Orientation to OLI corrosion techology AQSim April 2017 Think simulation!

Agenda Introduction to OLI, AQSim OLI corrosion technology Software Technology OLI corrosion technology Onto the software!

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.

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.

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.

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

Corrosion simulation with OLI For a selected set of components / alloys Corrosion of chemical attack Bulk solution in contact with a metal surface Generalized kinetic rate and localized corrosion Researching: stress corrosion and cracking Remaining asset life calculation Extreme value statistics Statistical model (pit depth versus time)

Corrosion simulation benefits Understand your corrosion environment Gain insights Corrosion mechanisms Rate limiting partial processes for your operating conditions Screen effects Process and material changes Other mitigation measures Confirm supplier recommendations Save lab time Reduce risk

Corrosion technology roadmap

Thermodynamics of corrosion Stability diagrams Corrosive, passivating and inert regions How ions partition between phases For both AQ and MSE systems 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

General corrosion model Ion diffusion to / from the corroding surface Anodic and cathodic surface reactions Flow effects on diffusion layer Polarization curves General corrosion rate Effects of scale For AQ systems

Localized corrosion model Model calculates Corrosion potential – pit forming Repassivation potential – pit filling When Ecorr is greater than Erp, localized corrosion regime

Extreme value statistics Extrapolate corrosion damage Pit depth, wall thickness, area & time data Statistical model Physical and environment factors must be constant Results Probability of failure, Pf Deepest pit mean value (given time and area) Time to first perforation Number of perforations / area of perforation

Model scope: Chemistry Corrosion thermodynamics The entire scope of OLI chemistry All contact surfaces and alloys Corrosion kinetics Chemistry (development ongoing) A subset of many common chemistries, including CO2-H2S corrosion

Model scope: Alloys Alloys Scheduled Alloys Carbon steel, stainless steels 13% Cr (type 410), 304, 316, 254SMO, 2205 duplex Aluminum Nickel-base alloys C-22, C-276, 625, 825, 600, 690 and Ni Copper-base alloys Cu, CuNi9010, CuNi7030 Scheduled Alloys Super 13Cr, Super 15Cr, 2507 duplex Alloy 2535, Alloy 28, Alloy 29

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