Surfactant Analysis & Adsorption on
Carbonate Minerals
Kun Ma, Yezi Dong, Leyu Cui, Yu Bian, Maura Puerto,
Sibani Lisa Biswal and George J. Hirasaki
Department of Chemical & Biomolecular Engineering
Rice University, Houston, TX
04/26/2011
Outline
★ Surfactant analysis
- Potentiometric titration
- High performance liquid chromatography
★ Adsorption on carbonate minerals
- Dolomite and carbonate sand
- Ionic and nonionic surfactants
- Simulation of transport of a finite slug
List of surfactants in this study
Trade name (Manufacturer)
Chemical name
Acronym
(in this study)
Agent X-3153-026 (Stepan)
sodium (C1618) alpha olefin sulfonate
AOS 1618
Petrostep S-2A (Stepan)
sodium (C1518) Internal olefin sulfonate IOS 1518
Steol CS-330 (Stepan)
sodium laureth sulfate, 3 moles EO
CS 330
-- (Arcos)
hexadecyltrimethylammonium bromide
CTAB
-- (Sigma-Aldrich)
dodecyltrimethylammonium bromide
DTAB
-- (Sigma-Aldrich)
hexadecylpyridinium chloride
CPC
Amphosol CS-50 (Stepan)
cocamidopropyl hydroxysultaine
CS 50
Mackam LAB (Rhodia)
lauryl and myristyl betaines
LAB
Mackam CB-35 (Rhodia)
coco betaines
CB
Tergitol 15-S-30 (Dow)
secondary alcohol ethoxylate, 31 EO
15-S-30
Potentiometric titration
• For anionic surfactants
(such as AOS 1618):
-- An ion selective electrode
(ISE, pHoenix, Cat. No.
SUR1502) is used for
aqueous titration;
-- TEGO ® trant A100 (~10-3
mol/L) is used as the
titrant;
-- Serial diluted SDS solution
is used to calibrate the
titrant.
Titration curves of SDS by hyamine and TEGO
High Performance Liquid Chromatography
Column
Guard Column
Storage Solution
Mobile phase
pH
Temperature
Pressure
Typical Flow Rate
Injection Volume
Dionex Acclaim Surfactant, 4.6 ×250mm (P/N 063203)
Dionex Acclaim Surfactant, 4.6 ×10mm (P/N 069701)
Acetonitril/0.1%Acetic Acid or Acetonitril/100mM NH4OAc at v/v 80/20
ACN/DI or Methanol/DI, 0%-100% organic in mobile phase
2.5-7.5
<60oC
<5500 psi
0.8-2.0 mL/min
5-50 µL
Analysis of zwitterionic surfactants
Cocamidopropyl
hydroxysultaine
brine
surfactant
0.435% AMPHOSOL CS-50 in Brine; Injection: 25
µL; Column Temperature: 25°C; Mobile Phase:
100mM Ammonium Acetate(pH5.5)/CAN, linear
gradient: 75/25-25/75 in 20 minutes; Flow rate: 1
ml/min; ELSD setting: 60°C, 3.5 Bar.
Successful separation of
high-salinity brine and
surfactants
Carbonate minerals for static adsorption
• Carbonate sand (limestone): 20/40 mesh, purchased from
Franklin Minerals, Nolanville TX, BET surface area 0.29
m2/gram.
• Dolomite powder: 200+ mesh, purchased from Vital Earth /
Carl Pool, BET surface area 0.97 m2/gram.
• Equilibration time for static adsorption experiments at room
temperature: 24 hours.
• Synthetic brine: NaCl 182.31 g/L, CaCl2 58.33 g/L,
MgCl2.6H2O 25.62 g/L.
Carbonate sand vs. dolomite powder
AOS1618 static adsorption in DI water
Carbonate 20/40
Dolomite powder
2
1.8
Adsorption (mg/m^2)
1.6
1.4
1.2
1
0.8
0.6
0.4
0.2
0
0
0.02
0.04
0.06
0.08
0.1
0.12
0.14
Equilibrium surfactant concentration (wt%)
0.16
0.18
Comparison of anionics
Comparison of cationics
Comparison of zwitterionics
Adsorption of TERGITOL 15-S-30
Adsorption plateaus
anionics
cationics
nonionics
zwitterionics
Surfactant adsorption model
Assumptions:
1. Surfactant is present in aqueous phase, but not in gaseous phase;
2. Surfactant adsorption can be described with a Langmuir-type isotherm.

 ( C sw S w  C sg S g )
  [ K sw
t

x
(S w
 C sw
x
C ss   s a s  s , max 
 (1   )
)  K sg
 C sw
1   C sw
 C ss
t

x

(S g
 ( C sw u w  C sg u g )
x
 C sg
x
)]
Static adsorption of anionic surfactant on dolomite
AOS1618 static adsorption on dolomite
(0%Na2CO3, 0%NaCl)
Experimental data
Fit by Langmuir isotherm
2
s
2
Surface excess (mg/m )
1.8
 s , max
1.6
1.4

 C sw
1   C sw
 s , max  1 . 688
1.2
1
  12 . 2 L / g
0.8
0.6
0.4
0.2
0
0
0.2
0.4
0.6
0.8
1
Residual concentration (g/L)
1.2
1.4
1.6
mg / m
2
Propagation of a finite slug (0.5 PV)
CONCENTRATION
CONCENTRATIONPROFILE
PROFILE
PROFILEat
atatttDDt=10
=0.1
=0.2
=0.3
=0.4
=0.5
=0.6
=0.7
=0.8
=0.9
=1.1
=1.2
=1.3
=1.4
=1.5
=1
=2
=3
=4
=5
CONCENTRATION
D
DIMENSIONLESS CONCENTRATION
CONCENTRATION
DIMENSIONLESS
1.2
FD(NX=1000)
FD(NX=1000)
MOC
MOC
1
0.8
0.6
0.4
0.4
0.2
0.2
00
00
0.1
0.1
0.2
0.2
Surfactant: AOS1618, 0.2% wt
Mineral: dolomite powder
No dispersion
0.7
0.6
0.5
0.4
0.3
0.3
0.4
0.5
0.6
0.7
DISTANCE
DIMENSIONLESS
DIMENSIONLESS DISTANCE
0.8
0.8
0.9
0.9
11
Effluent of a finite slug (0.5 PV)
EFFLUENT CONCENTRATION HISTORY
DIMENSIONLESS EFFLUENT HISTORY
1
FD(NX=1000)
MOC
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
0
2
4
Surfactant: AOS1618, 0.2% wt
Mineral: dolomite powder
6
8
10
12
DIMENSIONLESS TIME
14
16
18
20
Conclusions
★ Ethoxylated anionic surfactant CS 330 has lower adsorption than AOS 1618
or IOS 1518 on dolomite in DI water at room temperature.
★ The nonionic surfactant Tergitol 15-S-30 shows the lowest adsorption on
dolomite in DI water at room temperature among all the surfactants measured
so far.
★ For the cationic surfactant DTAB, the adsorption plateau is close to that of
CS 330 on dolomite in DI water at room temperature; however, other cationics
exhibit high adsorption, and a possible reason is that room temperature is close
to the temperature of phase transition (Kraft temperature).
★ The zwitterionic surfactants CS-50 and LB have high adsorption in both DI
water and synthetic brine.
Acknowledgment
This work was financially supported by ADNOC, ADCO, ZADCO,
ADMA-OPCO and PI, U.A.E.
Analysis of zwitterionic surfactants
Lauryl betaine
HPLC profile of MACKAM LAB (0.21 wt% lauryl
betaine) and MACKAM CB-35 (0.21 wt% lauryl
betaine) with an ELSD detector.
MACKAM CB-35
contains cetyl betaine
while MACKAM LAB
does not
Analysis of nonionic surfactants
0.2% Tergitol 15-S-30 in
Brine; Injection: 50 µL;
Column Temperature:
25°C; Mobile Phase:
100mM Ammonium
Acetate(pH5.5)/CAN,
linear gradient: 75/2525/75 in 20 minutes;
Flow rate: 1 ml/min;
ELSD setting: 60°C, 3.5
Bar.
Carbonate sand vs. dolomite powder
AOS1618 static adsorption in DI water
Carbonate 20/40
Dolomite powder
2.4
2.2
2
Adsorption (mg/g)
1.8
1.6
1.4
1.2
1
0.8
0.6
0.4
0.2
0
0
0.02
0.04
0.06
0.08
0.1
0.12
0.14
Equilibrium surfactant concentration (wt%)
0.16
0.18
Effect of carbonate / bicarbonate ions
Adsorption of MACKAM LAB
Future work
★ Continue current work in synthetic brine;
★ Potential determining ions for adsorption reduction;
★ Adsorption at elevated temperatures;
★ Evaluation of other foaming surfactants.