Table Of ContentA Guide to Using
OLI Analyzer Studio
Including Studio ScaleChem
Version 9.1
OLI Systems, Inc.
Copyright© 2014
OLI Systems, Inc.
All rights reserved.
The enclosed materials are provided to the lessees, selected individuals and agents of OLI Systems,
Inc. The material may not be duplicated or otherwise provided to any entity without the expressed
permission of OLI Systems, Inc.
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Suite 301
Cedar Knolls, NJ 07927
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[email protected]
www.olisystems.com
Disclaimer:
This manual was produced using the OLI/Analyzer Studio version 9.1 build 2 (9.1.2).
As time progresses, new data and refinements to existing data sets can result in values
that you obtain being slightly different than what is presented in this manual. This is a
natural progress and cannot be avoided. When large systematic changes to the
software occur, this manual will be updated.
Chapter 1 Welcome to OLI 7
Who is OLI Systems? ................................................................................................................ 7
What does OLI Systems do? ...................................................................................................... 9
Aqueous Simulation .................................................................................................... 9
Oil-Field Chemistry ..................................................................................................... 9
Corrosion Chemistry ................................................................................................... 9
Process Modeling ...................................................................................................... 10
Chapter 2 Introduction to Aqueous Speciation 11
Overview ................................................................................................................................. 11
What is the pH of the Following Stream? ................................................................. 11
Answer: ..................................................................................................................... 22
Speciation in Sour Water ......................................................................................................... 23
Sour Water Species.................................................................................................... 23
Chemistry Summary (Molecular Equilibrium) .......................................................... 23
Chemistry Summary (Electrolyte Equilibrium) ......................................................... 23
Calculating Partial Pressures ..................................................................................... 24
Considering only the Vapor-Liquid equilibria........................................................... 26
Considering the full OLI Speciation Model .............................................................. 26
An Example of Speciation ....................................................................................................... 28
Summary: ................................................................................................................................. 34
Chapter 3 Removing Nickel from Wastewater 35
The Removal of Nickel using OLI Analyzer Studio ................................................................ 35
How to run the tour? .................................................................................................. 36
The Tour Starts Here... .............................................................................................. 36
Scenario 1: Wastewater without additives ................................................................. 37
Scenario 2: Now, What about the Real Waste? ......................................................... 57
Scenario 3: Is All Really Lost? .................................................................................. 61
Final Thoughts... ...................................................................................................................... 62
Save, Save and then Save again ................................................................................. 63
Chapter 4 The Mathematical Model 65
Overview ................................................................................................................................. 65
Specific Problem ...................................................................................................................... 65
Recipe for Writing the Model .................................................................................... 66
The Components of the Simulator ........................................................................................... 68
The Database ............................................................................................................. 68
The Chemistry Model ................................................................................................ 68
The Generator ............................................................................................................ 69
The OLI Engine ......................................................................................................... 69
Phase Selection ........................................................................................................................ 69
Chapter 5 Solids Precipitation 73
Overview ................................................................................................................................. 73
The Tour .................................................................................................................................. 73
Objectives .................................................................................................................. 73
Let’s begin ................................................................................................................. 73
Selecting the precipitation point calculation .............................................................. 76
Expanding the Chemistry .......................................................................................... 79
Removing Solids ....................................................................................................... 80
A Guide to Using the OLI Studio Welcome to OLI • 1
Repeating the precipitation point calculation ............................................................ 81
Removing Dolomite .................................................................................................. 84
Units manager new look ............................................................................................ 85
Now would be a good time to save your files. .......................................................... 87
Chapter 6 Aqueous Thermodynamics 89
Overview ................................................................................................................................. 89
The Equilibrium Constant ........................................................................................................ 89
Question: ................................................................................................................... 89
Principal Thermodynamic Properties ...................................................................................... 90
HKF (Helgeson-Kirkham-Flowers)Equation of State, ............................................................. 91
The Helgeson Equation of State ................................................................................ 93
What is the standard State? ........................................................................................ 94
Excess Properties ..................................................................................................................... 95
Ionic Strength ............................................................................................................ 95
Definition of Aqueous Activity Coefficients ............................................................. 96
Modern Formulations ................................................................................................ 97
Neutral Species ........................................................................................................ 101
Multiphase Model .................................................................................................................. 102
Solid-Aqueous Equilibrium ..................................................................................... 102
Solid Phase Thermodynamic Properties .................................................................. 103
Mixed EOS Model ................................................................................................... 103
Limitations of the Current OLI Thermodynamic Model ....................................................... 104
Scaling Tendencies ................................................................................................................ 105
What is a scaling tendency?..................................................................................... 105
Calculating Osmotic Pressures .............................................................................................. 108
Summary ................................................................................................................................ 108
Chapter 7 Single Point Calculations 109
Objectives .............................................................................................................................. 109
Isothermal .............................................................................................................................. 110
Mix Calculations .................................................................................................................... 114
Bubble Point .......................................................................................................................... 121
Dew Point .............................................................................................................................. 125
Vapor Amounts/Fractions ...................................................................................................... 129
Chapter 8 Multiple Point Calculations 133
Objectives .............................................................................................................................. 133
Temperature ........................................................................................................................... 134
Pressure .................................................................................................................................. 145
Composition ........................................................................................................................... 150
pH (Mixer) ............................................................................................................................. 154
Cascading Mixers .................................................................................................................. 160
Secondary Surveys ................................................................................................................. 166
Contour Plots ......................................................................................................................... 170
Chapter 9 Water Analysis in Analyzer Studio: An Overview 173
Overview: .............................................................................................................................. 173
An Example: .......................................................................................................................... 173
Summary ................................................................................................................................ 185
Chapter 10 Water Analysis in Analyzer Studio: A Tour 187
A Guide to Using the OLI Studio Welcome to OLI • 2
Reconciling a Brine from an Oil Field ................................................................................... 187
The Application ....................................................................................................... 187
Tour Conventions .................................................................................................... 188
The tour Starts here! ................................................................................................ 188
Calculating Alkalinity ............................................................................................. 199
Creating a stream from the sample .......................................................................... 202
Chapter 11 Petroleum Calculations 203
Overview ............................................................................................................................... 203
Assays ...................................................................................................................... 203
Pseudocomponents .................................................................................................. 210
Chapter 12 Scope of Corrosion Analyzer 213
Overview ............................................................................................................................... 213
Thermodynamics of Corrosion ................................................................................ 213
Kinetics of general corrosion ................................................................................... 214
Other phenomena .................................................................................................... 214
Real-solution stability diagrams ............................................................................................ 214
Chapter 13 Generating Stability Diagrams in Corrosion Analyzer 215
An Example ........................................................................................................................... 215
How to Use Stability Diagrams ............................................................................................. 222
Chapter 14 Generation of Stability Diagrams 227
Construction of real-solution stability diagrams .................................................................... 227
Construction of equilibrium equations .................................................................... 227
Examples ................................................................................................................. 228
Cases when both the metal and ligands are subject to redox equilibria ................... 228
Simulated titrations ................................................................................................................ 229
Equilibrium lines for chemical reactions ............................................................................... 229
Determination of predominance areas ................................................................................... 230
Chapter 15 A Tour of Corrosion Analyzer 231
Overview ............................................................................................................................... 231
Iron in Water .......................................................................................................................... 231
Adding Hydrogen Sulfide ........................................................................................ 240
Chapter 16 Modeling the Effects of Acidity & Alkalinity on Corrosion 245
Overview ............................................................................................................................... 245
High Temperature Iron in Water ............................................................................. 245
How does the prediction of passivation relate to corrosion rate data? ..................... 248
Neutralization of Refinery Streams with Alkanolamines ........................................ 248
Chapter 17 Modeling the Effects of Complexation on Corrosion 253
Overview ............................................................................................................................... 253
Copper and Ammonia .............................................................................................. 253
Gold in the presence of Cyanides ............................................................................ 257
Chapter 18 Modeling the Effect of Oxidizing Inhibitors on Corrosion 261
Overview ............................................................................................................................... 261
A Guide to Using the OLI Studio Welcome to OLI • 3
Iron in the presence of chromates ............................................................................ 261
Iron in the presence of arsenates .............................................................................. 264
Chapter 19 Implications of Stability Diagrams on Cathodic Protection 267
Overview ............................................................................................................................... 267
Example: Iron at 25 and 300 degree centigrade ...................................................... 267
Chapter 20 Selective Oxidation and Reduction Chemistry 269
Overview ............................................................................................................................... 269
Creating the default oxidation case ......................................................................... 269
Selective Redox, removing an undesired oxidation state. ....................................... 271
Chapter 21 Introduction to Rates of Corrosion 275
Chemistry ............................................................................................................................... 275
Calculation types ................................................................................................................... 275
Metal Chemistry .................................................................................................................... 276
Flow conditions ..................................................................................................................... 277
Kinetics of general corrosion ................................................................................................. 278
Chapter 22 Rates of General Corrosion – A Tour 281
Overview ............................................................................................................................... 281
The Rates of Corrosion .......................................................................................................... 281
Setting up the calculation ........................................................................................ 283
Flow survey ............................................................................................................. 287
Chapter 23 Thermal Aging and Variations in Alloy Composition
Introduction 291
What can be simulated? ......................................................................................................... 291
Alloy Chemistry..................................................................................................................... 292
Calculation types ................................................................................................................... 292
Output specific to thermal aging ............................................................................................ 293
Chapter 24 Thermal Aging and Variations in Alloy Composition 295
Overview ............................................................................................................................... 295
Example 1: Thermal aging of alloy 600................................................................................. 296
Setting up the calculation ........................................................................................ 296
Analyzing the results ............................................................................................... 299
Example 2: Thermal aging of alloy 825................................................................................. 305
Setting up the calculation ........................................................................................ 306
Analyzing the results ............................................................................................... 308
Example 3: Localized corrosion of annealed and thermally aged duplex alloy 2205 ............ 310
Setting up the calculation ........................................................................................ 312
Analyzing the results ............................................................................................... 315
Setting up the calculation ........................................................................................ 317
Analyzing the results ............................................................................................... 318
Chapter 25 Extreme Value Statistics for Predicting Pitting Damage – Intro321
Extreme Value Statistics ........................................................................................................ 321
Input and Output .................................................................................................................... 322
Advantages and Disadvantages of EVS ................................................................................. 322
A Guide to Using the OLI Studio Welcome to OLI • 4
Chapter 26 Extreme Value Statistics for Predicting Pitting Damage – A
Tour 323
Overview ............................................................................................................................... 323
Example 1: Corrosion of aluminum alloy in tap water .......................................................... 324
Setting up the calculation (Pit depth prediction) ..................................................... 327
Analyzing the results ............................................................................................... 328
Setting up the calculations for engineering tasks ..................................................... 331
Example 2: Corrosion in Pipelines. ....................................................................................... 339
Example 3: Possible Case of Insufficient Data ...................................................................... 346
Chapter 27 Petroleum Fraction Thermodynamic Methods 351
Distillation Methods of the ASTM .......................................................................... 351
Average Bulk Density ............................................................................................. 351
Thermodynamic Methods ........................................................................................ 352
Chapter 28 How to create OLI Analyzers Chemical Diagrams 353
Chapter 29 Managing Private Databases in the OLI Analyzer 365
Selecting Databases ............................................................................................................... 365
How to load a private database into the OLI Analyzers ........................................................ 370
How to unload a database from the OLI Analyzers ............................................................... 377
Chapter 30 OLI Units Manager 379
Chapter 31 Tools | Options 387
Setting the Auto Save and Automatic Backup Features .......................................... 387
Changing the default file locations .......................................................................... 388
Turning off hardware acceleration .......................................................................... 391
Chapter 32 Modifying the plot, hiding curves 395
Chapter 33 Customizing the Report 403
Chapter 34 Displaying Transport Properties and Extra Thermodynamic
Parameters 409
Single Point Calculations ........................................................................................ 409
Survey Calculations ................................................................................................. 412
Chapter 35 Studio ScaleChem Overview 415
Why Use StudioScaleChem? ................................................................................................. 415
StudioScaleChem’s Development ......................................................................................... 415
Chapter 36 Studio ScaleChem Chemistry 417
Aqueous Chemistry ............................................................................................................... 417
StudioScaleChem Chemistry ................................................................................................. 417
The Standard Chemistry Model ............................................................................... 417
The Expanded Chemistry Model ............................................................................. 418
Hydrocarbon Petroleum Fractions ........................................................................... 418
Density .................................................................................................................... 419
A Guide to Using the OLI Studio Welcome to OLI • 5
Thermodynamic Methods (pseudo-components and petroleum fractions) .............. 419
Summary ................................................................................................................................ 419
Chapter 37 Studio ScaleChem Getting Started 421
Terminology .......................................................................................................................... 421
Analysis ................................................................................................................... 421
Reconciliation .......................................................................................................... 421
Calculating a Scaling Tendency .............................................................................. 422
Calculating a Scale Index ........................................................................................ 423
Putting together a calculation ................................................................................................ 423
Starting the StudioScaleChem Program .................................................................. 424
StudioScaleChem Tour ............................................................................................ 424
Brine and Gases ....................................................................................................... 433
Chapter 38 Studio ScaleChem Calculations 441
Calculations Overview ........................................................................................................... 441
Calculations: Adding a new brine sample ............................................................... 441
Calculations: Adding a Gas Sample ........................................................................ 442
Calculations: Adding an Oil sample ........................................................................ 444
Calculations: Hydrocarbon - Pseudocomponent approach ...................................... 444
Mix Calculation: Overview ................................................................................................... 449
Mix Calculation: Set Up .......................................................................................... 449
Saturate Calculations: Overview............................................................................................ 454
Saturate Calculations: Set Up .................................................................................. 454
Facility Calculation: Overview .............................................................................................. 459
Create the above brines ........................................................................................... 459
Facility Calculation: Set Up .................................................................................... 459
Chapter 39 Studio ScaleChem Interpreting Results 463
Overview ............................................................................................................................... 463
Valid Water Analysis Data .................................................................................................... 463
Assumptions ............................................................................................................ 463
Electroneutrality ...................................................................................................... 463
pH/Alkalinity ........................................................................................................... 466
Speciation ................................................................................................................ 468
Supersaturation of Solids ......................................................................................... 470
Summary Content .................................................................................................................. 471
Reconciliation summary .......................................................................................... 471
Gas Analysis ............................................................................................................ 471
Node Summary ........................................................................................................ 472
Overview of StudioScaleChem Output .................................................................................. 473
Summaries ............................................................................................................................. 473
Plot ......................................................................................................................................... 474
Determining the Default Plot ................................................................................... 474
Viewing Data ........................................................................................................... 474
Data Available ......................................................................................................... 475
A Guide to Using the OLI Studio Welcome to OLI • 6
Chapter 1 Welcome to OLI
Who is OLI Systems?
OLI Systems was founded in 1971 by Dr. Marshall Rafal. During the past four decades OLI has developed, at a cost of
almost $30,000,000, commercial computer software which has established the company as the world leader in simulating
aqueous-based chemical systems
OLI's unique capability is providing the world with the only predictive thermodynamic framework for calculating the
physical and chemical properties of multi-phase, aqueous-based systems. This framework is applicable to most multi-
component mixtures of chemicals in water, and is predictive over almost any conceivable temperature, pressure and
concentration of interest.
Employing this unique and powerful framework, the OLI Engine, supported by a very large, in-place databank, allows
users to predict the chemical and phase behavior (including aqueous, vapor, non-aqueous liquid and multiple solids), of
most mixtures of inorganic or organic chemicals in water. The resulting phase separation into aqueous, vapor, organic
liquid and multiple solids is performed automatically. In the laboratory, in steady-state or dynamic process conditions or
in the natural environment, the OLI Engine is broad-based and accurate.
OLI's world leadership is reflected in many ways, including authorship of AIChE's Handbook of Aqueous Electrolyte
Thermodynamics. OLI software is used by nearly all of the largest companies in the Chemicals and Oil & Gas sectors of
the Chemical Process Industries (CPI) as well as companies in other sectors such as Metals and Mining, Forest Products
and Pharmaceuticals. In addition, OLI software is used extensively in Environmental, E & C and Basic Research.
OLI has created several widely-used products:
OLI Engine
OLI's aqueous thermodynamics are at the heart of the OLI software. OLI
Engine refers to the thermodynamic database, thermodynamic framework, and
supporting numerical computation to simulate the chemical and phase behavior of
aqueous-based systems.
Analyzer Studio
Never has aqueous chemistry problem solving been easier. Analyzer Studio
combines ease of learning, ease of use with the power of the OLI Engine. It supports
single and multiple point calculations, utilizing OLI's extensive PUBLIC databanks.
Ionic input is possible. Analyzer Studio allows customers to input, store,
manipulate, adjust and reconcile laboratory data, with facilities to adjust laboratory
errors in pH and charge balance.
A Guide to Using the OLI Studio Welcome to OLI • 7
OLI Express
Prior to the Analyzers, access to the OLI Engine was through OLI Express. It
supports single ScratchPad and parametric Survey calculations for investigating
chemical behavior, pH, solubility, multiple phases, speciation, and other phenomena.
Environmental Simulation Program (ESP)
ESP is OLI’s steady-state flowsheet simulation package capable of simulating
rigorous environmental unit operations including stripping/scrubbing, pH control,
ion exchange, biotreatment, clarification, UF/RO, electrodialysis, and many others.
Feedback control and recycle convergence are included.
Corrosion Analyzer (now part of the OLI Studio)
CSP provides a framework to analyze metal and alloy redox solution chemistry
for any mixture of chemicals at almost any condition of interest. The package
provides for real-solution stability diagrams (e.g., Pourbaix and Yield) and accurate
prediction of electrical conductivity and ORP. CSP supports calculation of
predictive rates of corrosion for a limited set of chemistry.
DynaChem
Dynamic is a flowsheet simulation package for time-dependent and transient
processes. DynaChem includes support for scheduled entry feeds, PID control, open
and closed loop, feedback and feed-forward, multi-cascade, adaptive gain, pH,
compositional control and many others. Operator intervention to introduce upsets,
manually adjust valves and control settings is also possible.
ScaleChem
ScaleChem is OLI’s solution for oil-field applications including surface and
subsurface mineral scale prediction, saturation profiles, and produced/formation
water mixing. ScaleChem is based upon accurate fitting of binary, ternary and
quaternary data up for several common scales, and many more "not-so-common"
scales!
OLI is comprised of an extraordinary staff of advanced degree scientists and
engineers who enable OLI to maintain a high-level of Research & Development
while offering a full range of Support Services and Professional Services.
A Guide to Using the OLI Studio Welcome to OLI • 8
Description:This manual was produced using the OLI/Analyzer Studio version 9.1 build 2 (9.1
.2). As time progresses, new Oil-Field Chemistry . Corrosion Chemistry .
