaHCO3 / Na2CO 3.
ELECTROLYTES
GENX Model
Identical to GENE model except that solid precipitation equilibria
are not considered.
GEOT Model
Components:
H2O / CO2 / NH3 / H 2S / HCl / BaCl2 / CaCl2 / CuCl2 / FeIICl2 /
FeIIICl3 / KCl / LiCl / MgCl2 / MnCl2 / NaCl / Na2S / Na2SO3 /
Na2SO4 / PbCl2 / SrCl2 / ZnCl2 / Na4EDTA / Ca2EDTA / B(OH)3 /
BaCO3 / BaSO 4 / CaCO3 / CaSO4 / Fe3O4 / MgCO3 / (NH4)2SO4 /
SrCO3 / SrSO4
Ions:
OH-1 / NH4+1 / Ba+2 / BaOH+1 / Ca+2 / CaHCO 3+1 / CaOH+1 /
Cu+2/FeII+2 / FeIIHCO 3+1 / FeIIOH+1 / FeIII+3 / K +1 /LI+1 / Mg+2 /
MgCl+1 / MgHCO3+1 / Mn+2 / MnHCO3+1 / MnOH+1 / Na+1 / Pb+2 /
Sr+2 / Zn+2 / ZnHCO3+1 / H +1 / HCO3-1 / CO 3-2 / NH2CO 2-1 / HS-1 /
S-2 / Cl-1 / NaSO4-1 / HSO3-1 / SO3-2 / HSO 4-1 / SO4-2 / EDTA-4 /
B(OH)3OH-1

BaCO3 / BaSO 4 / CaCO3 / Fe3O4 / MgCO3 / (NH 4)2SO4 /
BATCH
SrCO3 / SrSO4
Ionic Equilibria:
H2O = H+1 + OH-1
CO2aq + H2O = H+1 + HCO3-1
NH3aq + H2O = NH4+1 + OH-1
H2Saq = H+1 + HS-1

ELECTROLYTES
Na4EDTAaq = 4Na+1 + EDTA-4
Ca2EDTAaq = 2Ca+2 + EDTA-4
-1 +1
B(OH)3aq + H2O = B(OH)3OH +H
-1 +1 -2
HCO3 =H + CO3
-1 -1
NH2CO2 + H2O = NH3aq + HCO3
-1 +1 -2
HS =H +S
+1 +2 -1
BaOH = Ba + OH
+1 +2 -1
CaHCO3 = Ca + HCO3
+1 +2 -1
CaOH = Ca + OH
+1 +2 -1
FeIIHCO 3 = FeII + HCO3
+1 +2 -1
FeIIOH = FeII + OH
-1 +1 -2
HSO3 =H + SO 3
-1 +1 -2
HSO4 =H + SO 4
+1 +2 -1
MgCl = Mg + Cl
+1 +2 -1
MgHCO3 = Mg + HCO3

MnHCO3+1 = Mn+2 + HCO3-1
MnOH+1 = Mn+2 + OH-1
NaSO4-1 = Na+1 + SO4-2
ZnHCO3+1 = Zn+2 + HCO3-1
BaCO3ppt = Ba+2 + CO3-2
BaSO4ppt = Ba+2 + SO4-2
CaCO3ppt = Ca+2 + CO3-2
ELECTROLYTES
Fe3O4ppt + 8H+1 = FeII+2 + 2FeIII+3 + 4H 2O
MgCO3ppt = Mg+2 + CO3-2
(NH 4)2SO4ppt = 2NH4+1 + SO 4-2
SrCO3ppt = Sr+2 + CO3-2
SrSO 4ppt = Sr+2 + SO4-2
Vapor-liquid equilibrium is considered for H 2O / CO2 / NH 3 / H2S.
OILF Model
Components:
H2O / CO2 / HCl / Na2SO4 / NaHCO 3 / Na2CO3 / MgCl2 / BaCl2 /
CaCl2 / NaCl / NaOH / KCl / BaSO4 / CaCO3 / CaSO 4 / BaCO3 /
Ca(OH)2 / K 2CO3 / K2SO4 / KHCO 3 / MgCO 3 / Mg(OH)2 / BaOH2 /
KOH / MgSO 4 / H2SO4
Ions:
OH-1 / BaOH+1 / CaHCO3+1 / Ca+2 / CaOH+1 / Cl-1 / CO3-2 /
HCO3-1 / H+1 / HSO4-1 / K+1 / MgCl+1 / MgHCO3+1 / Mg+2 /
Na+1 / NaSO4-1 / Ba+2 / SO 4-2

Na2SO4 / NaHCO3 / Na2CO 3 / MgCl2 / BaCl2 / CaCl2 / NaOH /
BATCH
KCl / BaSO4 / CaCO 3 / CaSO4 / BaCO3 / Ca(OH)2 / K2CO3 /
K2SO 4 / KHCO3 / MgCO3 / Mg(OH)2 / BaOH2 / KOH / MgSO4
Ionic Equilibria:
BaCl2ppt = Ba+2 + 2Cl-1
BaCO3ppt = Ba+2 + CO3-2
BaOH2ppt = Ba+2 + 2OH-1

ELECTROLYTES
BaOH+1 = Ba+2 + OH-1
BaSO4ppt = Ba+2 + SO4-2
CaHCO3+1 = Ca+2 + HCO3-1
CaOH+1 = Ca+2 + OH -1
+2 -2
CaSO4ppt = Ca + SO4
-1 +1
+1 -1
H2 O = H + OH
+1 -1
HClaq = H + Cl
-1 +1 -2
HCO3 =H + CO3
-1 +1 -2
HSO4 =H + SO 4
+1 -2
K2CO 3ppt = 2K + CO 3
+1 -2
K2SO 4ppt = 2K + SO 4

KClppt = K+1 + Cl-1
KHCO3ppt = K+1 + HCO3-1
KOHppt = K+1 + OH-1
MgCl2ppt = Mg+2 + 2Cl-1
MgCl+1 = Mg+2 + Cl-1
MgCO3ppt = Mg+2 + CO3-2
MgHCO3+1 = Mg+2 + HCO3-1
ELECTROLYTES
Mg(OH)2ppt = Mg+2 + 2OH-1
MgSO4ppt = Mg+2 + SO4-2
NaSO4-1 = Na+1 + SO4-2
Vapor-liquid equilibrium is considered for H 2O / CO2 / HCl.
Sour Water Systems

SW01 Model
Components:
H2O / CO2 / H2S / NH3 / CH4 / C6H5OH / NaOH / NaHCO 3 / Na2CO3 /
C2H6 / C3H8 / N 2 / HCl / HCN / H3PO4 / NaCl / NaHS / HCOOH
Ions:
OH-1 / Cl-1 / CN -1 / CO 3-2 / COOH -1 / H 2P2O7-2 / H2PO4-1 / H3P2O 7-1 /
-1 +1 -3 -2 -1 +1 -1 +1
HCO3 /H / HP2O7 / HPO 4 / HS / Na / NH2CO2 / NH4 /

C6H5O-1 / P2O 7-4 / PO4-3 / S-2

BATCH
NaHCO3 / Na2CO3 / NaOH / NaCl
Ionic Equilibria:
C6H5OHaq = H +1 + C6H5O -1
CO2aq + H2O = HCO3-1 + H+1
+1 -1
H2 O = H + OH
-2 +1 -3
H2P2O7 =H + HP 2O7
ELECTROLYTES
-1 +1 -2
H2PO4 =H + HPO4
+1 -1
H2Saq = H + HS
-1 +1 -2
H3P2O7 =H + H 2P2O7
+1 -1
HClaq = H + Cl
+1 -1
HCNaq = H + CN
-1 +1 -2
HCO3 =H + CO3
+1 -1
HCOOHaq = H + COOH
-3 +1 -4
HP2O 7 =H + P 2 O7
-2 +1 -3
HPO4 =H + PO 4
-1 +1 -2
HS =H +S
+1 -2
Na2CO 3ppt = 2Na + CO3
NH3aq + H2O = NH4+1 + OH-1

P2O 7-4 + H2O = 2PO 4-3 + 2H+1
Vapor-liquid equilibrium is not considered for H 3PO 4 / NaHCO 3 /
Na2CO3 / NaOH / NaCl / NaHS.
SW1X Model
Identical to SW01 model except that solid precipitation equilibria
are not considered.
SW02 Model
Components:
ELECTROLYTES
H2O / CO2 / H2S / NH 3 / CH4 / C 6H5OH / NaOH / NaHCO3 /
Na2CO 3 / HCl / NaCl / NaHS / HCN / ACETACID
Ions:
OH-1 / C6H5O-1 / Cl-1 / CN-1 / CO3-2 / HCO3-1 / H +1 / HS-1 /
Na2CO 3 / NH2CO2-1 / NH 4+1 / Acetate-1 / S-2

NaHCO3 / NaOH / Na2CO 3 / NaCl
Ionic Equilibria:
+1 -1
C6H5OHaq = H + C6H5O
-1 +1
+1 -1
H2 O = H + OH
+1 -1
H2Saq = H + HS
ACETACIDaq = H+1 + Acetate-1
HClaq = H+1 + Cl-1
HCNaq = H+1 + CN-1
HCO3-1 = H+1 + CO3-2
HS-1 = H+1 + S-2


BATCH
NH3aq + H2O = NH4+1 + OH-1
Vapor-liquid equilibrium is not considered for Acetic Acid /
ELECTROLYTES
NaHCO3 / NaOH / Na2CO 3 / NaHS / NaCl.
SW2X Model
are not considered.
SW03 Model
Components:
H2O / CO2 / H2S / NH 3 / CH4 / C 6H5OH / NaOH / NaHCO3 /
Na2CO 3 /C2H6 /C3H8 / N2 / HCl / HCN / C4H10 / NaCl / NaHS /
H2 / O2 / CO
Ions:
-1 -1 -1 -2 -1 +1 -1 +1 +1
OH / Cl / CN / CO3 / HCO3 /H / HS / Na / NH4 /
-1 -1 -2
NH2CO2 / C6H 5O /S

Na2CO 3 / NaOH / NaHCO 3 / NaCl
Ionic Equilibria:
C6H5OHaq = H +1 + C6H5O -1
CO2aq + H2O = HCO3-1 + H+1
H2O = H+1 + OH-1

H2Saq = H+1 + HS-1
HClaq = H+1 + Cl-1
HCNaq = H+1 + CN-1
HCO3-1 = H+1 + CO3-2
HS-1 = H+1 + S-2
ELECTROLYTES
NH3aq + H2O = NH4+1 + OH-1
Vapor-liquid equilibrium is not considered for Na2CO3 / NaOH /
NaHCO3 / NaHS / NaCl.
SW3X Model
are not considered.
SW04 Model
Components:
H2O / CO2 / H2S / NH 3 / CH4 / C6H5OH / NaOH / NaHCO3 /
Na2CO 3 / C2H6 / C 3H8 / N2 / C4H10
Ions:
OH-1 / CO3-2 / HCO3-1 / H +1 / HS-1 / Na+1 / NH2CO2-1 / NH4+1 /
C6H5O-1 / S-2

NaOH / NaHCO3 / Na2CO 3

Ionic Equilibria:
■ C6H5OHaq = H +1 + C6H5O -1
BATCH
-1 +1
■ CO2aq + H2O = HCO3 +H
■ H2O = H+1 + OH-1
+1 -1
■ H2Saq = H + HS
■ HCO3-1 = H+1 + CO3-2
-1 +1 -2
■ HS =H +S
ELECTROLYTES
■ Na2CO 3ppt = 2Na+1 + CO3-2
+1 -1
■ NaHCO3ppt = Na + HCO3
■ NaOHppt = Na+1 + OH -1
-1 -1
■ NH2CO2 + H2O = NH3aq + HCO3
■ NH3aq + H2O = NH4+1 + OH-1
Vapor-liquid equilibrium is not considered for NaOH / NaHCO 3 /
Na2CO3.
SW4X Model
are not considered.
SW05 Model
Components:
H2O / CO2 / H2S / NH 3
Ions:
OH-1 / HCO3-1 / H+1 / HS-1 / NH 2CO2-1 / NH4+1 / CO3-2 / S-2
Ionic Equilibria:
CO2aq + H2O = HCO3-1 + H+1
H2O = H+1 + OH-1

H2Saq = H+1 + HS-1
HCO3-1 = H+1 + CO3-2
HS-1 = H+1 + S-2
NH3aq + H2O = NH4+1 + OH-1
ELECTROLYTES
Caustic Systems
CAUS Model
Components:
H2O / Cl2 / HClO / HCl / SO2 / NaCl / Na 2SO3 / Na2SO4 /
NaOH / H2SO4
Ions:
OH-1 / ClO-1 / H+1 / HSO 3-1 / HSO4-1 / Na+1 / NaSO4-1 / Cl-1 /
S2O 5-2 / SO3-2 / SO4-2

NaCl / Na2SO3 / Na2SO4 / NaOH
Ionic Equilibria:
+1 -1
Cl2aq + H2O = H + Cl + HClOaq
+1 -1
H2 O = H + OH
+1 -1
HClaq = H + Cl
+1 -1
HClOaq = H + ClO
-1 +1 -2
HSO3 =H + SO 3
-1 +1 -2
HSO4 =H + SO 4


BATCH
NaSO4-1 = Na+1 + SO4-2
S2O 5-2 + H2O = 2SO 3-2 + 2H+1
SO2aq + H2O = HSO3-1 + H+1
Vapor-liquid equilibrium is considered for H2O / Cl2 / HClO / HCl /
ELECTROLYTES
SO2.
CAUX Model
Identical to CAUS model except that solid precipitation equilibria
are not considered.
CAU2 Model
Components:
H2O / NaOH / KOH
Ions:
-1 +1 +1 +1
OH /K / Na /H

NaOH / KOH
Ionic Equilibria:
H2O = H+1 + OH-1
KOHppt = K+1 + OH-1
Vapor-liquid equilibrium is considered for H 2O only.
CA2X Model
Identical to CAU2 model except that solid precipitation equilibria
are not considered.

Benfield Systems
BENF Model
Components:
H2O / CO2 / CO / C2H6 / C 2H4 / CH4 / H 2S / H2 / N2 / NH3 / C3H8 /
K2CO 3 / KHCO 3 / KHS / H 3PO4 / B(OH)3 / KOH
Ions:
OH-1 / CO3-2 / H2P2O7-2 / H 2PO4-1 / H 3P2O7-1 / HCO3-1 / H+1 /
HP2O7-3 / HPO4-2 / HS-1 / K+1 / NH2CO2-1 / NH4+1 / BO2-1 /
ELECTROLYTES
P2O 7-4 / PO4-3 / S-2

K2CO 3 / KHCO 3 / KOH
Ionic Equilibria:
-1 +1
+1 -1
H2 O = H + OH
-2 +1 -3
H2P2O7 =H + HP 2O7
-1 +1 -2
H2PO4 =H + HPO4
+1 -1
H2Saq = H + HS
-1 +1 -2
H3P2O7 =H + H 2P2O7
-1 +1 -2
HCO3 =H + CO3
P2O7-3 = H+1 + P 2O7-4
HPO4-2 = H+1 + PO 4-3
HS-1 = H+1 + S-2
K2CO 3ppt = 2K +1 + CO 3-2
KHCO3ppt = K+1 + HCO3-1

KOHppt = K+1 + OH-1

BATCH
NH3aq + H2O = NH4+1 + OH-1
P2O 7-4 + H2O = 2PO 4-3 + 2H+1
B(OH)3aq = BO2-1 + H 2O + H+1
Vapor-liquid equilibrium is not considered for K 2CO 3 / KHCO3 /
KHS / H3PO4 / B(OH)3 / KOH.
ELECTROLYTES
BENX Model
Identical to BENF model except that solid precipitation equilibria
are not considered.
Scrubber Systems
SCRU Model
Components:
H2O / CO2 / HCl / HCN / HCOOH / N2 / O2 / SO2 / NaOH / CaCO3 /
CaCl2 / NaCl / Na2CO3 / NaHCO 3 / NaCOOH / Ca(OH)2
Ions:
OH-1 / CaHCO3+1 / Ca+2 / CaOH+1 / Cl-1 / CN -1 / CO3-2 /
COOH-1 / HCO 3-1 / H+1 / HSO3-1 / Na+1 / CaCOOH+1 / S 2O5-2 / SO3-2

NaOH / CaCO3 / CaCl2 / NaCl / Na2CO3 / NaHCO 3 /
NaCOOH / Ca(OH)2
Ionic Equilibria:
+2 -1
CaCl2ppt = Ca + 2Cl
+2 -2
CaCO3ppt = Ca + CO3
+1 +2 -1
CaCOOH = Ca + COOH

CaOH+1 = Ca+2 + OH -1
CO2aq + H2O = HCO3-1 + H+1
H2O = H+1 + OH-1
HClaq = H+1 + Cl-1
HCNaq = H+1 + CN-1
ELECTROLYTES
HCO3-1 = H+1 + CO3-2
HCOOHaq = H+1 + COOH-1
HSO3-1 = H+1 + SO 3-2
NaCOOHppt = Na+1 + COOH-1
S2O 5-2 + H2O = 2SO 3-2 + 2H+1
SO2aq + H2O = HSO3-1 + H+1
Vapor-liquid equilibrium is considered for H2O / CO 2 / HCl / HCN /
HCOOH / N2 / O 2 / SO2.
LLE and Hydrate Systems

TWL1 Model
Components:
H2O / CO2 / H2S / NH 3 / CH4 / C6H5OH /Toluene / NaOH /
NaOH·H 2O / Na2CO3 / Na2CO3·10H2O / Na 2CO3·H2O /

Na2CO 3·7H2O / NaHCO3 / NaCl /NaHS / HCl / CaCl2 / CaCl2·H2O /
CaCl2·2H2O / CaCl2·4H2O / CaCl2·6H2O /Ca(HCO 3)2 / CaCO3 /

BATCH
Ca(OH)2 / NH4Cl / NH4HCO 3 / NH4HS
Ions:
OH-1 / HCO3-1 / NaCO3-1 / NH 2CO 2-1 / Cl-1 /HS -1 / C6H5O -1 /
CO3-2 / S-2 / CaCl+1 / CaHCO 3+1 / CaOH +1 / H+1 /
Na+1 / NH4+1 / Ca+2

ELECTROLYTES
CaCl2 / CaCO3 / Ca(OH)2 / Na2CO 3 /NaCl / NaHCO 3 / NaOH / NH4Cl /
NH4HCO3 / NH 4HS / CaCl2·H 2O / CaCl2·2H2O / CaCl2·4H2O /
CaCl2·6H2O / Na2CO3·10H2O / Na2CO3·H2O / Na2CO3·7H 2O /
NaOH·H2O
Ionic Equilibria:
+1 -1
C6H5OHaq = H + C6H5O
+2 -1
CaCl2·H2O = Ca + 2Cl + H 2O
+2 -1
CaCl2·2H2O = Ca + 2Cl + 2H2O
+2 -1
+2 -1
CaCl2aq = CaCl+1 + Cl-1
CaCl+1 = Ca+2 + Cl-1
CaCO3aq = Ca+2 + CO 3-2
Ca(OH)2ppt = Ca+2 + 2OH-

CaOH+1 = Ca+2 + OH -1
CO2aq + H2O = H+1 + HCO3-1
H2O = H+1 + OH-1
H2Saq = H+1 + HS-1
HClaq = H+1 + Cl-1
HCO3-1 = H+1 + CO3-2
HS-1 = H+1 + S-2
ELECTROLYTES
Na2CO 3·10H2O = 2Na+1 + CO3-2 + 10H2O
Na2CO 3·H2O = 2Na +1 + CO3-2 + H2O
Na2CO 3·7H2O = 2Na+1 + CO3-2 + 7H2O
NaCO3-1 = Na+1 + CO3-2
NaHCO3aq = Na+1 + HCO 3-1
NaOH·H 2O = Na+1 + OH -1 + 1H 2O
+1 -1
NaOHppt = Na + OH
+1 -1
NH3aq + H2O = NH4 + OH
+1 -1
NH4Clppt = NH4 + Cl
+1 -1
NH4HCO3ppt = NH4 + HCO3
+1 -1
NH4HSppt = NH4 + HS

Vapor-Liquid and Liquid-Liquid Equilibria:
Vapor-liquid equilibrium is considered for H 2O / C6H5OH / CH 4 /
CO 2 / H 2S / HCl / NH3 / Toluene.
BATCH
TWL2 Model
Components:
H2O / NaCl / NaHSO4 / Na2SO 4 / Na2SO4·10H2O /NaOH /
NaOH·H2O / Ca(HSO4)2 / CaSO 4 / CaSO4·2H2O / Ca(OH)2 /
HCl / N 2 / CH4 / Methanol / Ethanol / M-Xylene / Benzene /
Toluene / CaCl2 / CaCl2·H2O / CaCl2·2H2O / CaCl2·4H2O /

ELECTROLYTES
CaCl2·6H2O / HF / H2SO4 / CaF2 / NaF
Ions:
OH-1 / Cl-1 / HF2-1 / HSO4-1 / NaSO4-1 / F -1 / SO4-2 / H +1 /
CaCl+1 / CaF+1 / CaOH +1 / Na+1 / Ca+2

CaCl2 / CaF2 / Ca(OH)2 / CaSO4 / Na2SO4 / NaCl / NaF / NaHSO4/
NaOH / CaCl2·H2O / CaCl2·2H2O / CaCl2·4H2O / CaCl2·6H2O /
CaSO4·2H2O / Na2SO4·10H 2O / NaOH ·H2O
Ionic Equilibria:
CaCl2·H2O = Ca+2 + 2Cl-1 + H 2O
CaCl2·2H2O = Ca+2 + 2Cl-1 + 2H2O
CaCl2·4H2O = Ca+2 + 2Cl-1 + 4H2O
CaCl2·6H2O = Ca+2 + 2Cl-1 + 6H2O
CaCl2aq = CaCl+1 + Cl-1
CaCl+1 = Ca+2 + Cl-1
CaF2ppt = Ca+2 + 2F-1

CaF+1 = Ca+2 + F-1
CaOH+1 = Ca+2 + OH -1
CaSO4·2H2O = Ca+2 + SO4-2 + 2H2O
CaSO4ppt = Ca+2 + SO4-2
H2O = H+ + OH-1
ELECTROLYTES
HClaq = H+ + Cl-1
HF2-1 = F-1 + HFaq
HFaq = H+1 + F-1
HSO4-1 = H+1 + SO 4-2
Na2SO4·10H2O = 2Na+1 + SO4-2 + 10H2O
NaFaq = Na+1 + F-1
NaFppt = Na+1 + F-1
NaHSO4ppt = Na+1 + HSO4-1
NaOH·H 2Oppt = Na+1 + OH -1 + H2O
NaSO4-1 = Na+1 + SO4-2
Vapor-Liquid and Liquid-Liquid Equilibria:

Vapor-liquid equilibrium is considered for H 2O / Benzene / CH 4 /
Ethanol / HCl / HF / Methanol / M-Xylene / N2 / Toluene.

Alphabetical Component Index of Electrolyte Models
The Electrolyte models that contain a given component (or ionic
species) are listed directly underneath the component names in this
BATCH
index. The phases allowed for the components are given in paren-
theses following the component names, where:
AQ = aqueous phase (ion, ion pair, or dissolved neutral molecule)
CI = completely ionized aqueous electrolyte
V = vapor phase
S = solid phase
HC = hydrocarbon or non-aqueous liquid phase.
For example, it can be deduced from the index that aqueous calcium
ion, Ca+2(AQ), hydroxide ion, OH -1(AQ), calcium monohydroxide
ELECTROLYTES
ion pair, CaOH+1(AQ), and solid calcium hydroxide, Ca(OH)2(S)

are included in the CANA model. The CANX model has the same
components as CANA; however, solid phases of the components are
not allowed. Consequently, Ca(OH)2 in the CANX model is treated
as an aqueous electrolyte that is completely ionized (CI).

SW042 CANA1 TWL1
A SW1X2 CANX1 CaHSO4 (CI)
Acetacid (AQ) SW3X2 GEOT1 TWL2
SW023 SW4X2 OILF1 CaOH+1 (AQ)
SW2X3 TEA2 SCRU1 CANA1
Acetate-1 (AQ) C3H8 (V,AQ) SCRX1 CANX1
SW021 BENF6 TWL2 GEOT1
SW2X1 BENX6 Ca2EDTA (AQ) OILF1
DEA7 GEOT1 SCRU1
B DGA7 CaCl+1 (AQ) SCRX1
Ba+2 (AQ) DIPA7 TWL1 TWL1
GEOT1 HOTC7 TWL2 TWL2
OILF1 HOTX7 CaCl2 (CI) Ca(OH)2 (CI)
BaCl2 (CI) MDEA7 CANX1 CANX1
GEOT1 MEA7 GEOT1 SCRX1
BaCl2 (S) SW017 SCRX1 Ca(OH)2 (S)
OILF1 SW037 CaCl2 (S) CANA1
ELECTROLYTES
BaCO3 (S) SW047 CANA1 OILF1
GEOT1 SW1X7 OILF1 SCRU1
OILF1 SW3X7 SCRU1 TWL1
BaOH+1 (AQ) SW4X7 TWL1 TWL2
GEOT1 TEA7 TWL2 CaSO4 (AQ)
OILF1 C4H10 (V,AQ) CaCl2·H2O (S) CANX1
Ba(OH)2 (S) DEA6 TWL1 GEOT1
OILF1 DGA6 TWL2 CaSO4 (S,AQ)
BaSO4 (S) DIPA6 CaCl2·2H2O (S) CANA1
GEOT1 MDEA6 TWL1 OILF1
OILF1 MEA6 TWL2 TWL2
Benzene (V,AQ,HC) SW036 CaCl2·4H2O (S) CaSO4·2H2O (S)
TWL2 SW046 TWL1 TWL2
BO2-1 (AQ) SW3X6 TWL2 CH4 (V,AQ)
BENF1 SW4X6 CaCl2·6H2O (S) BENF1
BENX1 TEA6 TWL1 BENX1
B(OH)3 (AQ) C6H5O-1 (AQ) TWL2 DEA1
BENF1 SW011 CaCO3 (CI) DGA1
BENX1 SW021 SCRX1 DIPA1
GEOT1 SW031 CaCO3 (S) HOTC1
B(OH)3OH-1 (AQ) SW041 GEOT1 HOTX1
GEOT1 SW1X1 OILF1 MDEA1
SW2X1 SCRU1 MEA1
C SW3X1 TWL1 SW011
C2H4 (V,AQ) SW4X1 CaCOOH+1 (AQ) SW021
BENF2 TWL1 SCRU1 SW031
BENX2C2H6(V,AQ) C6H5OH (V,AQ) SCRX1 SW041
BENF2 SW011 CaF+1 (AQ) SW1X1
BENX2 SW021 TWL2 SW2X1
DEA2 SW031 CaF2 (S) SW3X1
DGA2 SW041 TWL2 SW4X1
DIPA2 SW1X1 CaHCO3+1 (AQ) TEA1
HOTC2 SW2X1 GEOT1 CH4 (V,AQ,HC)
HOTX2 SW3X1 OILF1 TWL1
MDEA2 SW4X1 SCRU1 TWL2
MEA2 C6H5OH (V,AQ,HC) SCRX1 Cl-1 (AQ)
SW012 TWL1 TWL1 CANA1
SW032 Ca+2 (AQ) Ca(HCO3)2 (CI) CANX1

CAUS1 BENX2 ACID2
CAUX1 DEA2 SCRU2 H
Cl21 DGA2 SCRX2 H+1 (AQ)
CLSF1 DIPA2 SW012 (all models)
GENE1 GENE2 SW1X2 H2 (V,AQ)
GENX1 GENX2 Cu+2 (AQ) ACID3
GEOT1 GEOT2 GEOT BENF3
HCL1 HOTC2 CuCl2 (CI) BENX3
OILF1 HOTX2 GEOT2 HOTC3
SALT1 MDEA2 HOTX3
SCRU1 MEA2 D SW033
SCRX1 OILF2 DEACO2-1 (AQ) SW3X3
SW011 SCRU2 DEA2 H2O (V,AQ)
SW021 SCRX2 DEAH (AQ) (all models)
SW031 SW012 DEA2 H2P2O7-2 (AQ)
SW1X1 SW022 DEAH2 +1 (AQ) ACID3
SW2X1 SW032 DEA2 BENF3
ELECTROLYTES
SW3X1 SW042 DGACO2-1 (AQ) BENX3

TWL1 SW052 DGA2 PHOS3
TWL2 SW1X2 DGAH (AQ) SW013
Cl2 (V,AQ) SW2X2 DGA2 SW1X3
CAUS1 SW3X2 DGAH2+1 (AQ) H2PO4 -1 (AQ)
CAUX1 SW4X2 DGA2 ACID3
CL21 TEA2 DIPACO2 -1 (AQ) BENF3
CLSF1 CO2 (V,AQ,HC) DIPA2 BENX3
GENE1 TWL1 DIPAH (AQ) PHOS3
GENX1 CO3-2 (AQ) DIPA2 SW013
ClO-1 (AQ) ACID2 DIPAH2+1 (AQ) SW1X3
CAUS1 BENF2 DIPA H2S (V,AQ)
CAUX1 BENX2 BENF3
CL21 DEA2 E BENX3
CLSF1 DGA2 EDTA-4 (AQ) DEA3
GENE1 DIPA2 GEOT2 DGA3
GENX1 GENE2 Ethanol (V,AQ,HC) DIPA3
CN-1 (AQ) GENX2 TWL2 GEOT3
ACID1 GEOT2 HOTC3
SCRU1 HOTC2 F HOTX3
SCRX1 HOTX2 F-1 (AQ) MDEA3
SW011 MDEA2 TWL2 MEA3
SW021 MEA2 Fe3O4 (S) SW013
SW031 OILF2 GEOT2 SW023
SW1X1 SCRU2 FeII+2 (AQ) SW033
SW2X1 SCRX2 GEOT2 SW043
SW3X1 SW012 FeIICl2 (CI) SW053
CO (V,AQ) SW022 GEOT2 SW1X3
ACID2 SW032 FeIIHCO3+1 (AQ) SW2X3
BENF2 SW042 GEOT2 SW3X3
BENX2 SW052 FeIII+3 (AQ) SW4X3
HOTC2 SW1X2 GEOT2 TEA3
HOTX2 SW2X2 FeIIICl3 (CI) H2S (V,AQ,HC)
SW032 SW3X2 GEOT2 TWL1
SW3X2 SW4X2 FeIIOH+1 (AQ) H2SO3 (CI)
CO2 (V,AQ) TEA2 GEOT2 CLSF3
ACID2 TWL1 SULF3
BENF2 COOH-1 (AQ) H2SO4 (CI)

CANA3 SCRX4 BENX4 K2CO3 (CI)
CANX3 SW014 PHOS4 BENX4
CAUS3 SW024 SW014 K2CO3 (S)
CAUX3 SW034 SW1X4 BENF4
CLSF3 SW1X4 HS-1 (AQ) OILF4
OILF3 SW2X4 BENF4 K2SO4 (S)
SULF3 SW3X4 BENX4 OILF4
TWL2 HCO3-1 (AQ) DEA4 KCl (CI)
H3P2 O7-1 (AQ) ACID4 DGA4 GEOT4
ACID3 BENF4 DIPA4 KCl (S)
BENF3 BENX4 GEOT4 OILF4
BENX3 DEA4 HOTC4 SALT4
PHOS3 DGA4 HOTX4 KHCO3 (CI)
SW013 DIPA4 MDEA4 BENX4
SW1X3 GENE4 MEA4 KHCO3 (S)
H3PO4 (CI) GENX4 SW014 BENF4
ACID3 GEOT4 SW024 OILF4
ELECTROLYTES
BENF3 HOTC4 SW034 KHS (CI)
BENX3 HOTX4 SW044 BENF4
PHOS3 MDEA4 SW054 BENX4
SW013 MEA4 SW1X4 KOH (CI)
SW1X3 OILF4 SW2X4 BENX4
HCl (CI) SCRU4 SW3X4 CA2X4
GEOT3 SCRX4 SW4X4 KOH (S)
HCl (V,AQ) SW014 TEA4 BENF4
CANA3 SW024 HSO3-1 (AQ) CAU24
CANX3 SW034 CAUS4 OILF4
CAUS3 SW044 CAUX4
CAUX3 SW054 CLSF4 L
CL23 SW1X4 GENE4 Li+1 (AQ)
CLSF3 SW2X4 GENX4 GEOT4
GENE3 SW3X GEOT4 LiCl (CI)
GENX3 SW4X4 SCRU4 GEOT4
HCL3 TEA4 SCRX4
OILF3 TWL1 SULF4 M
SCRU3 HCOOH (V,AQ) HSO4-1 (AQ) MDEAH (AQ)
SCRX3 ACID4 CANA4 MDEA4
SW013 SCRU4 CANX4 MDEAH2 +1 (AQ)
SW023 SCRX4 CAUS4 MDEA4
SW033 SW014 CAUX4 MEACO2-1 (AQ)
SW1X3 SW1X4 CLSF4 MEA4
SW2X3 HF2-1 (AQ) GEOT4
SW3X3 TWL2 OILF4 MEAH (V,AQ)
TWL1 HF (V,AQ,HC) SULF4 MEA4
TWL2 TWL2 TWL2 MEAH2+1 (AQ)
HClO (V,AQ) HP2O7 -3 (AQ) MEA4
CAUS3 ACID4 K Methanol (V,AQ,HC)
CAUX3 BENF4 K+1 (AQ) TWL2
CL23 BENX4 BENF4 Mg+2 (AQ)
CLSF3 PHOS4 BENX4 CANA4
GENE3 SW014 CA2X4 CANX4
GENX3 SW1X4 CAU24 GEOT4
HCN (V,AQ) HPO4-2 (AQ) GEOT4 OILF4
ACID4 ACID4 OILF4 MgCl+1 (AQ)
SCRU4 BENF4 SALT4 CANA4

CANX4 SW035 Na2CO3.10H2O (S) SW3X5
GEOT4 SW045 TWL1 SW4X5
OILF4 SW1X5 Na2S (CI) NaHCO3 (S)
MgCl2 (CI) SW3X5 GEOT5 GENE5
CANX4 SW4X5 Na2SO3 (CI) HOTC5
GEOT4 TEA5 CAUX5 OILF5
MgCl2 (S) N2 (V,AQ,HC) GEOT5 SCRU5
CANA4 TWL2 Na2SO3 (S) SW015
OILF4 Na+1 (AQ) CAUS5 SW025
MgCO3 (S) CA2X5 Na2SO4 (CI) SW035
GEOT5 CANA5 CANX5 SW045
OILF5 CANX5 CAUX5 TWL1
MgHCO3+1 (AQ) CAU25 GEOT5 NaHS (CI)
GEOT5 CAUS5 Na2SO4 (S) SW015
OILF5 CAUX5 CANA5 SW025
Mg(OH)2 (CI) GENE5 CAUS5 SW035
CANX5 GENX5 OILF5 SW1X5
ELECTROLYTES
Mg(OH)2 (S) GEOT5 TWL2 SW2X5

CANA5 HOTC5 Na2SO4.10H2O SW3X5
OILF5 HOTX5 TWL2 TWL1
MgSO4 (CI) OILF5 Na4EDTA (AQ) NaHSO4 (S)
CANX5 SALT5 GEOT5 TWL2
MgSO4 (S) SCRU5 NaCl (CI) NaOH (CI)
CANA5 SCRX5 CANX5 CA2X5
OILF5 SW015 CAUX5 CANX5
Mn+2 (AQ) SW025 GENX5 CAUX5
GEOT5 SW035 GEOT5 GENX5
MnCl2 (CI) SW045 OILF5 HOTX5
GEOT5 SW1X5 SCRX5 SCRX5
MnHCO3+1 (AQ) SW2X5 SW1X5 SW1X6
GEOT5 SW3X5 SW2X5 SW2X6
MnOH+1 (AQ) SW4X5 SW3X5 SW3X6
GEOT5 TWL2 NaCl (S) SW4X6
M-Xylene (V,AQ,HC) Na2CO3 (CI) CANA5 NaOH (S)
TWL2 GENX5 CAUS5 CANA6
HOTX5 GENE5 CAU26
N SCRX5 SALT5 CAUS6
N2 (V,AQ) SW1X5 SCRU5 GENE6
ACID5 SW2X5 SW015 HOTC6
BENF5 SW3X5 SW025 OILF6
BENX5 SW4X5 SW035 SCRU6
CL25 Na2CO3 (S) TWL1 SW016
CLSF5 GENE5 TWL2 SW026
DEA5 HOTC5 NaCOOH (CI) SW036
DGA5 OILF5 SCRX5 SW046
DIPA5 SCRU5 NaCOOH (S) TWL1
GENE5 SW015 SCRU5 TWL2
GENX5 SW025 NaF (S) NaOH·H2O (S)
HOTC5 SW035 TWL2 TWL1
HOTX5 SW045 NaHCO3 (CI) TWL2
MDEA5 TWL1 GENX5 NaSO4-1 (AQ)
MEA5 Na2CO3·H2O (S) HOTX5 CANA6
SCRU5 TWL1 SCRX5 CANX6
SCRX5 Na2CO3·7H2O (S) SW1X5 CAUS6
SW015 TWL1 SW2X5 CAUX6

GEOT6 SW3X6 BENF7 SCRU7
OILF6 SW4X6 BENX7 SCRX7
TWL2 TWL1 DEA7 SULF7
NH2CO2 -1 (AQ) NH4Cl (S) DGA7 SO4-2 (AQ)
ACID6 TWL1 DIPA7 CANA7
BENF6 NH4HCO3 (S) GEOT7 CANX7
BENX6 TWL1 HOTC7 CAUS7
GEOT6 NH4HS (S) HOTX7 CAUX7
SW016 TWL1 MDEA7 CLSF7
SW026 (NH4 )2 SO4 (S) MEA7 GEOT7
SW036 GEOT6 SW017 OILF7
SW046 SW027 SULF7
SW056 O SW037 TWL2
SW1X6 O2 (V,AQ) SW047 Sr+2 (AQ)
SW2X6 CLSF6 SW057 GEOT7
SW3X6 GENE6 SW1X7 SrCl2 (CI)
SW4X6 GENX6 SW2X7 GEOT7
ELECTROLYTES
TWL1 SCRU6 SW3X7 SrCO3 (S)
NH3 (V,AQ) SCRX6 SW4X7 GEOT7
ACID6 SW036 TEA7 SrSO4 (S)
BENF6 SW3X6 TWL1 GEOT7
BENX6 OH-1 (AQ) S2O5 -2 (AQ)
GEOT6 (all models)6 CAUS7
SW016 CAUX7 T
SW026 P CLSF7 TEACO2 -1 (AQ)
-4
SW036 P2O7 (AQ) GENE7 TEA7
SW046 ACID6 GENX7 TEAH (AQ)
SW056 BENF6 SCRU7 TEA7
SW1X6 BENX6 SCRX7 TEAH2+1 (AQ)
SW2X6 PHOS6 SULF7 TEA7
SW3X6 SW016 SO2 (V,AQ) Toluene (V,AQ,HC)
SW4X6 SW1X6 CAUS7 TWL1
NH3 (V,AQ,HC) Pb+2 (AQ) CAUX7 TWL2
TWL1 GEOT6 CLSF7
NH4+1 (AQ) PbCl2 (CI) GENE7 Z
ACID6 GEOT6 GENX7 Zn+2 (AQ)
BENF6 PO4-3 (AQ) SCRU7 GEOT7
BENX6 ACID6 SCRX7 ZnCl2 (CI)
GEOT6 BENF6 SULF7 GEOT7
SW016 BENX6 SO3-2 (AQ) ZnHCO3+1 (AQ)
SW026 PHOS6 CAUS7 GEOT7
SW036 SW016 CAUX7
SW046 SW1X6 CLSF7
SW056 GENE7
SW1X6 S GENX7
SW2X6 S-2 (AQ) GEOT7

ELECTROLYTES
Chapter 3
Generating a
User-Added Electrolyte Model
ELECTROLYTES
You can develop your own user-added electrolyte models with OLI
Systems, Inc. software or this tool. This chapter provides step-by-
step instructions on using the model generation features to create
user-added models for the SIMSCI PRO/II Electrolytes version.
The Electrolyte Utility Package (EUP)

A new EUP windows interface package has been developed for
PRO/II. This program provides you with functionality that facilitate
computer modeling of aqueous electrolyte solution chemistry. A
portion of the computer source code in the EUP is a subset of the
code used in the ProChem software package from OLI Systems,
Inc. The EUP’s source code is updated every time OLI releases a
new version of ProChem.
The EUP’s primary purpose is to generate user models for use with
PRO/II. From the user’s perspective, model generation consists
mainly of entering the names of the chemical components and
selecting the types of equilibrium phases (solid, liquid, or vapor)
that can occur in the chemical system of interest. The output from
this model-generation process includes an ASCII data file named
M##.DBS. These files contain all the information needed to run a
user-added electrolyte model in the PRO/II Electrolytes version.
Generating User-Added Models for PRO/II Electrolytes

SIMSCI has worked with OLI Systems Inc. to prepare a EUP that
generates user-added models for PRO/II Electrolytes. User-added
model generation corresponds to the creation of a data file,

M##.DBS, for an electrolyte model named where ## represents any
integer from 41 through 60. The M##. DBS file contains thermody-
namic and algorithmic equations specific to the model’s component
BATCH
list as well as pure component data, species interaction data, stoichi-

ometric coefficients for chemical reactions, and all other data quan-
tities that are used as knowns in the simultaneous solution of the
model’s equations. (See the SIMSCI Component and Thermody-
namic Data Reference Manual, Sections 1.2.9 and 1.2.10, for a dis-
cussion of these equations and data quantities.)
The first window is shown in Figure 3-1.

Figure 3-1: Welcome to the Electrolyte Utility Package
ELECTROLYTES
First, as the red border indicates, the user must select a user added
model name from the drop-down list box in the upper right hand
corner.
3-2 Generating a User-Added Electrolyte Model

Figure 3-2: User Model Name selected in the Electrolyte Utility Package
Model
ELECTROLYTES
Once a model name is selected, the rest of the window is now
active, and H2O has been selected as your first component in the
model.
Additional model species can be selected in a number of ways. You

can type directly into the list box if you are familiar with the OLI
species names, or you can search by name or formula using search
on the inflows tab.
➤ Type in HCL in the list box., and press the <Enter> key.
➤ Change the focus to the drop down list box and TYPE in “CA”.
➤ Press the <Search>button.CACL2 should appear in the list
box. Pressing the < << Add >button will transfer the inflow
species to the inflows list box. CAOH2 can be added in a simi-
lar manner.
We are now ready to generate a M41.MOD file by pressing the
<Generate Model Definition File> button shown at the bottom of
Figure 3-2. After the message “Model Definition File has been Gen-
erated” appears as shown in Figure 3-3 and any additional species
are added by the model definition step to the Inflows list we are
done with this initial portion of the model development effort.

Figure 3-3: Inflow Names Entered and Model Generated
BATCH
ELECTROLYTES
Before we discuss the final step to generating an electrolyte .dbs file

we can take the opportunity to review some of the other Tabs in the
package. Selecting the <Databanks> tab shows a pair of linked list
boxes that show the databanks present in the User directory. The
PUB and ORGANIC databanks are always accessed and are not
displayed in this window. Figure 3-4 show that we have two addi-
tional banks present, the GEOCHEM and ESTM banks that could
be used if desired.
Next the <Species> tab, shown in Figure 3-5, will show two list
boxes, the first containing all the species present in the Model and
the second list box on this tab will show the appropriate equilibrium
equations.

Figure 3-4: Additional Databanks Present in the working Directory
ELECTROLYTES
Figure 3-5: Species and Equations Present in the .MOD User Model
Definition File.

The next tab, the <Solids> tab, is where you can actually manipu-
late the model by either deleting solid species you wish not to be
considered in your model or to just consider the scaling tendency of
BATCH
the species. This tab is show in Figure 3-6. The final tab <Keyword
Input> contains a list box where users can enter information back-
wards compatible with older ProChem functionality.
Solid Review tab
ELECTROLYTES

Figure 3-6: DBS File Generation
ELECTROLYTES
After we have eliminated any solid species we don’t want consid-
ered we are ready to complete the generation of the .DBS. During
generation a message “Electrolyte Model is being generated” will
show in the message area as shown in Figure 3-7. When the file has
been generated a small notice window shown in Figure 3-8 will
appear and you can either repeat the process, building another data-
bank, or exit the program.
Figure 3-7: Model Generated Message
The M##.DBS file will be moved to the PRO/II USER directory

(simsci/proii511/user). At this time you can now select user added
model M41 from the Thermodynamic Data Selection DEW in PRO/
II.

Figure 3-8: ElectrolyteUser-Added Model Selection in PRO/I
BATCH
ELECTROLYTES

Chapter 4
Electrolytes in PRO/II GUI
ELECTROLYTES
Throughout the development of PRO/II Electrolytes, a major goal
has been to integrate the Electrolyte thermodynamic methods seam-
lessly into PRO/II’s graphical user interface (GUI). In other words,
as far as the unit operations are concerned, PRO/II Electrolytes
should operate as “just another thermodynamic method.” There are
several units still unavailable for use with Electrolytes, while others
have partial functionality or other special considerations. This docu-
ment discusses workarounds, where possible, for these limitations.
General Considerations
The most fundamental consideration that can make PRO/II Electro-
lytes different from other thermodynamic methods is that it is com-
pletely tied to the flash algorithm, K-value, enthalpy, and density
methods as developed by OLI Systems Inc. (Morris Plains, N.J.).
OLI’s flash algorithm does not work exactly the same as the “nor-
mal” flash in PRO/II; in some ways that is a plus, but it can create
problems for a few PRO/II unit operations. The following are
important differences between the two, along with statements
regarding the consequences of those differences:
■ There are conditions (most commonly where there is no aque-

ous liquid phase) in which OLI’s thermodynamic method is
simply not applicable. In such conditions, the flash will usually
fail to converge. This is in contrast to most non-electrolyte
PRO/II thermodynamic methods, in which the flash will usu-
ally return some sort of an answer even if you have chosen an
inappropriate method for the conditions.
■ There are occasionally valid conditions for which OLI’s flash

fails to converge. The most common of these failures occurs in

adiabatic flashes with nearly pure fluids that cross a phase
boundary; this case will be discussed below in Simple HX. The
only other known significant problem is that OLI can have
BATCH
problems converging a flash in which a large amount of a spar-

ingly soluble solid will precipitate out. This problem is allevi-
ated somewhat for internal flowsheet streams by implementing
an initial guess for solids based on the solids in the feed. This
can be done for external feed streams by putting an estimate of
the solid that will precipitate on the SOLID statement for the
stream.
■ There are some thermodynamic quantities that OLI does not

calculate. In particular, OLI does not return values for the
entropy or heat capacity of electrolyte streams. This means that
ELECTROLYTES
electrolyte thermodynamic methods cannot be used for units

that require entropy, such as the Gibbs reactor. Some units also
use heat capacity internally; in some cases special adjustments
have been made to the code for electrolyte thermodynamic
methods.
■ The list of specifications recognized by OLI’s flash is different

from that recognized by PRO/II’s flash. Many of the specifica-
tions can be translated, but some (such as isentropic flashes)
cannot.
■ OLI, under the current release of PRO/II Electrolytes, will now

do liquid/liquid equilibrium (LLE); that is, it can handle a sec-
ond (organic) liquid phase. However, this capability is limited
to non-column unit operations such as the flash drum and the
splitter.
Basic Unit Operations

SPEC, DEFINE, VARY
In general, all of the flowsheet parameters as listed in Section 43 of
the PRO/II Keyword Manual are available for cross-referencing, and
anything that can be varied with other thermodynamic methods can
be varied with electrolytes. There are some stream properties (for
example, D86 and WFRAC) that do not make sense for aqueous
electrolyte streams.
In addition, the electrolyte-specific stream property pH is available

for cross-referencing.
4-2 Electrolytes in PRO/II GUI

Flash Drum
As with all flash-type units, the most important caution is not to use
electrolyte thermodynamic methods at conditions where it is not
valid. Apart from that, most of the functionality of the unit is avail-
able for electrolytes. The flash drum is able to handle a second
(organic) liquid phase, as well as a vapor and/or precipitated solid
phase. As mentioned before, the ISENTROPIC flash is not available.
The DEWHC and DEWWATER options are not available (or meaning-
ful) because electrolyte methods do not decant water.
The TPSPEC construct is currently limited with electrolytes. The

one added feature is the ability to SPEC the pH of an outlet liquid
stream. The only other internal flash spec allowed is a vapor or liq-
ELECTROLYTES
uid flowrate as a fraction of the molar flowrate of a stream that is
the only feed to the unit:
SPEC STRM=L1, RATE, RATIO, STRM=F1, RATE, VALUE=0.8
The REFFEED construct may also be used to reference a combined
unit feed. One can simulate any other TPSPEC by putting the flash
drum inside a controller loop.
For example, to specify a liquid weight fraction:
CONTROLLER UID=C1
SPEC STRM=L1, COMP=2, FRACTION(W), VALUE=0.3
VARY FLASH=FL1, TEMP
Pump, Valve, Mixer, Splitter

These units all work normally with electrolytes. There is a potential
problem in the Valve, in which the adiabatic flash may fail to con-
verge for a nearly pure fluid if the user is crossing a phase boundary.
Frequently, this may be alleviated simply by taking the valve in two
(or more) steps; a stream that will not converge when being throt-
tled from 50 to 15 psi may converge if it is taken to 20 psi in one
valve and then down to 15 in a second valve (in the second case it
gets a better initial guess). Alternatively, the valve can be simulated
by putting an ISOT flash (or a vapor-fraction-specified flash) inside
a controller with a controller specification of zero duty on the flash.
Compressor or Expander
Both of these units require entropy and are consequently not avail-
able with PRO/II Electrolytes. There are, however, still cases where
they may be used in electrolyte flowsheets. For example, if the units

operate only on a vapor phase (steam, for example), there is no rea-
son not to use a non-electrolyte thermodynamic method. Also, if the
stream in question is nearly pure water, the units may be replaced
BATCH
by a flash drum to give the ∆P in the flowsheet, and then they may
be modeled separately using a pure water stream to design the unit
and feed back the correct temperature for the flash drum.
Pipe
This unit is functional with PRO/II Electrolytes. The Pipe might
have problems doing two-phase flow with nearly pure water
streams because it does adiabatic/fixed-duty flashes on which OLI
may fail. Of course, the Pipe requires viscosities and sometimes
surface tensions. See the comments on Transport Properties below
ELECTROLYTES
for availability in regards to electrolytes.
Heat Exchangers
Simple HX
The full functionality of this unit, including all the Spec types, is
available to PRO/II Electrolytes.
There is, however, one commonly encountered condition that can
cause a problem: when the hot side of an exchanger is condensing
steam (in the case of a multi-effect evaporator, the steam may come
as the vapor from the cold side of another HX). The HX does a
fixed-duty flash on this stream. Unfortunately, OLI has great diffi-
culty converging for pure steam crossing the two-phase region. The
remedy for this situation is to use non-electrolyte thermodynamic
methods for the side of the HX that uses condensing steam; because
it is a pure water stream, there is no need to use electrolyte thermo-
dynamic methods anyway.
Rigorous HX
This unit is fully functional with PRO/II Electrolytes.
LNGHX
This unit is fully functional with PRO/II Electrolytes. The com-
ments regarding the use of condensing steam (see the HX discus-
sion above) apply here as well.
Distillation Column
Some detailed hints with respect to the use of ELDIST may be
found in Section 5 of the PRO/II Electrolytes Training Manual. For

the most part, the functionality of ELDIST is the same as that of
Chemdist. That means, for example, that pumparounds are not
allowed, and the range of Specs available is limited. In contrast to
Chemdist, ELDIST does not allow the specification of component
flows or mole fractions in liquid product streams. This is because
the presence of ionic reactions sometimes makes it ambiguous as to
the “correct” way to report the composition of a liquid (this is the
problem known as “reconstitution”). It should be noted that, as with
other units, non-allowed Specs may be met by putting the column
inside a controller. Another limitation of ELDIST is neither VLLE
distillation nor liquid-liquid extraction is available. Column hydrau-
lics is also unavailable at present, but it will be enabled in the near
future.
ELECTROLYTES
Because electrolyte systems are often very non-ideal, ELDIST
sometimes has difficulty converging. Supplying initial estimates for
column tray temperatures and/or vapor-liquid flows (perhaps
obtained by solving a simplification of the problem) will often aid
convergence. Complete initial estimates (including compositions)
can be saved from one run with the PRINT PROFILE option. These
estimates will not only help similar columns converge, but they will
also save time because the ELDIST initial estimate generator is
somewhat time consuming.
Reactors
General Reactor
It should be remembered that, in PRO/II Electrolytes, you do not
necessarily need a Reactor to get a reaction. For example, water,
NaOH and HC1 will yield NaCl and H 2O in a flash drum or any
other unit that does a flash. For reactions in aqueous solution that
involve only a “rearrangement” of ions, the Reactor is not neces-
sary.
If it is desired to use a reactor with Electrolyte thermodynamic

methods, the user is currently limited to isothermal mode with the
NOHBAL option turned on. These limitations will probably be
lifted in later releases of PRO/II Electrolytes. Of course, fixed-duty
mode can be simulated by putting an isothermal reactor in a control-
ler loop.
Gibbs Reactor
This unit requires entropy, and therefore cannot be used with elec-
trolyte thermodynamic methods. Again, since PRO/II Electrolytes

performs a simultaneous phase and chemical equilibration, the
functionality of a Gibbs reactor would be redundant if the only reac-
tions were ionic rearrangements.
BATCH
Plug Flow and Continuously Stirred Tank Reactors

These units are not currently available with Electrolyte thermody-
namic methods. The primary reason for this is that neither unit is
able to handle components with phase type LS. Almost all reason-
able electrolyte models would contain such components.
Solids Handling Utilities

Dryer
ELECTROLYTES
This unit is not available with Electrolyte thermodynamic methods.

The main reason for this is that OLI has difficulty converging
flashes with lots of solid and little water. These would be conditions
likely to arise in the dryer. It might be possible to work around this
last problem by stringing multiple dryers in series to model one
unit.
RFilter, FCentrifuge, CCDecanter

These units have their full functionality with Electrolyte thermody-
namic methods. There is, however, one thing to watch out for. These
units are not designed to do phase equilibrium calculations, so if the
conditions are such that more solids will precipitate (or dissolve) in
the unit, solids may appear (or disappear) in the filtrate stream fol-
lowing solution of the unit.
Dissolver and Crystallizer

These two units may be used successfully with PRO/II Electrolytes
if care is taken in setting up the problem. If the only purpose is to
produce solid precipitate (or dissolve solids) to the equilibrium con-
centration, a flash drum should be used instead. The ability of OLI’s
flash to do SLE is a big advantage over PRO/II’s non-electrolyte
thermodynamic methods in this case. The crystallizer and dissolver
should be used with electrolytes in only two cases:
■ When the process does not reach equilibrium.
■ When it is important to know the particle size distribution

(PSD) of the product.
Both of these units are unable to go all the way to equilibrium (of
course, this is not an issue unless the kinetics are zero-order). In
such cases, the warning message will often say something like

“supersaturation limit reached.” The dissolver unit will also fail at
conditions such that all of the solid will dissolve. A flash drum
should be used in such cases.
As for the kinetics in these units, the parameters must be adjusted to
match experimental data. While the dissolver has a correlation to
predict mass transfer, that correlation is completely inappropriate
for electrolyte solutes. When testing different parameters to match
data, it is best (because of the problems getting to complete equilib-
rium) to start with “slow” kinetics and work your way up.
For electrolytes, both of these units operate only in isothermal

mode. Fixed-duty conditions may be simulated by putting the unit
in a controller loop.
ELECTROLYTES
Melter/Freezer
This unit exists only to circumvent non-electrolyte PRO/II’s inabil-
ity to do SLE, so it has no useful purpose for electrolytes and is
therefore disallowed.
Calculator
See comments above regarding what may be accessed with the
DEFINE statement.
Stream Calculator
This unit is fully functional with PRO/II Electrolytes.
Flowsheet Control
You are likely to get warnings in electrolyte problems about compo-
nents with undefined separation factors. This is because a PRO/II
Electrolytes model will add any components it has to what is on the
LIBID statement, so there will be more components in the simula-
tion than the user might have thought. As long as none of these
added components are produced in the simulation, these warnings
may be safely ignored.
Miscellaneous
It is also possible to encounter a flash failure in this unit when doing
feed blending, such as is commonly done to figure the rate of a
makeup stream. This is because the unit first does an adiabatic flash
on the entire blended feed, even if only one or two components are
going to be picked out with an FPROD statement. In some cases,
even though you may just be figuring the makeup rate of a pure

water stream, the blended feed may put you in a composition region
that OLI cannot solve (for example, 1 mole of H2O with 100 moles
CaCO3). The workaround for this case, if all you want is water in
BATCH
the makeup stream, is to make a dummy stream of pure solid

CaCO3 and put it into the blend with a factor of whatever is neces-
sary (-100, for example) to get rid of that component.
HCURVE
This unit works normally with Electrolytes. However, since electro-
lyte thermodynamic methods do not give you heat capacity or
entropy, those properties will be missing in the reports. The pseudo-
critical and petro reports are available, but are unlikely to give
meaningful quantities for electrolyte streams.
ELECTROLYTES
Phase Envelope
The Phase Envelope is available only with SRK and PR thermody-
namic methods and is therefore disallowed with Electrolytes.
Hydrates
The Hydrates unit does not have a method set associated with it;
therefore, it may be used with a stream exiting an electrolyte unit.
BVLE
The BVLE unit may be used with Electrolyte thermodynamic meth-
ods, provided water is one of the two components chosen for the
unit’s calculations. You must be careful not to specify the BVLE
unit such that it goes into a composition region where the flash will
not solve because there is too little water. It is probably preferable to
do BVLE-type analysis using the standalone flash capabilities avail-
able in the Electrolyte Utility Package.
Hextables
The Hextables utility is not yet available with Electrolyte thermody-
namic methods. The controllers, the optimizer, and recycle data all
work normally with electrolytes. See above, however, for comments
on what parameters can be used in SPEC and DEFINE statements.
With controllers and the optimizer, one must be careful not to allow
a VARY statement to create a condition where OLI cannot solve a
flash.

Case Study, Restart, Interactive
These options work exactly the same for Electrolyte problems as for
other problems.
Depressuring Unit
This unit is currently disallowed with Electrolytes.
Considerations Regarding Transport Properties

Currently, all transport property methods are allowed through key-
words with PRO/II Electrolytes (though most electrolyte models
will have at least one component for which TRAPP is not valid).
Vapor-phase transport methods should be chosen without regard to
ELECTROLYTES
the electrolyte nature of the problem; PETRO would typically be
the best option. For aqueous electrolyte streams, the recommended
method for the liquid phase is PURE, since the other methods in
PRO/II are primarily intended for hydrocarbon streams. The result-
ing transport properties will, for most liquid streams, be very close
to the values for pure water.
Output Considerations
To see what is going on in Electrolyte flowsheets, the user should
always use at least the PART setting (which is now the default) on
the PRINT ION flag. The user stream report writer works normally
with Electrolytes. There are, of course, several quantities, such as
heat capacities and entropies, which are not available. Several
others, such as RVP and GHV, will not be meaningful for
electrolyte streams. In addition, quantities such as NBP and TR,
which depend on averages of pure-component numbers, may not be
meaningful because some of the components in an electrolyte
problem are likely to be salts, for which (for example) there is no
NBP or TC in the library. For some of these numbers, dummy
numbers (usually water values) are “filled in” in the library to
satisfy PRO/II input checking; averages using these numbers will
not be very meaningful.
Speed Considerations
Compared to most other standard PRO/II thermodynamic methods,
Electrolytes is slow. This is unavoidable because it has to solve
chemical equilibria simultaneously with phase equilibria. For a
problem with the same number of components, Electrolytes will

typically be slower than a method like SRKM or NRTL by one or
two orders of magnitude.
One way to help the speed factor is to use the smallest model possi-
BATCH
ble that includes all the components in the problem. It would proba-
bly be a good investment (especially if the model is going to be
used many times) to generate in a small model (for example, four
components) if the alternative were to use a much larger pre-gener-
ated model. Problems also run faster in “no-solids” models, and so
these versions should be used if it is known that there is no chance
of solid precipitation.
Because of the time that may be required for solution, it becomes

more worthwhile to provide good initial guesses. Results from ear-
ELECTROLYTES
lier runs may be saved and used in subsequent problems; the PRINT
PROFILE option on the Column is particularly useful for this pur-
pose. While saving profiles may not be worth the trouble for normal
columns, it can be quite worthwhile for an electrolyte column.

Index
A Column hydraulics , 4-5

Component data
ELECTROLYTES
example, 1-9
Acid systems , 2-6 fixed list, 1-10
Acid waste stream-neutralization drums , 1-6 generating , 1-3
Amine systems , 2-5 name lists, 1-9
validity ranges , 1-11 overview, 1-5
Amine towers , 1-6 reconstituted, 1-8
Application guidelines , 1-11 Composition range , 1-11
Compressor , 4-3
Continuously stirred tank reactor , 4-6
B Controller
loop , 4-3
Balance constraints, mass and charge , 1-8 putting a column inside a, 4-5
putting an isothermal reactor inside a, 4-5
Benfield systems , 1-6, 2-25
specification , 4-3
Blended feed , 4-7
Convergence
BVLE unit , 4-8 difficulty , 4-4, 4-5
failure , 4-1
Crystallizer , 4-6
C
Calculations D
invalid , 1-12
Calculator
DEFINE statement , 4-2, 4-7, 4-8
description , 4-7
stream , 4-7 Depressuring unit , 4-9
Case study , 4-9 Dew water calculations , 1-12

Differences between electrolyte version and standard
Caustic systems , 2-23
PRO/II , 1-4
CCDecanter , 4-6
Dissolver , 4-6
Chemdist , 4-5
Distillation column , 4-4
Chemical equilibria , 4-9
Dryer , 4-6
Chlor-alkali plant processes , 1-6
Duty , 4-3
Column , 4-4 fixed , 4-7
PRO/II 5.11 Add-on Modules User’s Guide I-1

E F
Electrolyte methods Fail to converge , 4-1
acid stream neutralization , 1-6 FCentrifuge , 4-6
amine towers , 1-6
Feed, blended , 4-7
Benfield processes , 1-6
Feeds
chlor-alkali plant processes , 1-6
near saturation , 1-14
gas scrubbers/purification , 1-6
with little or no H2O , 1-14
important points , 1-7
in conjuction with non-electrolyte methods , 1-3 Flash
alternative to dissolver, 4-7
mixed thermodynamic applications , 1-12
scale formation prediction , 1-6 conditions , 4-1
solid salts manufacturing , 1-6 duty , 4-3
functionality , 4-3
sour water strippers , 1-6
isentropic , 4-2, 4-3
underground injection well studies , 1-6
ISOT , 4-3
ELECTROLYTES
Electrolyte models
pressure drop , 4-4
acid systems , 2-6
temperature , 4-4
amine systems , 2-5
TPSPEC , 4-3
Benfield systems , 2-25
built-in , 1-5 Flowsheet control , 4-7
caustic systems , 2-23 FPROD statement , 4-7
component index , 2-32 Free water decant , 1-12
entering component data , 1-9 Freezer , 4-7
generating a user-added , 1-5
Fugacity
hydrate systems , 2-27
calculating coefficients , 1-12
index , 2-2
vapor phase , 1-10
invalid calculations , 1-12
list of built-in , 2-1
LLE systems , 2-27
mixed salt systems , 2-9
G
pregenerated , 2-1
scrubber systems , 2-26 Gas scrubbers/purification , 1-6
selecting , 1-2 General data
sour water systems , 2-17 new ION keyword , 1-7
summary , 2-5 overview , 1-5
supported , 1-2 print statement , 1-7
unsupported , 1-2 General reactor , 4-5
user-added , 2-2 Gibbs reactor , 4-2, 4-5
Electrolyte utility package (EUP) , 2-2
main menu options , 3-1
Electrolytic column algorithm (ELDIST) H
advantages , 1-4
disadvantages , 1-4
HCURVE , 4-8
uses , 1-4
Heat capacity , 4-2, 4-8
ENTHALPY = ELEC example , 1-13
Heat exchanger
Entropy , 4-2, 4-8
LNGHX , 4-4
Entropy and heat capacity calculations , 1-12 rigorous , 4-4
Equilibrium simple , 4-4
calculations , 4-6 Hextables utility , 4-8
not reached , 4-6
Hydrate systems , 2-27
Expander , 4-3
I-2 Index
Hydrates unit , 4-8 O
I OLI method , 1-6

Output
limitations , 4-9
Index
component , 2-32
electrolyte models , 2-2
P
Initial estimate generator , 4-5
Interactive option , 4-9
Particle size distribution (PSD) , 4-6
Ionic species , 1-4
PETRO transport properties , 4-9
Ionic strength , 1-12
pH , 4-3
Isentropic flash , 4-2
Phase
Isothermal flash example , 1-8 envelope, 4-8
ELECTROLYTES
equilibria, 4-6, 4-9
type LS, 4-6
K Phase boundary , 4-3
Pipe , 4-4
Kinetics , 4-7 Plug flow reactor , 4-6
Pregenerated models , 2-1
L Pressure
drop, 4-4
range , 1-11
LIBID statement , 4-7 Print profile option , 4-5
Liquid phase, pure , 4-9 PRO/II’s graphical user interface (GUI)
Liquid/liquid equilibrum (LLE) , 4-2 capability , 4-1
Lists limitations , 4-1
components , 1-10 Pump , 4-3
thermodynamic methods , 1-10
LLE systems , 2-27
valiidy ranges , 1-11 R
LNGHX heat exchanger , 4-4
Reactor
continuously stirred tank reactor, 4-6
M general, 4-5
Gibbs , 4-5
Melter , 4-7 isothermal, 4-5
plug flow, 4-6
Mixed salt systems , 2-9
Reconstituted components , 1-8
Mixer , 4-3
References , 1-15
Restart option , 4-9
N RFilter , 4-6
Rigorous heat exchanger , 4-4
Newton-Raphson method , 1-4
Nonaqueous electrolyte systems , 1-12
Non-ideal aqueous electrolytic distillation , 1-4
S
NRTL (Chen’s) method , 1-6
Scale formation prediction , 1-6

Scrubber systems , 2-26 OLI , 1-6
Simple heat exchanger , 4-4 special case , 1-13
Solid salts manufacturing , 1-6 transport properties , 1-11
Solid species , 4-2 Transport properties , 1-11

limitations , 4-9
Solids
drying , 4-6 True aqueous solution species , 1-8
filtering , 4-6
no-solids models , 4-10
producing precipitate , 4-6 U
Solids handling utilities
ccdecanter , 4-6 Underground injection well studies , 1-6
crystallizer , 4-6 Unit operations
dissolver , 4-6 BVLE , 4-8
dryer , 4-6 calculator , 4-7
fcentrifuge , 4-6 calculator, stream , 4-7
ELECTROLYTES
freezer , 4-7 ccdecanter , 4-6

melter , 4-7 compressor , 4-3
rfilter , 4-6 controller loop , 4-3
Sour water systems , 1-6, 2-17 crystallizer , 4-6
SPEC statement , 4-2 dissolver , 4-6
SPEC statements , 4-8 distillation column , 4-4
dryer , 4-6
Speed , 4-9
expander , 4-3
Splitter , 4-3 fcentrifuge , 4-6
Stream calculator , 4-7 flash , 4-3
Stream data input , 1-13 flowsheet control , 4-7
Supersaturation limit , 4-7 freezer , 4-7
HCURVE , 4-8
Surface tension , 4-4
heat exchanger, LNGHX , 4-4
heat exchanger, rigorous , 4-4
heat exchanger, simple , 4-4
T hextables utility , 4-8
hydrates , 4-8
Temperature range , 1-11 melter , 4-7
Thermodynamic data mixer , 4-3
composition range , 1-11 overview of available , 1-5
fugacity , 1-12 phase envelope , 4-8
overview , 1-5 pipe , 4-4
pressure range , 1-11 pump , 4-3
temperature range , 1-11 reactor, continuously stirred tank reactor , 4-6
Thermodynamic methods reactor, general , 4-5
application guidelines , 1-11 reactor, Gibbs , 4-5
available , 1-6 reactor, isothermal , 4-5
built-in , 1-2 reactor, Plug flow , 4-6
choosing multiple , 1-10 rfilter , 4-6
fixed list , 1-10 SPEC, DEFINE, VARY , 4-2
limitations , 4-1 splitter , 4-3
mixed , 1-12 supported , 1-1
non-electrolyte , 4-4 valve , 4-3
NRTL (Chen’s) , 1-6 User-added models , 2-2
I-4 Index
V methods for determining coefficients, 1-12
VARY statement , 4-2, 4-8
Validity ranges Viscosity , 4-4

Amine systems , 1-11
general , 1-11
LLE sytstems , 1-11 W
Valve , 4-3
Vapor-phase fugacity Water, removing , 4-6
calculating , 1-10
ELECTROLYTES

Electrolyte

Загружено:

Сведения о документе

Авторское право

Доступные форматы

Поделиться этим документом

Поделиться или встроить документ

Параметры публикации

Этот документ был вам полезен?

Это неприемлемый материал?

Авторское право:

Доступные форматы

Electrolyte

Загружено:

Авторское право:

Доступные форматы

ELECTROLYTE MODULE

Chapter 2 Electrolyte Models

PRO/II 5.11 Add-On Modules User’s Guide iii

Chapter 3 Generating a User-Added Electrolyte Model

Chapter 4 Electrolytes in PRO/II GUI

PRO/II 5.11 Add-On Modules User’s Guide v

Using the Electrolyte Module

PRO/II 5.11 Add-On Modules User’s Guide 1-1

apply to fixed component lists with a predefined set of thermody-

Note: Electrolyte models cannot be used to calculate the follow-

● Non-aqueous electrolyte systems.

● Water dew points.

1-2 Electrolyte Module

➤ Select Electrolyte in the Category list.

You should be careful when using non-electrolyte and electrolyte

When using Electrolyte thermodynamic methods, the OLILIB com-

Generating Electrolyte Components

PRO/II 5.11 Add-On Modules User’s Guide 1-3

➤ Select Generate Electrolyte Components from the Input menu.

All electrolyte components for the flowsheet (including compounds

Electrolytic Column Algorithm (ELDIST)

The Electrolytic Column Algorithm is selected from the Column

Note: Electrolytic thermodynamic models support only VLE, and

● Rigorously models ionic equilibrium systems.

● Side columns are not supported.

● Pumparounds and tray hydraulics are not available

● Certain column specifications and variables are not

1-4 Electrolyte Module

■ Electrolyte Component Data — Description of the COMPO-

■ Electrolyte Thermodynamic Data — Description of the

■ Generating a User-Added Electrolyte Model — Description

■ Electrolytes in PRO/II Flowsheeting — Overview of the

PRO/II Electrolytes is composed of an integrated set of programs

PRO/II 5.11 Add-On Modules User’s Guide 1-5

completely non-aqueous (again, with water content as low as

■ Gas scrubbers/purification using carbonate, amine, or caustic

■ Sour water strippers

■ Acid waste stream-neutralization drums

■ Scale formation prediction for wells and pipes (oilfields, geo-

■ Underground injection well studies

■ Solid salts manufacturing (potash, caustic, carbonates, etc.)

■ Chlor-alkali plant processes.

1-6 Electrolyte Module

■ PRO/II Electrolytes is designed for use in aqueous electrolyte

■ PRO/II Electrolytes has one new unit operation (ELDIST), a

■ The Electrolyte Utility Package (EUP) supplied with PRO/II

Electrolyte General Data

NONE No electrolyte-specific output is printed.

PRO/II 5.11 Add-On Modules User’s Guide 1-7

cies in the aqueous solution. Adds, for ELDIST

ALL Gives all output given by PART option. Adds Elec-

are reported as molalities for the true chemical

True Aqueous Solution Species and Reconstituted Components

1-8 Electrolyte Module

Electrolyte Component Data

Note: In contrast to conventional PRO/II, the Electrolytes version

Components can be renamed for printing purposes using the PRO/II

Components in OLI’s databanks that are not covered in the SIMSCI

PRO/II 5.11 Add-On Modules User’s Guide 1-9

thermodynamic methods for K-values, enthalpy, and density. The

Note: See the PRO/II Reference Manual for a summary of the

PRO/II Electrolytes for the calculation of thermodynamic quanti-

The name of the selected electrolyte model is treated in the input as

When multiple thermodynamic methods are needed for an applica-