Think Simulation! Adventures in Electrolytes OLI Electrolyte Simulation AJ Gerbino Pat McKenzie May 2015

 Introductions  Introduction to OLI, AQSim ◦ Software ◦ Technology  Application discussion

 Name  Responsibility  Water chemistry interest  Areas of practice

 Core competencies ◦ Electrolyte thermodynamics ◦ Process simulation ◦ Aqueous corrosion science  Products ◦ Software ◦ Consulting services  Model development  Data development A Technology Company

 Mission: To help clients understand and solve water-based process chemistry applications ◦ OLI applications consulting ◦ OLI training ◦ OLI software sales  Business Development Director for OLI ◦ Worldwide except China, Japan, India, SE Asia  CorrScience: local representation in Calgary OLI Partner Company

 Oil & Gas ◦ Exploration and production ◦ Refining  Chemicals  Power / nuclear power  Metals and mining  Water treatment  Pulp and paper  Engineering companies  Research companies Broad spectrum of industries

Think Simulation! Adventures in Electrolytes OLI Electrolyte Simulation The primary delivery of OLI technology is through several software products

 Physical and chemical properties of multi-component systems  Solid-Liquid-Vapor-Organic ◦ equilibrium ◦ kinetics framework ◦ reduction / oxidation  Advanced mechanisms ◦ mass transfer ■ ion exchange All OLI software Some OLI components Water chemistry

 Real-solution Pourbaix diagrams  Polarization curves  Rates of uniform (general) corrosion  Worst-case pitting rate ◦ Corrosion potential versus Repassivation potential  Extreme value statistics EVS (asset life)… Corrosion Prediction

 -50 to 300 C  0 to 1500 bar  0 to 30 molal ionic strength  5,500 species database ◦ ~2000 solids ◦ ~2500 organics ◦ 85 elements and their aqueous species AQ Model

 0 to 1 mol fx solute  90% of T c  0 to 1500 bar  40% of the AQ framework  Can be more challenging to interpret Mixed Solvent Electrolyte Model Non-aqueous electrolytes 2 nd electrolyte phase Sublimation as a new phenomenon Rewrite / many ‘wish list’ improvements

Stream Analyzer Corrosion Analyzer  Real-solution Pourbaix diagrams  Polarization curves  OLI’s corrosion science Studio ScaleChem  Upstream focus  Single point, survey, mix & separate  Ionic input / data reconciliation

OLI-only Thermodynamics Alliance Partners: OLI Engine  in Aspen HYSYS  in Aspen Plus  in gProms  in IDEAS  in UniSim Design  in PRO/II Coming in 2016 OLI as a property method  OLI Flowsheet: ESP  Electrolyte Simulation Program

 Target: Duplicate physical process ◦ Convert disparate analytical data ◦ Determine representative streams / conditions  Result: reduces laboratory / pilot plant tests ◦ Focus on likely optimum  Result: anticipate process changes ◦ Develop trends of T, P, comp ◦ Determine benefits & consequences in advance

Process Schematic Conditions Scenarios Setpoints Output Recommendations Step 1 Step 2 Step 3 Modifications Stream/Analysis Data Software Interpretation

Think Simulation! Adventures in Electrolytes OLI Electrolyte Simulation The key to OLI acceptance is the ability to predict the properties of multi-component, complex systems

 Speciated model ◦ Liquid, vapor, and solid phases  Standard-state properties ◦ Helgeson-Kirkham-Flowers-Tanger equation  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

 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  Speciation based on solvated protons (e.g., H 3 O + )

Symbols are experimental Curves are OLI predicted

Think Simulation! Adventures in Electrolytes OLI Electrolyte Simulation Process simulation experts are available to setup and / or review of simulations

 Application building screening and advice  Hotline technical support for clients  Turnkey leases = software + consulting ◦ Application setup ◦ Application review  Applications consulting ◦ Delivered in reports or presentations Leases Turnkey Leases Consulting

 Public Training ◦ At OLI (with training credits) ◦ Regional in Houston, Calgary, Aberdeen ◦ Web classes (once every 3 months)  Custom training ◦ Onsite at your company ◦ Via custom web classes ◦ Combination of web training + applications support  initial 2 hour class geared to your application specific  weekly or biweekly follow-up, review and advice

 OLI application screening : chemistry  Validation spreadsheets  Thermophysical modeling service  MSE Regression class

Onto your application!