Embed Size (px)
Citation preview
Advances in Electrolyte
Thermodynamics
MSE thermo 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
Scope
•
•
•
•
•
•
•
•
New Chemistries in 2012 - 2014
•
•
•
•
•
•
•
•
•
•
•
•
New Chemistries in 2012 - 2014
•
•
•
•
•
•
•
•
•
•
•
•
•
•
•
Revisions and Extensions in 2012 - 2014
•
•
•
•
•
•
•
•
•
•
•
•
•
•
Rare earth elements:
Addressing critical material needs
•
•
•
•
•
•
•
•
•
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
0
1
2
3
4
5
6
7
8
-60 -40 -20 0 20 40 60 80 100 120
m N
dC
l 3
T / oC
Zelikman 1971 Zuravlev et al. 1971 Bunyakina et al. 1991,1992Shevtsova et al. 1961 Kost et al. 1970 Dilebaeva et al. 1973Zhuravlev et al. 1980 Zhuravlev et al. 1973 Bayanov et al. 1979Shevtsova et al. 1968 Friend and Hale 1940, 1940a Matignon 1906sokolova et al. 1980 Sokolova et al. 1981 Sokolova et al. 1981Williams et al. 1925 Nikolaev et al. 1978 Sokolova et al. 1979Sokolova et al. 1979 Nikolaev et al. 1977 Shevtsova et al. 1958Sopueva et al. 1978 Calc. - NdCl3.6H2O Calc. - NdCl3.7H2OCalc. - NdCl3.8H2O Calc. - Ice
NdCl3.6H2O
NdCl3.7H2O
NdCl3.8H2O
Ice
0
0.5
1
1.5
2
2.5
3
3.5
4
4.5
-70 -60 -50 -40 -30 -20 -10 0 10 20 30 40 50 60 70
mE
uC
l 3
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
Solubility of Nd(OH)3 and Eu(OH)3
Primary effects:
pH and T
Secondary
effects: ionic
environment
(NaCl, NaClO4,
etc.)
Qualitatively
similar behavior
of 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 E
u(O
H) 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
to
tal
(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) cr100C
150C - NaCF3SO3 - Wood(2002) cr150C
200C - NaCF3SO3 - Wood(2002) cr200C
250C - NaCF3SO3 - Wood(2002) cr250C
290C - NaCF3SO3 - Wood(2002) cr290C
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
Predicting mercury behavior in hydrocarbon – water –
CO2 – H2S systems
1.0E-07
1.0E-06
1.0E-05
0 10 20 30 40 50 60
x-H
g0
t, C
Solubility of Hg0 in Hydrocarbons:n-alkane vs. aromatic
n-C10H22
n-C8H18
n-C7H16
n-C6H14
isopropylbenzene (C9)
o-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
0 100 200 300
x-H
g0
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
Hg carbonate and
sulfide
HgCO3 + H2O (in presence of
CO2)
25~90C, 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)_
tota
l, m
ol·
kg-1
pH
solubility of HgCO3.2HgO (25C)
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
0 300 600 900 1200 1500 1800
HgS
, mo
l·kg
-1
p, atm
Solubility of HgSRefs: 1964D & 1961D
150C, Na2S=0.178m
50C, Na2S=0.178m
50C, Na2S=0.269m
50C, Na2S=0.52m
HgS + H2O (in presence of
sulfides)
17~270C, Ps~1800 atm
CO2 capture in mixed-salts
•
•
Miscibility gap
Modeling carboxylic acid chemistry:
Methacrylic acid
•
•
90
100
110
120
130
140
150
160
170
0 0.2 0.4 0.6 0.8 1
t[C
]
x MAA
Chubarov et al. 1974Chubarov et al. 1974 (y)Danov et al. 1991Danov et al. 1991 (y)Eck and Maurer 2003Eck and Maurer 2003 (y)Frolov et al. 1962Frolov et al. 1962 (y)MSEMSE (y)
-5
0
5
10
15
0 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
Modeling carboxylic acid chemistry:
Methacrylic acid
•
•
•
•
•
•
-2
-1
0
1
2
3
4
0.002 0.0022 0.0024 0.0026 0.0028 0.003 0.0032 0.0034
log
K2
v
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 0 50 100 150 200 250 300
pK
a
t[C]
Dong et al. 2008Larsson 1932Peralta et al. 2005Pomogailo et al. 200MSE
-1
-0.8
-0.6
-0.4
-0.2
0
0.2
0.4
0.6
0.8
1
0 50 100 150 200 250
% d
iffe
ren
ce
to
DIP
PR
eq
ua
tio
n
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
Filling important gaps in MSE
•
•
•
•
•
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
0 1 2 3 4 5 6 7
x O
2
m NaCl
Millero et al. (2002b), 0.5°CMillero et al. (2002b), 5°CMillero et al. (2002b), 10°CMillero et al. (2002b), 15°CMillero et al. (2002b), 20°CMillero et al. (2002a), 25°CSherwood1991LimnolOceanogr235-cal.25°CMillero et al. (2002b), 25°CMacArthur (1915), 25°CMillero et al. (2002b), 30°CMillero et al. (2002b), 35°CMillero et al. (2002b), 40°CMillero et al. (2002b), 45°C
Oxygen solubility in NaCl solution, POxygen = 0.2094
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
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
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
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
Hst
apH log
In MEG + water solutions
(mixed solvent-based):
MEGHOHccpH
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
Removal of H2S through formation of
thianes (S-substitutes of triazinane ring):
R=CH3
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, m
ol·
kgH
2O
-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
Improving density predictions
0
200
400
600
800
1000
1200
1400
1600
0.1 1 10 100
de
nsi
ty, k
g·m
3
P, MPa
Lines: volume translated-SRK220K
250K
270K
290K
300K
305K
315K
330K
350K
400K
450K
500K
550K
500
•
•
•
•
•
•
Pure CO2
Liquid density:
CO2 + salt + H2O
1028
1030
1032
1034
1036
1038
1040
1042
1044
1046
1048
0.0 0.5 1.0 1.5
De
nsi
ty, k
g·m
3
m-CO2
Song et al. 2005densities in CO2 + seawater
10C, 70 bar10C, 80 bar10C, 90 bar10C, 100 bar10C, 110 bar10C, 120 bar10C, 130 bar
1035
1040
1045
1050
1055
1060
1065
0 50 100 150 200 250 300
de
nsi
ty, k
g·m
3
P, atm
Teng and Yamasaki, 1998densities of synthetic sea water + CO2
5C
10C
15C
20C
•
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
-30 0 30 60 90 120 150 180 210
the
rma
l c
on
du
cti
vit
y, W
.m-1
.K-1
t, oC
pure H2O
xMEG=0.0882
xMEG=0.225xMEG=0.26
xMEG=0.5
xMEG=0.75pure MEG
0.1
1
10
100
0 30 60 90 120 150 180
vis
co
sit
y,
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
su
rfa
ce
te
ns
ion
, m
N.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
sp
ecif
ic c
on
du
cta
nce
, 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
Databank statistics
•
•
•
•
•
•
•
•
•
•
•
•
Overall, MSE databank
is ~44% the size of AQ
databank
AQ
•
•
•
•
•
•
•
MSE
•
•
•
•
Which model to use?
Which model to use?
••
•
•
•
•
•
•
•
•
•
••
•
•
•
•
Plans for the Future
•
•
•
•
•
•
•
•
•
•
•
•
•
•
•
•
