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Peiming Wang Ronald Springer Margaret Lencka Robert Young Jerzy Kosinski Andre Anderko. Advances in Thermophysical Property Prediction. 24 th Conference October 23-24, 2007. THINK SIMULATION!. Opening new doors with Chemistry. Scope. OLI’s two thermodynamic models: aqueous and MSE

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slide1

Peiming Wang

Ronald Springer

Margaret Lencka

Robert Young

Jerzy Kosinski

Andre Anderko

Advances in Thermophysical Property Prediction

24th Conference October 23-24, 2007

THINK SIMULATION!

Opening new doors with Chemistry

scope
Scope
  • OLI’s two thermodynamic models: aqueous and MSE
  • Outline of the mixed-solvent electrolyte (MSE) thermodynamic model
  • Application highlights
  • Summary of MSE databanks
  • Predictive character of the model
  • Modeling transport properties
    • New model for thermal conductivity
  • Model and databank development plans
structure of oli thermodynamic models both aqueous and mse
Structure of OLI thermodynamic models (both aqueous and MSE)
  • Definition of species that may exist in the liquid, vapor, and solid phases
  • Excess Gibbs energy model for solution nonideality
  • Calculation of standard-state properties
    • Helgeson-Kirkham-Flowers-Tanger equation for ionic and neutral aqueous species
    • Standard thermochemistry for solid and gas species
  • Algorithm for solving phase and chemical equilibria
oli thermodynamic models aqueous and mse
OLI Thermodynamic Models:Aqueous and MSE
  • The difference between the models lies in
    • Solution nonideality model
    • Methodology for defining and regressing parameters
  • Aqueous model
    • Solution nonideality model suitable for solutions with ionic strength below ~30 molal and nonelectrolyte mole fraction below ~0.3
    • Extensive track record and large databank
  • MSE model
    • Solution nonideality model eliminates composition limitations
    • Development started in 2000 and model became commercial in early 2006
    • Smaller, but rapidly growing databank
    • Includes many important systems not covered by the aqueous model
mse framework
MSE Framework
  • Thermophysical framework to calculate
    • Phase equilibria and other properties in aqueous and mixed-solvent electrolyte systems
      • Electrolytes from infinite dilution to the fused-salt limit
      • Aqueous, non-aqueous and mixed solvents
      • Temperatures up to 0.9 critical temperature of the system
    • Chemical equilibria
      • Speciation of ionic solutions
      • Reactions in solid-liquid systems
outline of the mse model solution nonideality
Outline of the MSE model:Solution nonideality

Excess Gibbs energy

LR Debye-Hückel theory for long-range electrostatic interactions

LC Local composition model (UNIQUAC) for neutral molecule interactions

II Ionic interaction term for specific ion-ion and ion- molecule interactions

mse thermodynamic model application highlights
MSE thermodynamic model:Application highlights
  • Predicting deliquescence of Na – K – Mg – Ca – Cl – NO3 brines
    • Challenge: Simultaneous representation of water activity and solubility for concentrated multicomponent solutions based on parameters determined from binary and selected ternary data
  • Phase behavior of borate systems
    • Challenge: Complexity of SLE patterns; multiple phases
  • Properties of transition metal systems
    • Challenge: Interplay between speciation and phase behavior
na k mg ca cl no 3 system

NaNO3 – H2O

Na – K – Mg – Ca – Cl – NO3 system
  • Step 1: Binary systems – solubility of solids
  • The model is valid for systems ranging from dilute to the fused salt limit

Mg(NO3)2 – H2O

na k mg ca cl no 3 system step 1 binary systems water activity
Na – K – Mg – Ca – Cl – NO3 system:Step 1: Binary systems – water activity
  • Deliquescence experiments
  • Water activity decreases with salt concentration until the solution becomes saturated with a solid phase (which corresponds to the deliquescence point)
step 2 ternary systems
Step 2: Ternary systems
  • Solubility in the system NaNO3 – KNO3 – H2O at various temperatures
  • Activity of water over saturated NaNO3 – KNO3 solutions at 90 C: Strong depression at the eutectic point
step 3 verification of predictions for multicomponent systems
Step 3: Verification of predictions for multicomponent systems
  • Deliquescence data simultaneously reflect solid solubilities and water activities
  • Break points reflect solid-liquid transitions

Mixed nitrate systems at 140 C

borate chemistry complexity due to multiple competing solid phases
Borate chemistry:Complexity due to multiple competing solid phases

Na – B(III) – H – OH system

borate chemistry complexity due to multiple competing solid phases13
Borate chemistry:Complexity due to multiple competing solid phases

Mg – B(III) – H – OH

Ca – B(III) – H – OH

lead chemistry
Lead chemistry

PbCl2 + HCl

  • Solubility patterns are strongly influenced by speciation (Pb-Cl and Pb-SO4 complexation)

PbSO4 + H2SO4

lead chemistry15
Lead chemistry
  • With speciation and ionic interactions correctly accounted for, mixed sulfate – chloride systems are accurately predicted

PbSO4 + HCl

PbSO4 + NaCl

transition metal systems

Solubility of WO3 in acidic

Cl- and NO3- environments

Transition metal systems
  • Specific effects of anions on the solubility of oxides
  • Prediction of pH – accounting for hydrolysis of cations

pH of Cr salts

mixed organic inorganic systems
Mixed organic – inorganic systems

H2SO4

  • Solubility of oxalic acid in mineral acid systems

HNO3

HCl

chemistry coverage in the msepub databank 1
Chemistry Coverage in the MSEPUB Databank (1)
  • Binary and principal ternary systems composed of the following primary ions and their hydrolyzed forms
    • Cations: Na+, K+, Mg2+, Ca2+, Al3+, NH4+
    • Anions: Cl-, F-, NO3-, CO32-, SO42-, PO43-, OH-
  • Aqueous acids, associated acid oxides and acid-containing mixtures
    • H2SO4 – SO3
    • HNO3 – N2O5
    • H3PO4 – H4P2O7 – H5P3O10 – P2O5
    • H3PO2
    • H3PO3
    • HF
    • HCl
    • HBr
    • HI
  • H3BO3
  • CH3SO3H
  • NH2SO3H
  • HFSO3 – HF – H2SO4
  • HI – I2 – H2SO4
  • HNO3 – H2SO4 – SO3
  • H3PO4 with calcium phosphates
  • H – Na – Cl – NO3
  • H – Na – Cl – F
  • H – Na – PO4 - OH
chemistry coverage in the msepub databank 2
Chemistry Coverage in the MSEPUB Databank (2)
  • Inorganic gases in aqueous systems
    • CO2 + NH3 + H2S
    • SO2 + H2SO4
    • N2
    • O2
    • H2
  • Borate chemistry
    • H+ - Li+ - Na+ - Mg2+ - Ca2+ - BO2- - OH-
    • H+ - Li+ - Na+ - BO2- - HCOO- - CH3COO- - Cl- - OH-
  • Silica chemistry
    • Si(IV) – H+ - O - Na+
  • Hydrogen peroxide chemistry
    • H2O2 – H2O – H - Na – OH – SO4 – NO3
chemistry coverage in the msepub databank 3
Chemistry Coverage in the MSEPUB Databank (3)
  • Transition metal aqueous systems
    • Fe(III) – H+ – O – Cl-, SO42-, NO3-
    • Fe(II) – H+ – O – Cl-, SO42-, NO3-, Br-
    • Sn(II, IV) – H+ – O – CH3SO3-
    • Zn(II) – H+ – Cl-, SO42-, NO3-
    • Zn(II) – Li+ - Cl-
    • Cu(II) – H+ – SO42-, NO3-
    • Ni(II) – H+ – Cl-, SO42-, NO3-
    • Ni(II) – Fe(II) – H+ - O – BO2-
    • Cr(III) – H+ - O – Cl-, SO42-, NO3-
    • Cr(VI) – H+ - O – NO3-
    • Ti(IV) – H+ – O – Ba2+ – Cl-, OH-, BuO-
    • Pb(II) – H+ - O – Na+ - Cl-, SO42-
  • Mo(VI) – H+ – O – Cl-, SO42-, NO3-
  • Mo(IV) – H+ - O
  • Mo(III) – H+ - O
  • W(VI) – H+ - O – Na+ – Cl-, NO3-
  • W(IV) – H+ - O
chemistry coverage in the msepub databank 4
Chemistry Coverage in the MSEPUB Databank (4)
  • Miscellaneous inorganic systems in water
    • NH2OH
    • NH4HS + H2S + NH3
    • Li+ - K+ - Mg2+ - Ca2+ - Cl-
    • Na2S2O3
    • Na+ - BH4- – OH-
    • Na+ - SO32- - SO2-OH-
    • BaCl2
  • Most elements from the periodic table in their elemental form
  • Base ions and hydrolyzed forms for the majority of elements from the periodic table
chemistry coverage in the msepub databank 5
Chemistry Coverage in the MSEPUB Databank (5)
  • Organic acids/salts in water and alcohols
    • Formic
      • H+ - Li+ - Na+ - Formate - OH-
      • Formic acid – MeOH - EtOH
    • Acetic
      • H+ - Li+ - Na+ - K+ - Ba2+ - Acetate - OH-
      • Acetic acid – MeOH – EtOH – CO2
    • Citric
      • H+ - Na+ - Citrate - OH-
    • Oxalic
      • H+ - Oxalate – Cl- - SO42-, NO3-, MeOH, EtOH, 1-PrOH
    • Malic
    • Glycolic
  • Adipic
    • H+ - Na+ - Adipate
    • Adipic acid – MeOH, EtOH
  • Nicotinic
    • H+ - Na+ - Nicotinate
    • Nicotinic acid - EtOH
  • Terephthalic
    • H+ - Na+ - Terephthalate
    • Terephthalic acid – MeOH, EtOH
  • Isophthalic
    • Isophthalic acid - EtOH
  • Trimellitic
    • Trimellitic acid - EtOH
chemistry coverage in the msepub databank 6
Chemistry Coverage in the MSEPUB Databank (6)
  • Hydrocarbon systems
    • Hydrocarbon + H2O systems
      • Straight chain alkanes: C1 through C30
      • Isomeric alkanes: isobutane, isopentane, neopentane
      • Alkenes: ethene, propene, 1-butene, 2-butene, 2-methylpropene
      • Aromatics: benzene, toluene, o-, m-, p-xylenes, ethylbenzene, cumene, naphthalene, anthracene, phenantrene
      • Cyclohexane
    • Hydrocarbon + salt generalized parameters
      • H+, NH4+, Li+, Na+, K+, Mg2+, Ca2+, Cl-, OH-, HCO3-, CO32- NO3-, SO42-
chemistry coverage in the msepub databank 7
Chemistry Coverage in the MSEPUB Databank (7)
  • Organic solvents and their mixtures with water
    • Alcohols
      • Methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, cyclohexanol
    • Glycols
      • Mono, di- and triethylene glycols, propylene glycol, polyethylene glycols
    • Phenols
      • Phenol, catechol
    • Ketones
      • Acetone, methylisobutyl ketone
    • Aldehydes
      • Butylaldehyde
    • Carbonates
      • Diethylcarbonate, propylene carbonate
chemistry coverage in the msepub databank 8
Chemistry Coverage in the MSEPUB Databank (8)
  • Organic solvents and their mixtures with water
    • Amines
      • Tri-N-octylamine, triethylamine, methyldiethanolamine
    • Nitriles
      • Acetonitrile
    • Amides
      • Dimethylacetamide, dimethylformamide
    • Halogen derivatives
      • Chloroform, carbon tetrachloride
    • Aminoacids
      • Methionine
    • Heterocyclic components
      • N-methylpyrrolidone, 2,6-dimethylmorpholine
chemistry coverage in the msepub databank 9
Chemistry Coverage in the MSEPUB Databank (9)
  • Polyelectrolytes
    • Polyacrylic acid
      • Complexes with Cu, Zn, Ca, Fe(II), Fe(III)
  • Mixed-solvent inorganic/organic system
    • Mono, di- and triethylene glycols - H – Na – Ca – Cl – CO3 – HCO3 - CO2 – H2S – H2O
    • Methanol - H2O + NaCl, HCl
    • Ethanol – LiCl - H2O
    • Phenol - acetone - SO2 - HFo - HCl – H2O
    • n-Butylaldehyde – NaCl - H2O
    • LiPF6 – diethylcarbonate – propylene carbonate
  • Mixed-solvent organic systems
    • HAc – tri-N-octylamine – toluene – H2O
    • HAc – tri-N-octylamine – methylisobutylketone – H2O
    • Dimethylformamide – HFo – H2O
    • MEG – EtOH – H2O
chemistry coverage in the msepub databank 10
Chemistry Coverage in the MSEPUB Databank (10)
  • GEMSE databank
    • MSE counterpart of the GEOCHEM databank
      • Minerals that form on an extended time scale
    • Contains all species from GEOCHEM
    • 7 additional silicates and aluminosilicates have been included
  • CRMSE databank
    • MSE counterpart of the CORROSION databank
      • Various oxides and other salts that may form as passive films but are unlikely to form in process environments
predictive character of the model
Predictive character of the model
  • Levels of prediction
    • Prediction of the properties of multicomponent systems based on parameters determined from simpler (especially binary) subsystems
      • Extensively validated for salts and organics
      • Subject to limitations due to chemistry changes (e.g. double salts)
    • Prediction of certain properties based on parameters determined from other properties
      • Extensively validated (e.g.,speciation or caloric property predictions)
predictive character of the model29
Predictive character of the model
  • Levels of prediction - continued
    • Prediction of properties without any knowledge of properties of binary systems
      • Standard-state properties: Correlations to predict the parameters of the HKF equation
        • Ensures predictive character for dilute solutions
      • Properties of solids: Correlations based on family analysis
      • Parameters for nonelectrolyte subsystems
        • Group contributions: UNIFAC estimation
        • Quantum chemistry + solvation: CosmoTherm estimation
          • Also has limited applicability to electrolytes as long as dissociation/chemical equilibria can be independently calculated
determining mse parameters based on cosmotherm predictions
Determining MSE parameters based on COSMOtherm predictions
  • Solid-liquid-liquid equilibria in the triphenylphosphate-H2O system
  • Only two data points are available: melting point and solubility at room T
  • Predictions from COSMOtherm are consistent with the two points and fill the gaps in experimental data
determining mse parameters based on cosmotherm predictions31
Determining MSE parameters based on COSMOtherm predictions
  • Solid-liquid-liquid equilibria in the P-H2O system
  • Predictions from COSMOtherm are shown for comparison
transport properties in the oli software
Transport properties in the OLI software
  • Available transport properties:
    • Diffusivity
    • Viscosity
    • Electrical conductivity
  • These models were developed first in conjunction with the aqueous model and then extended to mixed-solvent systems
  • A new model for calculating thermal conductivity has been recently developed
thermal conductivity in mixed solvent electrolyte solutions
Thermal Conductivity in Mixed-Solvent Electrolyte Solutions

lms0̶ thermal conductivity of the mixed solvent

Δlelec̶ contribution of electrolyte concentration

Derived from a local composition approach

contribution of

individual ion

species-species interaction

thermal conductivity of solvent mixtures

Thermal conductivity of solvent mixtures

cyclohexane + CCl4 + benzene and

cyclohexane + CCl4 + toluene

organic + water mixtures at 20ºC

electrolytes in non aqueous and mixed solvents

Electrolytes in Non-aqueous and Mixed Solvents

ZnCl2+ethanol

ZnCl2+ethanol+water

further development of mse
Further Development of MSE
  • Thermophysical property models
    • Implementation of thermal conductivity in OLI software
    • Development of a surface tension model
  • Major parameter development projects
    • Refinery overhead consortium (in collaboration with SwRI)
      • Development of parameters for amines and amine hydrochlorides
    • Hanford tank chemistry in MSE
    • Modeling hydrometallurgical systems (University of Toronto)
    • Transition metal chemistry including complexation
    • Natural water chemistry (including common scales) with methanol and glycols
    • Urea chemistry
    • Other projects as defined by clients
summary
Summary
  • OLI’s two thermophysical property packages
    • Mixed-solvent electrolyte model
      • Thermophysical engine for the future
      • General, accurate framework for reproducing the properties of electrolyte and nonelectrolyte systems without concentration limits over wide ranges of conditions
      • Parameter databanks are being rapidly expanded
      • New thermophysical properties (thermal conductivity, surface tension) are being added
    • Aqueous model
      • Widely used and reliable
      • Continues to be maintained and parameters continue to be added as requested by clients