OLI technology & electrolyte simulation AQSim August 2017 Think simulation!

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

Introductions Name Position in company Background Simulation experience Simulation interest?

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.

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.

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.

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

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.

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

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,

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

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 4000+ 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.

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.

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.

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

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

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 2016. 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

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

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.

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

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?

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.

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

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

Assistance in OLI applications An OLI license includes Application building screening and advice Phone and email 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

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

Questions? Onto your application!