Surfactant Analysis

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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
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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

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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
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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
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High Performance Liquid Chromatography
Column Dionex Acclaim Surfactant, 4.6 250mm (P/N 063203)
Guard Column Dionex Acclaim Surfactant, 4.6 10mm (P/N 069701)
Storage Solution Acetonitril/0.1Acetic Acid or Acetonitril/100mM NH4OAc at v/v 80/20
Mobile phase ACN/DI or Methanol/DI, 0-100 organic in mobile phase
pH 2.5-7.5
Temperature lt60oC
Pressure lt5500 psi
Typical Flow Rate 0.8-2.0 mL/min
Injection Volume 5-50 µL
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Analysis of zwitterionic surfactants
Cocamidopropyl hydroxysultaine
brine
surfactant
0.435 AMPHOSOL CS-50 in Brine Injection 25 µL
Column Temperature 25C Mobile Phase 100mM
Ammonium Acetate(pH5.5)/CAN, linear gradient
75/25-25/75 in 20 minutes Flow rate 1 ml/min
ELSD setting 60C, 3.5 Bar.
Successful separation of high-salinity brine and
surfactants
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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.

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Carbonate sand vs. dolomite powder
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Comparison of anionics
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Comparison of cationics
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Comparison of zwitterionics
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Adsorption of TERGITOL 15-S-30
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Adsorption plateaus
anionics
cationics
zwitterionics
nonionics
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Surfactant adsorption model

• Assumptions
• Surfactant is present in aqueous phase, but not
  in gaseous phase
• Surfactant adsorption can be described with a
  Langmuir-type isotherm.

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Static adsorption of anionic surfactant on
dolomite
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Propagation of a finite slug (0.5 PV)
Surfactant AOS1618, 0.2 wt Mineral dolomite
powder No dispersion
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Effluent of a finite slug (0.5 PV)
Surfactant AOS1618, 0.2 wt Mineral dolomite
powder
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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.
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Acknowledgment
This work was financially supported by ADNOC,
ADCO, ZADCO, ADMA-OPCO and PI, U.A.E.
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Thank you!
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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
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Analysis of nonionic surfactants
0.2 Tergitol 15-S-30 in Brine Injection 50 µL
Column Temperature 25C Mobile Phase 100mM
Ammonium Acetate(pH5.5)/CAN, linear gradient
75/25-25/75 in 20 minutes Flow rate 1 ml/min
ELSD setting 60C, 3.5 Bar.
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Carbonate sand vs. dolomite powder
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Effect of carbonate / bicarbonate ions
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Adsorption of MACKAM LAB
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Future work

• ? Continue current work in synthetic brine
• ? Potential determining ions for adsorption
  reduction
• ? Adsorption at elevated temperatures
• ? Evaluation of other foaming surfactants.