Download - Adsorption of Betaines
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Adsorption of Betaines
Hadi ShamsiJazeyi, George J. Hirasaki, Rafael Verduzco
Rice UniversityChemical and Bio-molecular Engineering Department
18th Annual Meeting of Rice University Consortium for Process in Porous Media
April 21, 2014
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Outline
Introduction
Adsorption measurement
Can polyacrylate reduce adsorption of lauryl betaine?
Different chemicals as sacrificial agent for betaines
Effect of pH (surface charge) on adsorption of betaines
Effect of anionic surfactant on pH dependency of betaine adsorption
Hypothesis: molecular mechanism of adsorption of betaines
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Introduction
Surfactant adsorption on the rock is a major cost issue for EOR
Betaine is a class of zwitterionic surfactants (with two opposite
charge on each surfactant molecule)
Adsorption of betaine can be very high at certain conditions
Polymeric sacrificial agent (sodium polyacrylate) was tested for
reducing adsorption of anionic surfactants and showed up to
80% reduction in total cost of materials
We study conditions by which the adsorption of betaine is minimum
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Measurement of Concentration and Adsorption of Lauryl Betaine
Plateau region of adsorption isotherms
should be measured.
Both initial and equilibrium
concentrations are measured.
Equilibrium concentration should be
far enough from initial concentration, so
that the noise in measurement can be
neglected.
Concentration of betaine is measured
by two phase titration at pH<1
We made sure that the anionic
surfactant has no effect on betaine
measurement at this low pH
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Can Polyacrylate Reduce Adsorption of Lauryl Betaine?Adsorption on Kaolinite
Room Temperature, Batch Adsorption Study
Adsorption on SilicaRoom Temperature
Batch Adsorption Study
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0
1
2
3
4
5
6
Ads
orpt
ion
(mg/
g)
b)
0
5
10
15
20
25
30
35
Ads
orpt
ion
(mg/
g)
a)Different chemicals as sacrificial agent for betaines
Adsorption on Kaolinite Adsorption on Silica
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Effect of pH (surface charge) on adsorption of betaines
Adsorption on Kaolinite Adsorption on Silica
Increase in pH Adsorption Decreases then Increases and may Plateau
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Effect of pH on Zeta Potential and Surface Charge
Increase in pH More Negative Charge on the Surface of Rock
2 3 4 5 6 7 8 9 10 11 12 13
-160
-140
-120
-100
-80
-60
-40
-20
0
20
Silica
Kaolinite
Equilibrium pHZe
ta P
oten
tial (
mV)
Ionic strength = 0.1 MRoom temperature
Kaolinite data from: D.J.A. Williams, K.P. Williams, Electrophoresis and zeta potential of kaolinite, J. Colloid Interface Sci., 65 (1978) 79-87
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Effect of pH on the Charge of Lauryl Betaine
Increase in pH in the Basic Region Has No Significant Effect on Charge of Lauryl Betaine
0 2 4 6 8 10 12 140
2
4
6
8
10
12
14 0% NaCl2.5% NaCl5% NaCl10% NaCl
Calculated pH based on addition of NaOH or HCl
Expe
rimen
tal p
H
Acidic RegionTitrated with HCl
Negative charge of the betaine goes start to vanish
Basic RegionTitrated with NaOH
Both positive and negative charges are
present
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Summary of Experimental Evidence
Adsorption of lauryl betaine decreases
with increase in pH, but in a basic pH
range, adsorption increases and may
plateau.
This basic pH range starts at pH 10 and
12 for silica and Kaolinite, respectively.
It was shown that the charge of betaine
does not change in the pH range that the
adsorption trend changes
It was also shown that the surface of the
rocks (silica or Kaolinite) becomes more
negative with increase in pH
Adsorbent Surface -- -- -- -- -- -- -- -- -- -- -- -- --
Repulsive force on negative charge of
betaine
Attractive force on Positive charge of
betaine
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Hypothetic molecular mechanism for adsorption of betaines 1 3 5
Increase in pHDecrease in Adsorption
Increase in pHIncrease in Adsorption
Adsorbent Surface1
+ + + -- + -- + + + -- + + + --
Adsorbent Surface+ + -- -- + -- + + + -- + -- + +
Adsorbent Surface+ -- -- -- + -- + -- -- + + -- -- +
Adsorbent Surface -- -- -- -- -- + -- -- -- + -- -- --
Adsorbent Surface -- -- -- -- -- -- -- -- -- -- -- -- --
5
1
2
3
4
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Effect of anionic surfactant on pH dependency of betaine adsorptionAdsorption on Kaolinite @ 0% NaCl Adsorption on Kaolinite @ 2.5% NaCl
6 8 10 12 140
5
10
15
20
25
30
35
No sodium octonate used
sodium octonate:betaine = 1:2 (mass ratio)
Betaine:Sodium Octanate (1:1 Mass ratio)
Equilibrium pH
Bet
aine
Ads
orpt
ion
(mg/
g)
6 8 10 12 140
2
4
6
8
10
12
14
No sodium octonate
betaine:sodium octonate (1:1 mass ra-tio)
Equilibrium pH
Bet
aine
Ads
orpt
ion
(mg/
g)
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How Anionic Surfactant Reduces Adsorption of Betaines?
Adsorbent Surface+ + + -- + -- + + + -- + + + --
Adsorbent Surface -- -- -- -- -- -- -- -- -- -- -- -- --
Adsorbent Surface -- -- -- -- -- -- -- -- -- -- -- -- --
Adsorbent Surface+ + + -- + -- + + + -- + + + --
Adsorption of betaine in the
absence of anionic
surfactant
Adsorption of betaine in the presence of
anionic surfactant
Mechanism in low pH range(where positive charges exist)
Competitive Adsorption
Mechanism in high pH range(where only negative charges are
dominant)Betaine-anionic surfactant
interactions
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Conclusions
Many chemicals tested to reduce adsorption of lauryl betaine, including
sodium polyacrylate, but the reduction in adsorption is not as desired.
The effect of pH on adsorption of lauryl betaine on silica and Kaolinite was
investigated.
With increase in pH, adsorption decreased and reached a minimum but
then increased or reached a plateau.
Although increase in pH makes the charge of the surface more negative, it
does not have any effect on charge of betaine at pH>7
Bending of the betaine molecule due to increased negative surface charge
is hypothesized to be responsible for a second increase in adsorption.
Anionic surfactant can reduce the adsorption of betaine. This is explained
by competitive adsorption and interaction between betaine and anionic
surfactant.
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Back-Up Slides
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List of surfactants
Trade or descriptive
nameChemical structure Activity
(%) Supplier
Neodol-67(N) bC16-17(CH3-CH-CH2-O)7-SO4Na 22.88 STEPAN
IOS15-18(I)
R-CH(OH)-CH2-CH(SO3)-R (~75%)R-CH=CH-CH(SO3-)-R
(~25%)where R+R’ = C12-15
21.29 STEPAN
NI-BlendA Blend of Neodol-67-7PO-Sulfate
and IOS15-18 (N:I)=4:1
-- --
MACKAM LB-35 C12-N+-COO- 27.9 Rhodia
3