1. OLI technology & electrolyte simulation
AQSim
October 2017
Think simulation!

2. Agenda Introductions Introduction to OLI, AQSim Application discussion
Software
Technology
Application discussion

3. Introductions Name Position in company Background
Simulation experience
Simulation interest?

4. Who is OLI? A Technology Company Core competency Products
Mission: To further the electrolyte science
Core competency
Electrolyte thermodynamics
Experimental data mining and development
Process simulation
Aqueous corrosion science
Products
Software
Sponsored research
In business 45 years, core competency is electrolyte thermodynamics research and development. (consider size of company of prospect) 8 full time electrolyte physical chemists & thermodynamicists.
From this work we have developed expertise in experimental data mining and contracting labs for data, in process simulation and mathematical techniques. electrolyte and simulation experts. Marshall was at Exxon and became interested in challenging mathematical convergence models. Electrolytes have very challenging mathematical behavior.
When you work with OLI you work primarily work through SW. Sometimes you will work with OLI to extend the model or the data.

5. Who is AQSim? OLI Partner Company Using (exclusively) OLI technology
Mission: To empower clients to solve water chemistry issues
Using (exclusively) OLI technology
OLI applications consulting
OLI training
OLI software sales
Business Development Director for OLI
Worldwide except China, Japan, India, SE Asia
Most often when you work with OLI, you work through AQSim. Business development directors for OLI. Office in OLI, work closely together. Mission…OLI to further electrolyte science, AQSim to empower clients to solve water chemistry applications. AQSim works exclusively with OLI.

6. OLI Clients Oil & Gas Water treatment Chemicals Power / nuclear power
Broad spectrum of industries
Oil & Gas
Water treatment
Chemicals
Power / nuclear power
Metals and mining
Pulp and paper
Engineering companies
Research companies
OLI is found anywhere that water is present. The team of thermodynamists have created a broad database to be used in many markets. The software is general, you give it meaning by defining your chemistry.

7. Three aspects of simulation work together for comprehensive modeling
OLI Capabilities
Three aspects of simulation work together for comprehensive modeling

8. Chemistry Simulation with OLI
Water chemistry behavior
Physical and chemical properties of multi-component systems
Solid-Liquid-Vapor-Organic equilibrium
Advanced mechanisms
Kinetics framework
Reduction / oxidation
Mass transfer
Surface reactions
Advanced properties
ORP
Osmotic Pressure, etc.)
Equilibrium-based system w multiple phases grounded in first principle thermodynamics. Strength is Equation Of State and Activity models for calculations.
In addition, software can model kinetics and redox, mass transfer and surface reactions, if that suits your needs. For the kinetic framework you need to supply the kinetic data. Finally, advanced properties such as osmotic pressure for membrane, thermal conductivity for heat exchangers, water activity for hydrates.

9. Flowsheet Simulation with OLI
Process behavior using two-prong approach
Electrolyte primary: OLI Flowsheet: ESP
Developed by OLI consortium in 1990
When OLI-only thermodynamics
Updated UI for water treatment in 2016
OLI Alliance Partner strategy
Couple OLI thermodynamics with other methods
Reach a broad flowsheet simulation market
Lessen the learning curve
Simsci, AspenTech, Honeywell, Andritz, PSE
Remains an active OLI strategy

10. Corrosion Simulation with OLI
Corrosion Prediction
Thermodynamics of corrosion
Real-solution Pourbaix diagrams
Uniform (general) corrosion
Polarization curves
Localized corrosion
Worst-case pitting rate
Extreme value statistics EVS
Calculate remaining asset life
Add on to the base product.
We do thermodynamics of corrosion using our speciation model. That tells us if corrosion is possible and we show it through stability diagrams.
We also offer a uniform general kinetic model, that primarily addresses the corrosion of chemical attack,
when the bulk solution is in contact with the metal surface. (Who is the audience?) Calculating anodic and cathodic half-reactions to produce polarization curve.
From solving the general corrosion model, we can also calculate a worst case pitting rate.
Finally, we can calculate remaining asset life with a statistical model using your pit depth measurements,

11. Two separate methods for describing electrolyte behavior
OLI Frameworks
Two separate methods for describing electrolyte behavior

12. Two OLI frameworks Aqueous (AQ) Mixed Solvent Elec (MSE)
Strong electrolyte theory based on research of Debye-Huckel, Pitzer, and Bromley
Mixed Solvent Elec (MSE)
Aqueous & non-Aqueous electrolyte theory A superset of the AQ Framework
Thermodynamic range
-50 to 300 C
0 to 1500 bar
0 to 30 molal ionic strength
5,500 species database
~2000 solids
~2500 organics
85 elements
Thermodynamic range
90% of Critical Temperature
0 to bar
0 to 1 mol fraction solute
2,700 species (Q1 2017)
~1050 solids
~770 organics
75 elements
Two frameworks AQ and MSE
Depending on chemistry and conditions, you would use one or the other
AQ strong electrolyte model introduced in the 20th century and it assumes water as dominant species. Excellent for a wide variety of systems where water is dominant.
Good for heavy brines, brackish water
330C temp limit, 1500 bar pressure limit, 30 molal ionic strength.
Trouble with highly miscible systems - H2SO4, MEG, Methanol, HF - AQ model breaks down
In the 21st century new theories have developed that expand beyond the limitation of this model, the MSE model encompasses all of the AQ model and goes beyond to the highly miscible, higher T, P and also electrolytes with no water.

13. OLI framework design Speciation model Standard-state properties
Liquid, vapor, and solid phases
Standard-state properties
Helgeson-Kirkham-Flowers-Tanger Equation of State for ionic and neutral aqueous species
Standard thermo-chemistry for solid and gas species
Excess properties Gibbs energy model
Solution non-ideality
Algorithms
For solving phase and chemical equilibria
Whats’s going on in that black box? OLI says that any good Elec framework should have 4 components: Work in speciated model, in terms of ions, vapors, precipitates not molecular flows. EOS for ideal conditions (25C, 1atm, infinite dilution) - Helgeson. Activity model for non-ideality away from the reference state uses minimization of Gibbs free energy. Algorithms to solve mathematically challenging systems.
Thermo, so work w EOS for standard state props, proprietary activity model for non-ideality. Publish model in papers.
Algorithms needed for real-world scenarios, need to handle phase boundaries, what happens when change phases.

14. Advances in the MSE framework
Kept the same Helgeson Equation of State
Added a more complex activity model
Debye – Huckel long range term
New ionic interaction (middle-range) term
Electrolytes ranging from dilute solutions  pure solutes
Short-range term for interactions
Between neutral molecules based on the UNIQUAC model
Modeling water as H3O+ and OH-
What’s the breakthrough of the MSE model? Helgeson found in ‘88, solid, stopped looking. Difference is first in the activity model. More complicated allowing for higher concentration limits. Model (equations) is public, but underlying data is proprietary, our competitive edge. 3-term activity model, equations published, better granularity to cover the higher concentrations.
Other difference is that we began to model water with the hydronium ion rather than the hydrogen ion. This is more physically representative of what is really happening in water.
Why? We were getting a better data fit when developing the model.
Hydronium – why care? You may not, makes a math difference, gives better data fit.
Cannot go back and forth readily between the 2 models since we have different component definitions.

15. Delivery of electrolyte science through software
OLI Products
Delivery of electrolyte science through software

16. OLI Studio Stream Analyzer Corrosion Analyzer Studio ScaleChem
Single point & survey
Mix & separate
Ionic input, data reconciliation
Corrosion Analyzer
Stability diagrams
Polarization curves
Studio ScaleChem
Reservoir saturation
Mixing waters (compatibility)
Water, gas, oil analysis
Regardless of which OLI component interests you, we always like to start in OLI Studio - the clearest way to view OLI technology. Look at single points, surveys/trends. Can take ionic input to balance water samples. Simple mixers and separation.
Can plug in CA for corrosion studies
SSC – focus for production chemistry

17. OLI Flowsheets OLI-only Thermodynamics OLI Flowsheet: ESP Aspen Plus
Electrolyte Simulation Program
OLI Flowsheet: ESP
Aspen Plus
Aspen HYSYS
gPROMS
UniSim Design
PRO/II
IDEAS
Alliance Partners: OLI Engine in …
OLI as a property method
25 years experience in electrolyte flowsheet simulation, sour water stripping, membranes, solvent regeneration, new UI released in OLI – only thermodynamics.
If you have access to any of our alliance partner products, we recommend you stay with them! And use OLI as a property method within their flowsheet.
Andritz = IDEAS
Schneider Elec = Pro-II
HON = UniSim Design
Aspen = Aspen Plus or HYSYS

18. Modeling the physical process to explain and predict behavior
Simulation Power
Modeling the physical process to explain and predict behavior

19. How OLI tools help clients
Target: To duplicate the physical process ... using mathematics and chemistry
Result: To focus laboratory / pilot plant tests
... finding the likely optimum
Result: anticipate process changes
... reducing cost, process upsets, and risk
Good slide for mechanical eng who wonder why do process simulation.

20. Typical Approach Conditions Scenarios Setpoints Stream/Analysis Data
Software
Output
Recommendations
Interpretation
Our goal is to understand, can we model your process?
You have some inputs, you treat the software as a black box, you get output, and if OLI is modeling your process, you are in a very strong position to make recommendations..
What the key is interpretation. So that we would like to focus our time with you on helping interpreting
Step through inputs, process, etc. INTERPRETATION.
Process
Schematic
Step 2
Step 3
Modifications
Step 1

21. OLI Technology
The key to OLI acceptance is the ability to predict the properties of multi-component, complex systems
But of course the software is not a black box, what is the technology we are using?

22. NH3, H2SO4, H2O 100% water to 100% sulfuric
Symbols are experimental points
Curves are OLI predictions
Ternary system, arbitrarily picked for looks. Series of isotherms, symbols are experimental that came from the literature, from peer reviewed paper, lines are OLI predictions. Chosen to show we can deal with complex mathematical behavior, especially across phase changes. Other is that this is a validation plot. Each MSE system includes a plot to verify what experimental data was used and how well we match on the data prediction.
Shows challenging mathematical behavior. Is one of our validation plots, for each set of species we trace back where the data came from and how well we match. Plots are not made available publicly, but we will work with our clients to provide them on request.
Not a lab, mine literature for data. Sometimes commission lab for client-specific needs.

23. OLI Advisors
Process simulation experts are available to setup and / or review of simulations

24. OLI tools for clients OLI application screening
Chemistry
Process
Validation spreadsheets
Thermophysical modeling service
MSE Regression class

25. Assistance in OLI applications
An OLI license includes
Application building screening and advice
Phone and technical support for clients
Starting Smart with OLI
Software + AQSim support retainer for
Applications setup and review
Technology transfer on your specific case(s)
OLI Simulation Studies
Expert case setup and solution
Delivered in spreadsheets, reports, presentations

26. Training in OLI Public Training Custom training
At OLI office NJ USA (complimentary)
Regional in Houston, Calgary, Aberdeen
Web classes (once every 3 months)
Custom training
Onsite at your company
Custom web training
Convenient to your time zone
Training on your applications
Followup Q/A sessions on your cases

27. Questions?
Onto your application!