1. Orientation to OLI Flowsheet: ESP
Starting a new case
AQSim
March 2017
Think simulation!

2. Agenda Introduction to OLI, AQSim OLI Flowsheet: ESP overview
Software
Technology
OLI Flowsheet: ESP overview
Onto the software!

3. 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.

4. 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.

5. 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.

6. 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.

7. 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.

8. 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.

9. Chemistry Simulation with OLI
Water chemistry behavior using the OLI Studio
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.

10. Flowsheet Simulation with OLI
Process behavior using two-prong approach
Electrolyte primary: ESP Original
Developed by OLI consortium in 1990
Supplanted by 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
Returning to Flowsheet: ESP
New product using ESP Original solver
Target: electrolyte flowsheets, e.g., water treatment

11. OLI Flowsheet: ESP content
V9.5.2 Available Blocks
Sixteen generalized blocks with many configurations
Standard: mixer, separator, flow splitter, settler, filter, heat exchanger
Advanced: neutralizer, component splitter, compressor, turbine
Multi-Stage: absorber, distillation (including mass transfer limited)
Future version
sensitivity, membranes, calculation, electrolyzer, extractor, precipitator, & others
Will not be ported
biotreatment, x-crystallizer

12. Orientation Getting started: resources available
Many example templates
Can work one-on-one to explain fine points
Conversion from ESP Original cases is easy
Starting a new case: focus for today
Specifying blocks and connections
Adding controllers
Challenge: working with multi-stage blocks
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

13. Questions?
Let’s get started!