Orientation to OLI Flowsheet: ESP Starting a new case AJ Gerbino Mike Kochevar Pat McKenzie January 2017 Think simulation!

Agenda Introduction to OLI, AQSim OLI Flowsheet: ESP overview Software Technology OLI Flowsheet: ESP overview 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

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

Orientation Getting started: resources available Many example templates 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

Questions? Let’s get started!