Advances in Electrolyte Thermodynamics Thermophysical Electrical - - PowerPoint PPT Presentation

▶
advances in electrolyte thermodynamics thermophysical
SMART_READER_LITE
LIVE PREVIEW

Advances in Electrolyte Thermodynamics Thermophysical Electrical - - PowerPoint PPT Presentation

Jun 12, 2023 453 likes •763 views

Advances in Electrolyte Thermodynamics Thermophysical Electrical Electrical conductivity conductivity property frameworks Viscosity Viscosity AQ thermo MSE thermo Standard-state: Standard- HKF (via fitting Self - state: HKF Self -

slide-1
SLIDE 1

Advances in Electrolyte Thermodynamics

slide-2
SLIDE 2

MSE thermo

Standard- state: HKF (direct) GEX: MSE no limit on concentration Solid phases: thermochemical properties

AQ thermo

Standard-state: HKF (via fitting equations) GEX: Bromley- Zemaitis I < 30m; xorg < 0.3 Solid phases: equilibrium constants (Kfits)

Surface tension Interfacial tension

2nd liquid phase: MSE (ionic) 2nd liquid phase: SRK (non-ionic)

Electrical conductivity Electrical conductivity Viscosity Viscosity Self - diffusivity Thermal conductivity Self - diffusivity Interfacial phenomena: ion exchange, surface complexation, molecular adsorption

Thermophysical property frameworks

slide-3
SLIDE 3

Scope

slide-4
SLIDE 4

New Chemistries in 2012 - 2014

slide-5
SLIDE 5

New Chemistries in 2012 - 2014

slide-6
SLIDE 6

Revisions and Extensions in 2012 - 2014

slide-7
SLIDE 7

Rare earth elements: Addressing critical material needs

slide-8
SLIDE 8

Solubility of NdCl3 and EuCl3 in aqueous solutions NdCl3 + H2O EuCl3 + H2O  Similarity of phase behavior of chlorides  Searching for regularities in phase behavior of rare-earth elements

1 2 3 4 5 6 7 8

  • 60
  • 40
  • 20

20 40 60 80 100 120

m NdCl3 T / oC

Zelikman 1971 Zuravlev et al. 1971 Bunyakina et al. 1991,1992 Shevtsova et al. 1961 Kost et al. 1970 Dilebaeva et al. 1973 Zhuravlev et al. 1980 Zhuravlev et al. 1973 Bayanov et al. 1979 Shevtsova et al. 1968 Friend and Hale 1940, 1940a Matignon 1906 sokolova et al. 1980 Sokolova et al. 1981 Sokolova et al. 1981 Williams et al. 1925 Nikolaev et al. 1978 Sokolova et al. 1979 Sokolova et al. 1979 Nikolaev et al. 1977 Shevtsova et al. 1958 Sopueva et al. 1978

  • Calc. - NdCl3.6H2O
  • Calc. - NdCl3.7H2O
  • Calc. - NdCl3.8H2O
  • Calc. - Ice

NdCl3.6H2O NdCl3.7H2O NdCl3.8H2O Ice 0.5 1 1.5 2 2.5 3 3.5 4 4.5

  • 70
  • 60
  • 50
  • 40
  • 30
  • 20
  • 10

10 20 30 40 50 60 70

mEuCl3 T / oC

Sokolova 1987 Sokolova 1987 Nikolaev et al. 1977 Powel 1959 Nikolaev et al. 1978 Kotlyar-Sharipov et al. 1977 Nikolaev et al. 1967 Nikolaev et al. 1971 Spedding et al. 1974 Spedding et al. 1975 Spedding et al. 1977 Spedding et al. 1967 Wang et al. 2007 Sokolova 1987

  • Calc. - Ice
  • Calc. - EuCl3.8H2O
  • Calc. - EuCl3.6H2O

EuCl3.8H2O Ice EuCl3.6H2O

slide-9
SLIDE 9

Solubility of Nd(OH)3 and Eu(OH)3

 Primary effects: pH and T  Secondary effects: ionic environment (NaCl, NaClO4, etc.)  Qualitatively similar behavior

  • f various REEs

1.00E-10 1.00E-09 1.00E-08 1.00E-07 1.00E-06 1.00E-05 1.00E-04 1.00E-03 1.00E-02 1.00E-01 1.00E+00 3 5 7 9 11 13 15

m Eu(OH)3

pH

  • Calc. @ 25C - 0.001m HClO4
  • Calc. @ 25C - 0.1m NaOH
  • Calc. @ 25C - 0.001m HCl
  • Calc. @ 50C - 0.001m HClO4
  • Calc. @ 50C - 0.001m HCl
  • Calc. @ 50C - 0.1m NaOH
  • Calc. @ 100C - 0.001m HClO4
  • Calc. @ 100C - 0.001m HCl
  • Calc. @ 100C - 0.1m NaOH
  • Calc. @ 150C - 0.001m HClO4
  • Calc. @ 150C - 0.001m HCl
  • Calc. @ 150C - 0.1m NaOH

Eu(OH)3

1.E-11 1.E-10 1.E-09 1.E-08 1.E-07 1.E-06 1.E-05 1.E-04 1.E-03 1.E-02 1.E-01 1.E+00 3 4 5 6 7 8 9 10 11 12 13 14 15

Nd total (m) pH Nd(OH)3 crystalline

  • --- Nd(OH)3 amorphous

30C - NaCF3SO3 - Wood (2002) am 30C 50C - NaCF3SO3 - Wood (2002) am 50C 100C - NaCF3SO3 - Wood (2002) cr 100C 150C - NaCF3SO3 - Wood (2002) cr 150C 200C - NaCF3SO3 - Wood (2002) cr 200C 250C - NaCF3SO3 - Wood (2002) cr 250C 290C - NaCF3SO3 - Wood (2002) cr 290C 25C - 0.1 m NaCl - Silva (1982) cr 25C - 0.1 m NaCl 22C - 0.01 m NaClO4 - Makino (1993) am 22C - 0.01 m NaClO4 25C - 0.1 m NaCl - Neck (2009) am 25C - 0.1 m NaCl 25C - 0.5 m NaCl - Neck (2009) am 25C - 0.5 m NaCl 25C - 2.6 m NaCl - Neck (2009) am 25C - 2.6 m NaCl 25C - 5.6 m NaCl - Neck (2009) am 25C - 5.6 m NaCl 25C - 0.1 m NaCl - Rao (1996) cr 25C - 5.6 m NaCl - Runde (1994) cr

Nd(OH)3

slide-10
SLIDE 10
  • Predicting mercury behavior in hydrocarbon – water –

CO2 – H2S systems

1.0E-07 1.0E-06 1.0E-05 10 20 30 40 50 60

x-Hg0 t, C

Solubility of Hg0 in Hydrocarbons: n-alkane vs. aromatic

n-C10H22 n-C8H18 n-C7H16 n-C6H14 isopropylbenzene (C9)

  • -xylene (c8)

toluene (c7) benzene (c6) aromatic n-alkane

1.0E-10 1.0E-09 1.0E-08 1.0E-07 1.0E-06 1.0E-05 1.0E-04 100 200 300

x-Hg0 t, C

Solubility of Hg0 in water

Ps - 1994M Ps - 1971GH Ps - Sorokin et al. 1978 500 bar - Sorokin et al. 1978 1000 bar-Sorokin et al 1978

Elemental mercury in oil and gas environments

slide-11
SLIDE 11

Hg carbonate and sulfide

  • HgCO3 + H2O (in presence of

CO2)

25~90C, Ps~1 atm

1.0E-04 1.0E-03 1.0E-02 1.0E-01 1.0E+00 1 2 3 4 5 6 7 8

Hg(II)_total, mol·kg-1 pH

solubility of HgCO3.2HgO (25C)

pCO2=1atm, NaClO4=0.5m pCO2=1atm, NaClO4=3m pCO2=0.5atm, NaClO4=3m 0.00 0.02 0.04 0.06 0.08 0.10 0.12 0.14 0.16 0.18 300 600 900 1200 1500 1800

HgS, mol·kg-1 p, atm

Solubility of HgS

Refs: 1964D & 1961D

150C, Na2S=0.178m 50C, Na2S=0.178m 50C, Na2S=0.269m 50C, Na2S=0.52m

  • HgS + H2O (in presence of

sulfides)

17~270C, Ps~1800 atm

slide-12
SLIDE 12

CO2 capture in mixed-salts

  • Miscibility gap
slide-13
SLIDE 13

Modeling carboxylic acid chemistry: Methacrylic acid

  • 90

100 110 120 130 140 150 160 170 0.2 0.4 0.6 0.8 1

t[C]

x MAA

Chubarov et al. 1974 Chubarov et al. 1974 (y) Danov et al. 1991 Danov et al. 1991 (y) Eck and Maurer 2003 Eck and Maurer 2003 (y) Frolov et al. 1962 Frolov et al. 1962 (y) MSE MSE (y)

  • 5

5 10 15 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 t[C]

x MAA

Bruhl 1880 Chubarov et al. 1978 LLE Chubarov et al. 1978 SLE Eck and Maurer 2003 LLE Eck and Maurer 2003 SLE Efremov et al. 1981 Hino et al. 2011 Karabaev et al. 1985 Kolesnikv et al. 1979 Oswald and Urquharta 2011 Rabinovich et al. 1967 MSE

VLE LLE + SLE

slide-14
SLIDE 14

Modeling carboxylic acid chemistry: Methacrylic acid

  • 2
  • 1

1 2 3 4 0.002 0.0022 0.0024 0.0026 0.0028 0.003 0.0032 0.0034 log K2v 1/T Jasperson et al. 1989 4.0 4.5 5.0 5.5 6.0 6.5

7.0 7.5 8.0

  • 50

50 100 150 200 250 300 pKa t[C] Dong et al. 2008 Larsson 1932 Peralta et al. 2005 Pomogailo et al. 200 MSE

  • 1
  • 0.8
  • 0.6
  • 0.4
  • 0.2

0.2 0.4 0.6 0.8 1 50 100 150 200 250 % difference to DIPPR equation t[C]

Braude and Evans 1956 Daubert et al. 1987 Chubarov et al. 1989 (eq) Chubarov et al. 1978 Chubarov et al. 1974 Eck and Maurer 2003 (eq) Eck and Maurer 2003 Frolov et al. 1962 Gachokidse 1947 Jasperson et al. 1989 Li et al. 1989 Leontiev et al. 1970 Meitzner 1940 Ratchford et al. 1944 Stull 1947 Van-chin-syan et al. 1996 White 1943 MSE

Gas-phase dimerization Acid dissociation Pure acid vapor pressure

slide-15
SLIDE 15

Filling important gaps in MSE

slide-16
SLIDE 16

Filling important gaps in MSE

  • 0.E+00

1.E-06 2.E-06 3.E-06 4.E-06 5.E-06 6.E-06 7.E-06 8.E-06 9.E-06 1 2 3 4 5 6 7

x O2 m NaCl

Millero et al. (2002b), 0.5°C Millero et al. (2002b), 5°C Millero et al. (2002b), 10°C Millero et al. (2002b), 15°C Millero et al. (2002b), 20°C Millero et al. (2002a), 25°C Sherwood1991LimnolOceanogr235-cal.25°C Millero et al. (2002b), 25°C MacArthur (1915), 25°C Millero et al. (2002b), 30°C Millero et al. (2002b), 35°C Millero et al. (2002b), 40°C Millero et al. (2002b), 45°C

Oxygen solubility in NaCl solution, POxygen = 0.2094

slide-17
SLIDE 17

H2S – NaCl – H2O mixtures

  • Salting-out effect of

NaCl in both the VLE and LLE regions

  • Pressure effect is

different in the VLE and LLE regions

  • Three-phase VLLE

pressure is nearly independent of NaCl

slide-18
SLIDE 18

Prediction of pH Systems containing acid gases

  • Experimental data are

scarce

  • Problems with

reproducible measurements in saline systems

  • Prediction is essential
  • pH rapidly decreases

with acid gas partial pressure and then plateaus

CO2 + H2O

slide-19
SLIDE 19

Prediction of pH Systems containing acid gases

  • Salt content

reduces pH

  • Effect of

nonideality – interactions with ions

  • Data are scattered
  • Pure prediction is

well within the scattering of data

CO2 + NaCl + H2O

slide-20
SLIDE 20

3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0 0.0 0.2 0.4 0.6 0.8 1.0 1.2

pH (m NaHCO3)0.5 (mol·kg solvent-1)0.5 MEG = 90 wt%, PCO2~1atm

80˚C, pH 80˚C, pHst 25˚C, pH 25˚C, pHst

 

 

H st

a pH log

In MEG + water solutions (mixed solvent-based):

 

  

 

MEGH O H

c c pH

3

log

In aqueous solutions (water-based):

pH in mixed-solvent systems

MEG + H2O + NaHCO3 + NaCl

Both protonated solvent species, H3O+ and MEGH+, contribute to the solution pH

2 H2O = H3O+ + OH- 2 HOC2H4OH(aq) = HOC2H4OH2

+ + HOC2H4O-1

MEG + water + salt mixtures

slide-21
SLIDE 21

Removal of H2S through formation of thianes (S-substitutes of triazinane ring):

R=CH3

slide-22
SLIDE 22

Modeling H2S scavenging: 1,3,5-trimethyl-1,3,5-triazinane + H2S

0.0000 0.0005 0.0010 0.0015 0.0020 0.0025 2 3 4 5 6 7 8 9 10 11 12

S, mol·kgH2O-1 pH

Gonzalez, et al. 2011 MSE S in solid phase total S = 0.00235 mol·kgH2O-1 S in C4H9NS2·2CH3NH2(aq) S in C4H9NS2(aq) Un-scavenged S: C6H15N3=0.0062 mol·kgH2O-1

pH dependence of scavenging capacity:

  • The combined effects of

formation of C4H9NS2·2CH3NH2(s) and C4H9NS2·2CH3NH2(aq) cause the decrease of total H2S concentration with pH

  • C4H9NS2(aq) is important only

at lower pH

slide-23
SLIDE 23

Improving density predictions

200 400 600 800 1000 1200 1400 1600 0.1 1 10 100

density, kg·m3 P, MPa

Lines: volume translated-SRK

220K 250K 270K 290K 300K 305K 315K 330K 350K 400K 450K 500K 550K 500

  • Pure CO2
slide-24
SLIDE 24

Liquid density: CO2 + salt + H2O

1028 1030 1032 1034 1036 1038 1040 1042 1044 1046 1048 0.0 0.5 1.0 1.5

Density, kg·m3 m-CO2

Song et al. 2005 densities in CO2 + seawater

10C, 70 bar 10C, 80 bar 10C, 90 bar 10C, 100 bar 10C, 110 bar 10C, 120 bar 10C, 130 bar

1035 1040 1045 1050 1055 1060 1065 50 100 150 200 250 300

density, kg·m3 P, atm

Teng and Yamasaki, 1998 densities of synthetic sea water + CO2

5C 10C 15C 20C

slide-25
SLIDE 25

0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8

  • 30

30 60 90 120 150 180 210 thermal conductivity, W.m-1.K-1 t, oC

pure H2O xMEG=0.0882 xMEG=0.225 xMEG=0.26 xMEG=0.5 xMEG=0.75 pure MEG 0.1 1 10 100 30 60 90 120 150 180 viscosity, cP t, oC pure H2O pure MEG xMEG=0.25

35.0 40.0 45.0 50.0 55.0 60.0 65.0 70.0 75.0 0.0 0.2 0.4 0.6 0.8 1.0 surface tension, mN.m-1 x-MEG

25C, Won, et al. 1981 25C, Habrdova, et al. 2004 25C, Hoke & Chen, 1991 25C, Horibe, et al. 1996 30C, Nakanish et al 1971 30C, Hoke & Chen, 1991 50C, Hoke & Chen, 1991 80C, Hoke & Chen, 1991 100C, Hoke & Chen, 1991 120C, Hoke & Chen, 1991

Thermal conductivity

MEG + water

Viscosity Surface tension

0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.10 0.0 0.3 0.6 0.9 1.2

specific conductance, S.cm-1 NaCl, mol.kg solvent-1

NaHCO3=0.25 mol.kg solvent-1 x' MEG=0 x' MEG=0.2 x' MEG=0.998

MEG + water MEG + water

MEG + H2O + NaHCO3 + NaCl

Electrical conductivity

Other Thermophysical Properties: MEG Systems

slide-26
SLIDE 26

Databank statistics

  • Overall, MSE databank

is ~44% the size of AQ databank

slide-27
SLIDE 27

AQ

  • MSE
  • Which model to use?
slide-28
SLIDE 28

Which model to use?

slide-29
SLIDE 29

Plans for the Future