Sacrificial Agent for Reducing Adsorption
of Anionic Surfactants
By: Hadi ShamsiJazeyi, George J. Hirasaki, Rafael Verduzco
Rice University
Chemical and Bio-molecular Engineering Department
17th Annual Meeting of
Rice University Consortium for Process in Porous Media
April 29, 2013
Problem Definition
Materials and Methods
Results and Discussions
Experimental Evidence for the effect
of anhydrite on adsorption of anionic
surfactants?
Does polyacrylate reduce adsorption
of different anionic surfactants on
different rocks and minerals?
Why Sodium Polyacrylate?
Any role for Mw of polyacrylate?
What is the adsorption of polyacrylate
in comparison with anionic surfactant?
Effect of salinity and divalent ions on
application of polyacrylate as
sacrificial agent.
How does application of polyacrylate
affect the total material cost?
How dynamic and static adsorption
tests compares?
Conclusions
Anhydrite reacts with Sodium Carbonate!
Can Polyacrylate be used?
Adsorption of anionic surfactant on a
positively-charged surface of
rock/mineral
First-layer adsorption is governed by
electrostatics
Second-Layer adsorption can
happen at high concentrations
2
Anhydrite reacts with Sodium Carbonate!
Can Polyacrylate be used?
Adsorption of anionic surfactant can
be decreased by turning the surface
charge negative when an alkali is
used to raise the pH above pHpzc
2
Anhydrite reacts with Sodium Carbonate!
Can Polyacrylate be used?
2
Anhydrite reacts with Sodium Carbonate!
Can Polyacrylate be used?
2
Introduction and Problem Definition
Materials and Methods
Results and Discussions
Experimental Evidence for the effect
of anhydrite on adsorption of anionic
surfactants?
Does polyacrylate reduce adsorption
of different anionic surfactants on
different rocks and minerals?
Why Sodium Polyacrylate?
Any role for Mw of polyacrylate?
What is the adsorption of polyacrylate
in comparison with anionic surfactant?
Effect of salinity and divalent ions on
application of polyacrylate as
sacrificial agent.
How does application of polyacrylate
affect the total material cost?
How dynamic and static adsorption
tests compares?
Conclusions
List of surfactants
Trade or
descriptive
name
Chemical 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-Blend
A Blend of Neodol-67-7PO-Sulfate
and IOS15-18
(N:I)=4:1
--
--
Petro-step
S13B
i-C13-(PO)7 –SO4Na
85.50
TIORCO
3
List of polyacrylates
Trade or
descriptive
name
FLOSPERSE
1000
FLOSPERSE
3000
Chemical structure
Activity
(%)
Supplier
Sodium Polyacrylate (Mw=2200 Da)
44
SNF
44
SNF
Sodium Polyacrylate (Mw=4500 Da)
FLOSPERSE
15000
Sodium Polyacrylate (Mw=150 KDa)
FLOPAM
AN 995 BPM
Sodium Polyacrylate (Mw~3 MDa)
ACUMER
1100
Sodium Polyacrylate (Mw=4500 Da)
47-49
DOW Chem.
Poly(acrylic
sodium salt)
Sodium Polyacrylate (Mw= 5100 Da)
100
SigmaAldrich
30
100
SNF
SNF
4
Measurement of Adsorption
 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 anionic surfactant is measured using potentiometric titration.
 Concentration of sodium polyacrylate is measured using a colorimetric method.
5
Introduction and Problem Definition
Materials and Methods
Results and Discussions
Experimental Evidence for the effect
of anhydrite on adsorption of anionic
surfactants?
Does polyacrylate reduce adsorption
of different anionic surfactants on
different rocks and minerals?
Why Sodium Polyacrylate?
Any role for Mw of polyacrylate?
What is the adsorption of polyacrylate
in comparison with anionic surfactant?
Effect of salinity and divalent ions on
application of polyacrylate as
sacrificial agent.
How does application of polyacrylate
affect the total material cost?
How dynamic and static adsorption
tests compares?
Conclusions
Anhydrite Can Affect Sodium Carbonate and Increase
Adsorption of Anionic Surfactant
SAR = (# of moles of sodium carbonate) / (# of moles of anhydrite)
10
9
8
Pure Calcite + 5 % Anhydrite
No Sacrificial Agent
(SAR=0)
Adsorption (mg/g)
7
6
SAR=0.6
5
SAR=0.7
0.9
0.8
4
Variable SAR (24 h Eq. time)
1.3
Variable SAR (72 h Eq. time)
1.2
3
2.5
2
2.6
1% Sodium Carbonate + Pure
Calcite (SAR=∞)
1
Adsorption of NI-Blend, Initial
Concentration of NI-Blend = 0.5 %
0
0.0
0.1
0.2
0.3
0.4
0.5
3.5 % NaCl Salinity, Room
Temperature, 24 h Equilibrium Time
Equilibrium Concentration (wt%)
6
Introduction and Problem Definition
Materials and Methods
Results and Discussions
Experimental Evidence for the effect
of anhydrite on adsorption of anionic
surfactants?
Does polyacrylate reduce adsorption
of different anionic surfactants on
different rocks and minerals?
Why Sodium Polyacrylate?
Any role for Mw of polyacrylate?
What is the adsorption of polyacrylate
in comparison with anionic surfactant?
Effect of salinity and divalent ions on
application of polyacrylate as
sacrificial agent.
How does application of polyacrylate
affect the total material cost?
How dynamic and static adsorption
tests compares?
Conclusions
Characterization of the Rocks/Minerals
Adsorbent
(Powdered
Rock/Mineral)
purified
calcite
industrial
calcite
Multi-point
BET
Surface
Area* (m2/g)
1.318
1.608
T-Method
External
Surface
Area (m2/g)
1.222
1.297
T-Method
Average
Anhydrite
Micro-Porous
Pore
Percentage
Pore Volume Diameter
(%)
(cc/g)
(nm)
5.008E-5
1.617E-5
1.820
1.780
Other Notes
0.07
(99.5 wt% CaCO3)
Alfa Aesar
[Lot # C270009]
0.11
97.00 wt% CaCO3
(38.80 wt% Ca)
Franklin Industrial
Minerals
Carlpool
dolomite
0.7846
0.7426
1.726E-5
4.181
1.76
(20.00 wt% Ca)
(10.00 wt% Mg)
Earthsafe
Organics
Carlpool Products
Indiana
limestone
0.9851
0.9850
1.421E-7
4.363
0.82
Kocurek Industries
purified
kaolinite
20.8655
19.5626
5.832E-4
4.969
0.03
Sigma-Aldrich
[Lot # 048K0046]
powdered
Berea
sandstone
2.6750
2.6730
3.341E-4
1.149
NA
Kocurek Industries
7
Adsorption (mg/g)
Polyacrylate vs. Sodium Carbonate for Reducing
Adsorption of NI-Blend on Different Rocks/Minerals
7
After Addition of 1 wt % Na2CO3
6
After Addition of 2500 ppm of
Sodium Polyacrylate (4500 Da)
Room Temperature,
24 h Equilibrium time
Initial Concentration of
NI-Blend = 0.5 wt%
Rotary Mixer (4-5 rpm)
up to 18
8
W/O Sacrificial Agent
5
4
3
2
Almost Zero Adsorption
after addition of 2500 ppm
Na-Polyacrylate
1
0
Carlpool
Dolomite
Franklin
Industrial Calcite
Kaolinite
Indiana
LimeStone
Powderized
Berea Sandstone
8
Reducing Adsorption of Two Different Surfactants
using Polyacrylate on Carlpool Dolomite
2.5
2.5
Without
Sacrificial Agent
2
Adsorption (mg/g)
NI-Blend
2
Adsorption (mg/g)
S13B
1.5
1.5
After adding
2500 ppm
Sodium
Polyacrylate
(Mw=4500 Da)
1
0.5
0
1
NI-Blend
S13B
0.5
0
0
500
1000
1500
2000
2500
Initial Concentration of Sodium Polyacrylate (Mw=4500 Da) (ppm)
3000
9
Introduction and Problem Definition
Materials and Methods
Results and Discussions
Experimental Evidence for the effect
of anhydrite on adsorption of anionic
surfactants?
Does polyacrylate reduce adsorption
of different anionic surfactants on
different rocks and minerals?
Why Sodium Polyacrylate?
Any role for Mw of polyacrylate?
What is the adsorption of polyacrylate
in comparison with anionic surfactant?
Effect of salinity and divalent ions on
application of polyacrylate as
sacrificial agent.
How does application of polyacrylate
affect the total material cost?
How dynamic and static adsorption
tests compares?
Conclusions
Adsorption of NI-Blend (mg/g)
Reducing Adsorption of NI-Blend on Carlpool Dolomite:
Polyacrylate vs. Different Chemicals
2.0
Monomer Sacrificial Agents
Polymeric Sacrificial Agents
1.6
1.2
Sodium polyacrylates
with different Mw from
different vendors
0.8
0.4
0.0
10
Sodium Polyacrylate vs. Other Sacrificial Agents
in the Literature
Adsorption of NI-Blend on Carlpool dolomite
(mg/g)
2.0
Poly(EthyleneGlycol) Methyl Ether (Mw=5000 Da)
1.8
Sodium Metaborate
1.6
sodium carbonate
1.4
Sodium Polyacrylate (Mw=4500 Da)
1.2
1.0
0.8
0.6
0.4
0.2
0.0
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
Concentration of added Sacrificial Agent (wt %)
11
Introduction and Problem Definition
Materials and Methods
Results and Discussions
Experimental Evidence for the effect
of anhydrite on adsorption of anionic
surfactants?
Does polyacrylate reduce adsorption
of different anionic surfactants on
different rocks and minerals?
Why Sodium Polyacrylate?
What is role for Mw of polyacrylate?
What is the adsorption of polyacrylate
in comparison with anionic surfactant?
Effect of salinity and divalent ions on
application of polyacrylate as
sacrificial agent.
How does application of polyacrylate
affect the total material cost?
How dynamic and static adsorption
tests compares?
Conclusions
Effect of Molecular Weight of
Polyacrylate on adsorption of anionic surfactant
1.8
Sodium Propionate
(Repeating Unit of Sodium
Polyacrylate)
Adsorption of NI-Blend (mg/g)
1.6
1.4
SNF FLOSPERSE 1000
(Sodium Polyacrylate
Mw=2200 Da)
1.2
1.0
SNF FLOSPERSE 3000
(Sodium Polyacrylate
Mw=4500 Da)
0.8
SNF FLOSPERSE 15000
(Sodium Polyacrylate
Mw=150,000 Da)
0.6
0.4
SNF FLOPAM AN 995 BPM
(Sodium Polyacrylate
Mw=2.5-3.5 M Da)
0.2
0.0
0
500
1000
1500
2000
2500
Initial Concentration of Sacrificial Agents Added (ppm)
12
Introduction and Problem Definition
Materials and Methods
Results and Discussions
Experimental Evidence for the effect
of anhydrite on adsorption of anionic
surfactants?
Does polyacrylate reduce adsorption
of different anionic surfactants on
different rocks and minerals?
Why Sodium Polyacrylate?
What is role for Mw of polyacrylate?
What is the adsorption of polyacrylate
in comparison with anionic surfactant?
Effect of salinity and divalent ions on
application of polyacrylate as
sacrificial agent.
How does application of polyacrylate
affect the total material cost?
How dynamic and static adsorption
tests compares?
Conclusions
Adsorption of Polyacrylate (Mw=4500Da) on Carlpool Dolomite
2.0
1.8
Initial Concentration of Polymer = 0.5 %wt
Initial Concentration of Surfactant Varies
All solution @ 3.5 % NaCl, Room Temperature
Dolomite (from Carlpool) 20% Ca, 10% Mg
NI-Blend Adsorption
Adsorption (mg/g)
1.6
1.4
Compare Adsorption of NI-Blend
and that of Sodium Polyacrylate
(Mw=4500Da) on the same
Adsorbent (Carlpool Dolomite)
1.2
1.0
0.8
Polyacrylate Adsorption
0.6
0.4
0.2
0.0
No Surfactant
0.3 wt% NI-Blend
Added
0.5 wt% NI-Blend
Added
Adsorption of NIBlend
13
Introduction and Problem Definition
Materials and Methods
Results and Discussions
Experimental Evidence for the effect
of anhydrite on adsorption of anionic
surfactants?
Does polyacrylate reduce adsorption
of different anionic surfactants on
different rocks and minerals?
Why Sodium Polyacrylate?
What is role for Mw of polyacrylate?
What is the adsorption of polyacrylate
in comparison with anionic surfactant?
Effect of salinity and divalent ions on
application of polyacrylate as
sacrificial agent.
How does application of polyacrylate
affect the total material cost?
How dynamic and static adsorption
tests compares?
Conclusions
Effect of salinity
NI-Blend Adsorption
Carlpool Dolomite
2.5
2.0
Adsorption of NI-Blend on Carlpool
Dolomite (mg/g)
Adsorption of NI-Blend on Powdered
Berea Sandstone (mg/g)
NI-Blend Adsorption
Powdered Berea Sandstone
No sacrificial agent added
2
After addition of 2500 ppm
sodium polyacrylate
(Mw=4500 Da)
1.5
1
0.5
1.8
1.6
1.4
1.2
No sacrificial agent added
1.0
0.8
After addition of 2500 ppm
sodium polyacrylate
(Mw=4500 Da)
0.6
0.4
0.2
0
0.0
0
1
2
3
NaCl Salinity (wt %)
4
0
1
2
3
NaCl Salinity (wt %)
4
14
Effect of divalent ions
NI-Blend Adsorption
Kaolinite
5.0
On Pure Kaolinite W/O
Sacrificial Agent
20
15
10
5
4.0
On Pure Calcite W/O
Sacrificial Agent
3.5
3.0
On Pure Calcite W/ 2500
ppm Sodium Polyacrylate
(4500 Da)
2.5
2.0
1.5
1.0
Initial Solution Becomes Hazy
On Pure Kaolonite W/ 2500
ppm Sodium Polyacrylate
(4500 Da)
NI-Blend Adsorption (mg/g)
25
4.5
Initial Solution becomes Hazy
NI-Blend Adsorption (mg/g)
30
NI-Blend Adsorption
Pure Calcite
0.5
0.0
0
0
1000
2000
3000
Concentration of added CaCl2 (ppm)
0
1000
2000
3000
Concentration of Added CaCl2 (ppm)
15
Effect of divalent ions
4
On Powdered Berea Sandstone W/
2500 ppm Sodium Polyacrylate
(4500 Da)
3
2
1
0
0
1000
2000
3000
Concentration of Added CaCl2 (ppm)
3.0
On Carlpool Dolomite W/O
Sacrificial Agent
2.5
On Carlpool Dolomite W/ 2500 ppm
Sodium Polyacrylate (4500 Da)
2.0
1.5
1.0
0.5
Initial Solution Becomes Hazy
On Powdered Berea Sandstone W/O
Sacrificial Agent
NI-Blend Adsorption (mg/g)
5
NI-Blend Adsorption on Carlpool
Dolomite
Initial Solution Becomes Hazy
NI-Blend Adsorption (mg/g)
NI-Blend Adsorption on
Powdered Berea Sandstone
0.0
0
1000
2000
3000
Concentration of Added CaCl2 (ppm)
16
Introduction and Problem Definition
Materials and Methods
Results and Discussions
Experimental Evidence for the effect
of anhydrite on adsorption of anionic
surfactants?
Does polyacrylate reduce adsorption
of different anionic surfactants on
different rocks and minerals?
Why Sodium Polyacrylate?
What is role for Mw of polyacrylate?
What is the adsorption of polyacrylate
in comparison with anionic surfactant?
Effect of salinity and divalent ions on
application of polyacrylate as
sacrificial agent.
How does application of polyacrylate
affect the total material cost?
How dynamic and static adsorption
tests compares?
Conclusions
Economical Study:
Effect of Reservoir/Injection (Alfa Dimensionless Number)
*
*
* *
*
*
*
*
*
*
17
Economical Study:
Effect of Cost of Polyacrylate to Cost of Surfactant
Cost Dimensionless Number
**
**
* *
*
*
*
*
18
Introduction and Problem Definition
Materials and Methods
Results and Discussions
Experimental Evidence for the effect
of anhydrite on adsorption of anionic
surfactants?
Does polyacrylate reduce adsorption
of different anionic surfactants on
different rocks and minerals?
Why Sodium Polyacrylate?
What is role for Mw of polyacrylate?
What is the adsorption of polyacrylate
in comparison with anionic surfactant?
Effect of salinity and divalent ions on
application of polyacrylate as
sacrificial agent.
How does application of polyacrylate
affect the total material cost?
How dynamic and static adsorption
tests compares?
Conclusions
Dynamic Adsorption of 0.5 wt% NI-blend
on Carlpool Dolomite with no sacrificial agent
19
Dynamic Adsorption of 0.5 wt% NI-blend
On Carlpool Dolomite with 1000 (ppm) sodium polyacrylate
20
Comparison of Static and Dynamic Adsorptions
NI-Blend Adsorption
(mg/g)
PAR = (# of repeating units in polyacrylate) / (# of moles of anhydrite)
1.8
1.6
1.4
1.2
1
0.8
0.6
0.4
0.2
0
dynamic test
Pure Calcite +
5% Anhydrite
without Sacrificial
Agent
Various PAR
Polyacrylate on
Calcite no
anhydrite
NI-blend Adsorption
(mg/g)
0 ppm sodium
polyacrylate
static test
1000 ppm sodium 2500 ppm sodium
polyacrylate
polyacrylate
8.9
7.9
6.9
5.9
4.9
3.9
2.9
1.9
0.9
-0.1
0
0.1
0.2
0.3
0.4
Equilibrium Concentration of NI-blend (wt%)
0.5
22
Introduction and Problem Definition
Materials and Methods
Results and Discussions
Experimental Evidence for the effect
of anhydrite on adsorption of anionic
surfactants?
Does polyacrylate reduce adsorption
of different anionic surfactants on
different rocks and minerals?
Why Sodium Polyacrylate?
What is role for Mw of polyacrylate?
What is the adsorption of polyacrylate
in comparison with anionic surfactant?
Effect of salinity and divalent ions on
application of polyacrylate as
sacrificial agent.
How does application of polyacrylate
affect the total material cost?
How dynamic and static adsorption
tests compares?
Conclusions
Conclusion
1. Sodium polyacrylate strongly reduces adsorption of different anionic surfactants
on different rocks/minerals more than other traditional sacrificial agents even in
presence of anhydrite.
2. No high molecular weight polyacrylate to be used (4500 Da is enough).
3. Adsorption of sodium polyacrylate does NOT change with presence of anionic
surfactant, and is almost 1/4th of the adsorption of NI-Blend on same rock.
4. Effect of salinity and divalent ions in the brine was tested. In the absence of
anhydrite, sodium polyacrylate acts as a better sacrificial agent in purified water.
In the presence of anhydrite, purification of water does NOT add advantage.
5. By choosing the optimal concentration of polyacrylate the total material cost of a
dynamic injection can be significantly reduced.
23
THANK YOU
25
Back-Up Slides
26
Is Polyacrylate Affecting the titration of Surfactant?
Sodium Polyacrylate has
negative charge in neutral pH
Does this mean that Sodium
Polyacrylate can interfere with
measuring concentration of
anionic (sulfate-based)
surfactant?
Surfactant has
negative charge in neutral pH
27
Is Polyacrylate Affecting the titration of Surfactant?
(…Continued)
40
Our strategy is to do the potentiometric titration at
pH=3 so that the polyacrylate does not have any
charge, but sulfate-based anionic surfactant does.
Volume of titrant used for EP (cc)
7
6
5
4
3
2
1
-0.2
The surfactant used is S13B.
Concentration
of Surfactant = 0.75 %
W/O Polymer
Concentration of Polymer Added =
0.56 %
pH
3
was
provided
in the titration
W/ Polyacrylate
experiment using HCl solution.
The source of Polyacrylate is
Acumer 1100.
two solutions were made. The first
y = 10.985x
one has ~0.75% of surfactant at 3.5
R² = 0.9982
% NaCl. The second one has ~0.75%
of surfactant, ~0.56% of polymer at
3.5 % NaCl.
Different sample sizes were taken
from these two solutions, diluted to
about 30 (g) using DI-Water, and then
HCl was added and pH was
measured to be about 3. Then,
0.2
0.4
0.6 titration was done by potentiometric
titration.
0
1E-15
Sample Size (cc)
28
Measurement of Concentration of Sodium Polyacrylate
(Colorimetric Method)
Effect of S13B On
Colorimetric
Measurement
29
Dynamic Adsorption of 0.5 wt% NI-blend
on Carlpool Dolomite with 2500 (ppm) sodium polyacrylate
21