OLI technology & electrolyte simulation AJ Gerbino Pat McKenzie AQSim 2016

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

Introductions Name Responsibility Water chemistry interest Areas of practice

Who is OLI A Technology Company Core competencies Products Electrolyte thermodynamics Process simulation Aqueous corrosion science Products Software Consulting services Model development Data development

AQSim OLI Partner 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: excluding China, India, Japan, SE Asia

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

OLI Software The primary delivery of OLI technology is through several software products

Process Simulation Software Water chemistry 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

Corrosion Simulation Software Corrosion Prediction 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)…

AQ model strengths / limits -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

MSE model strengths / limits Mixed Solvent Electrolyte Model 0 to 1 mol fx solute 90% of Tc 0 to 1500 bar 50% of the AQ framework Can be more challenging to interpret Non-aqueous electrolytes 2nd electrolyte phase Sublimation as a new phenomenon Rewrite / many ‘wish list’ improvements

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

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

How OLI tools help clients 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

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

OLI Technology The key to OLI acceptance is the ability to predict the properties of multi-component, complex systems

OLI electrolyte thermodynamics 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

Moving to the MSE model 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., H3O+)

NH3, H2SO4, H2O 100% water to 100% salt Symbols are experimental Curves are OLI predicted

Chemistry in refining overheads Corrosion source Amine-HCl salt deposits on hot metal surfaces Prevention Prevent salt formation Method Operate refinery unit above “salt point” T Challenge What is a safe temperature? Solution Predict sublimation point and dew point Ts in mixtures

Chemistry in refining overheads OLI consortium formed 10 years ago Measurements and data regressions 20 amine hydrochlorides added to OLI Proprietary until Nov 2015 Now part of the OLI MSE databank

Amines from the consortium Trimethylamine TMA Cyclohexylamine 3-methoxypropylamine MOPA 2-dimethylaminoethanol DMEA Diethanolamine DEA Dimethylisopropanolamine DMIPA Dimethylamine DMA Ethylenediamine EDA Monoethanolamine MEA Morpholine

Amines Methylamine Methyldiethanolamine MDEA Ethylamine N-methylmorpholine Diglycolamine DGA Diethylamine N-butylamine Sec-butylamine

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

OLI assistance in applications 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

OLI assistance in applications OLI application screening : chemistry Validation spreadsheets Thermophysical modeling service MSE Regression class

Questions? Onto your application!