cationic surfactant adsorption on natural carbonate mineral
DESCRIPTION
Cationic Surfactant Adsorption on Natural Carbonate Mineral. Leyu Cui, Kun Ma and George J. Hirasaki Sponsored by The Petroleum Institute/ADNOC Rice University. Outline. Materials: Surfactants and Minerals Adsorption on natural and synthetic minerals Salinity influence on adsorption. - PowerPoint PPT PresentationTRANSCRIPT
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Cationic Surfactant Adsorption on Natural Carbonate Mineral
Leyu Cui, Kun Ma and George J. Hirasaki Sponsored by The Petroleum
Institute/ADNOCRice University
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Outline
• Materials: Surfactants and Minerals
• Adsorption on natural and synthetic minerals
• Salinity influence on adsorption
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Outline
• Materials: Surfactants and Minerals
• Adsorption on natural and synthetic minerals
• Salinity influence on adsorption
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Surfactants• SDS (anionic): sodium dodecyl
sulfate (CH3(CH2)11OSO3Na), 288.38 g/mol, ≥99.0%, Sigma-Aldrich.
• CPC (cationic): hexadecylpyridinium chloride monohydrate (C21H38ClN · H2O), 358.00 g/mol, 99.0-102.0%, Sigma-Aldrich.
• Ethomeen C12 (cationic): ethoxylated amine from AKZO NOBEL Co. C12’s molecular weight is 288 g/mol.
4
R = Coco group (≈ 8 to 16 carbon)
x =y=1
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Minerals• Dolomite: from Carl Pool Co. 200+ mesh. The BET
surface area is 0.97 m2/g.
• Limestone: from Franklin Minerals. 20/40 mesh. The BET surface area is 0.29 m2/g
• Calcite: from Alfa Aesar Company. The BET surface area is 1.67 m2/g.
• US Silica: from US silica Min-U-Sil-10. Surface area is 1.16 m2/g.
• Kaolin: from Sigma-Aldrich. Surface area is 26.61 m2/g.
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Outline
• Materials: Surfactant and Minerals
• Adsorption on natural and synthetic minerals
• Salinity influence on adsorption
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Adsorption of CPC on calcite and silica
7
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Adsorption on synthetic calcite
8
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Adsorption on natural carbonates
9
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Why is adsorption larger on limestone and dolomite compared to calcite?
• Hypothesis: Natural limestone and dolomite contain silicate minerals that adsorb cationic surfactants– Clays and chert (silica)– Analyze with XPS and EDX
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Analysis of surface chemistry (XPS)
11
calcite (Alfa
Aesar)
dolomite (Carl Pool)
limestone (Franklin)
ADCO core (#6 Well SB-426)
kaolin (Sigma Aldrich)
0
4
8
12
16
20
Atomic composition of various materials
Ca Mg Al Si
Atom
ic c
ompo
sitio
n (%
)
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Distribution of Si on dolomite (EDX)
12
SEM image of dolomite powder
(Carl Pool)
Red spots indicate silicon
(1.35% by atomic
composition)
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Outline
• Materials: Surfactants and Minerals
• Adsorption on natural and synthetic minerals
• Salinity influence on adsorption
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Cloud Point of C12
2 4 6 8 100
20
40
60
80
100
120
140
ClearCloudy
pH, at room temperature
Tem
pera
ture
()
℃
1% C12 in DI Water
2 4 6 8 100
20
40
60
80
100
120
140
Clear6Cloudy
pH, at room temperatureTe
mpe
ratu
re (
)℃
1% C12 in Brine (182.31g/L NaCl, 77.25 g/L CaCl2·2H2O
25.62 g/L MgCl2 6H∙ 2O)pH is adjusted by acetic acid
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pH of Solution under 2 atm CO2
and equilibrium with mineral
Simulated by Phreeqc software
Dolomite Calcite Silica Kaolin0
1
2
3
4
5
6
75.90 5.81
3.76 4.024.93 4.87
3.303.71
DI waterBrine
pH
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Reduce Adsorption by adjusting salinity
Calcite Dolomite Silica Kaolin0
1
2
3
4
5
6
0.47
2.21
5.33
1.79
0.56
1.39
4.26
1.23
C12
Adso
rptio
n at
the
plat
eau
(mg/
m2)
(182.31g/L NaCl, 77.25 g/L CaCl2·2H2O 25.62 g/L MgCl2 6H∙ 2O)
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Reduce Adsorption by adjusting salinity
Calcite Dolomite Silica Kaolin0
1
2
3
4
5
6
0.47
2.21
5.33
1.79
0.56
1.39
4.26
1.231.33
5.41
1.481.10
4.91
C12
Adso
rptio
n at
the
plat
eau
(mg/
m2)
(Same Ionic Strength as in brine)
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Cations Concentration during Adsorption Test on Silica
DI Brine NaCl MgCl2
Al3+ (mol/L) 0 0 0 0
Ca2+ (mol/L) 0 5.78E-01 0 0
Mg2+(mol/L) 0 1.39E-01 0 1.695
Na+ (mol/L) 0 0 4.91 0
Silica0
2
4
65.33
4.265.41 4.91
Ads
orpti
on a
t th
e pl
atea
u (m
g/m
2)
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Cations Concentration during Adsorption Test on Kaolin
DI Brine NaCl
Al3+ (mol/L) 7.18E-05 5.20E-04 1.94E-04
Ca2+ (mol/L) 0 5.77E-01 0
Mg2+(mol/L) 0 1.39E-01 0
Na+ (mol/L) 0 3.44 4.91
Kaolin0
0.5
1
1.5
2 1.79
1.231.48
Adso
rptio
n at
th
e pl
atea
u (m
g/m
2)
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Cations Concentration during Adsorption Test on Dolomite
DI Brine NaCl MgCl2
Al3+ (mol/L) 0 0 0 0
Ca2+ (mol/L) 6.47E-03 5.64E-01 8.35E-03 9.88E-03
Mg2+(mol/L) 6.53E-03 1.45E-01 9.36E-03 1.67
Na+ (mol/L) 0 0 4.90 0
Dolomite0
0.51
1.52
2.5 2.21
1.39 1.331.10
Adso
rptio
n at
the
plat
eau
(mg/
m2)
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Analysis of surface chemistry (XPS)
21
calcite (Alfa
Aesar)
dolomite (Carl Pool)
limestone (Franklin)
ADCO core (#6 Well SB-426)
kaolin (Sigma Aldrich)
0
4
8
12
16
20
Atomic composition of various materials
Ca Mg Al Si
Atom
ic c
ompo
sitio
n (%
)
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Al3+ influence on adsorption on Silica
Kaolin+SiO2/Brine Kaolin/Brine SiO2/BrineAl3+ (mol/L) 5.71E-04 5.20E-04 0Ca2+ (mol/L) 5.77E-01 5.77E-01 5.78E-01Mg2+(mol/L) 1.39E-01 1.39E-01 1.39E-01Na+ (mol/L) 3.44 3.44 3.44
Test the adsorption on the mixture of silica and dolomite.
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C12 Adsorption on Silica
0
1
2
3
4
5
6 5.33
4.26
5.414.91
2.65DI BrineNaClMgCl2Brine(with kaolin)
Silica
Adso
rptio
n aft
er
plat
eau/
(mg/
m^2
)
The adsorption on silica is reduced to around half in the presence of only 5.74×10-4 mol/L Al3+.
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Conclusions• Cationic surfactant has less adsorption than
anionic on pure carbonate surface (synthetic calcite).
• Cationic surfactants have larger adsorption on natural carbonate sands (dolomite and limestone), silica and kaolin.
• The natural carbonate sands have substantial clays and/or silica.
• The adsorption can be effectively reduced by trivalent ions (Al3+) and divalent ions (Ca2+).
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Question?
Thank you!
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Backup- activityDolomite activity
DI Brine NaCl MgCl2Al3+ 0 0 0 0Ca2+ 3.22E-03 4.86E-01 5.82E-03 7.17E-03Mg2+ 3.31E-03 2.32E-01 1.14E-02 2.153Na+ 0 4.598 5.92 0
Silica activityDI Brine NaCl MgCl2
Al3+ 0 0 0 0Ca2+ 0 4.99E-01 0 0Mg2+ 0 2.23E-01 0 2.189Na+ 0 4.60E+00 5.896 0
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Backup-activityKaolin activity
DI Brine NaClAl3+ 5.69E-05 2.29E-05 8.73E-06Ca2+ 0 4.99E-01 0Mg2+ 0 2.23E-01 0Na+ 0 4.60E+00 5.90E+00
Kaolin+SiO2Brine
Al3+ 2.51E-05Ca2+ 4.99E-01Mg2+ 2.23E-01Na+ 4.60E+00
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Static Adsorption Test under 2 atm CO2
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Static Adsorption Test under 2 atm CO2
Pressure Vessel
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Chemicals in Two Phase TitrationMB solution: Methylene blue solution, which contains
0.03g/L (0.802mM) Methylene Blue, 50g/L Na2SO4,
6mL/L Sulfuric Acid (Fumic 20%). The methylene blue
(MW= 373.9 g/mole) structure is shown beside:
SDES: Sodium dodecyl ether sulfate with 3 EO
from Stepan. Trade name is STEOL CS 330,
lot # is 0-15021. MW=422 g/mol.
TEGO: 1,3-Didecyl-2-methylimidazolium chloride from
Fisher Scientific. The structure is shown beside:
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Colormetric Two Phase Titration