Sacrificial Agent for Reducing Adsorption

of Anionic Surfactants

By: Hadi ShamsiJazeyi, George J. Hirasaki, Rafael Verduzco

Rice UniversityChemical and Bio-molecular Engineering Department

17th Annual Meeting of Rice University Consortium for Process in Porous Media

April 29, 2013

Conclusions

Results and Discussions

Materials and Methods

Problem Definition

Why Sodium Polyacrylate? Any role for Mw of polyacrylate?

Does polyacrylate reduce adsorption of different anionic surfactants on

different rocks and minerals?

Effect of salinity and divalent ions on application of polyacrylate as

sacrificial agent.

What is the adsorption of polyacrylate in comparison with anionic surfactant?

Experimental Evidence for the effect of anhydrite on adsorption of anionic

surfactants?

How does application of polyacrylate affect the total material cost?

How dynamic and static adsorption tests compares?

Anhydrite reacts with Sodium Carbonate! Can Polyacrylate be used?

2

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

Anhydrite reacts with Sodium Carbonate! Can Polyacrylate be used?

2

Adsorption of anionic surfactant can be decreased by turning the surface

charge negative when an alkali is used to raise the pH above pHpzc

Anhydrite reacts with Sodium Carbonate! Can Polyacrylate be used?

2

Anhydrite reacts with Sodium Carbonate! Can Polyacrylate be used?

2

Conclusions

Results and Discussions

Materials and Methods

Introduction and Problem Definition

Why Sodium Polyacrylate? Any role for Mw of polyacrylate?

Does polyacrylate reduce adsorption of different anionic surfactants on

different rocks and minerals?

Effect of salinity and divalent ions on application of polyacrylate as

sacrificial agent.

What is the adsorption of polyacrylate in comparison with anionic surfactant?

Experimental Evidence for the effect of anhydrite on adsorption of anionic

surfactants?

How does application of polyacrylate affect the total material cost?

How dynamic and static adsorption tests compares?

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

-- --

Petro-step S13B i-C13-(PO)7 –SO4Na 85.50 TIORCO

3

List of polyacrylatesTrade or

descriptive name

Chemical structure Activity (%) Supplier

FLOSPERSE 1000 Sodium Polyacrylate (Mw=2200 Da) 44 SNF

FLOSPERSE3000

Sodium Polyacrylate (Mw=4500 Da) 44 SNF

FLOSPERSE15000 Sodium Polyacrylate (Mw=150 KDa) 30 SNF

FLOPAMAN 995 BPM Sodium Polyacrylate (Mw~3 MDa) 100 SNF

ACUMER 1100 Sodium Polyacrylate (Mw=4500 Da) 47-49 DOW Chem.

Poly(acrylic sodium salt) Sodium Polyacrylate (Mw= 5100 Da) 100 Sigma-

Aldrich

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

Conclusions

Results and Discussions

Materials and Methods

Introduction and Problem Definition

Why Sodium Polyacrylate? Any role for Mw of polyacrylate?

Does polyacrylate reduce adsorption of different anionic surfactants on

different rocks and minerals?

Effect of salinity and divalent ions on application of polyacrylate as

sacrificial agent.

What is the adsorption of polyacrylate in comparison with anionic surfactant?

Experimental Evidence for the effect of anhydrite on adsorption of anionic

surfactants?

How does application of polyacrylate affect the total material cost?

How dynamic and static adsorption tests compares?

Anhydrite Can Affect Sodium Carbonate and Increase Adsorption of Anionic Surfactant

0.0 0.1 0.2 0.3 0.4 0.50

1

2

3

4

5

6

7

8

9

10

Equilibrium Concentration (wt%)

Adso

rptio

n (m

g/g)

Adsorption of NI-Blend, Initial Con-centration of NI-Blend = 0.5 %

3.5 % NaCl Salinity, Room Tem-perature, 24 h Equilibrium Time

2.6

1.3

0.9SAR=0.6

SAR=0.70.8

1.22.5

1% Sodium Carbonate + Pure Calcite (SAR=∞)

Variable SAR (24 h Eq. time)

Variable SAR (72 h Eq. time)

Pure Calcite + 5 % AnhydriteNo Sacrificial Agent

(SAR=0)

6

SAR = (# of moles of sodium carbonate) / (# of moles of anhydrite)

Conclusions

Results and Discussions

Materials and Methods

Introduction and Problem Definition

Why Sodium Polyacrylate? Any role for Mw of polyacrylate?

Does polyacrylate reduce adsorption of different anionic surfactants on

different rocks and minerals?

Effect of salinity and divalent ions on application of polyacrylate as

sacrificial agent.

What is the adsorption of polyacrylate in comparison with anionic surfactant?

Experimental Evidence for the effect of anhydrite on adsorption of anionic

surfactants?

How does application of polyacrylate affect the total material cost?

How dynamic and static adsorption tests compares?

Characterization of the Rocks/Minerals

Adsorbent (Powdered

Rock/Mineral)

Multi-point BET

Surface Area* (m2/g)

T-Method External

Surface Area (m2/g)

T-Method Micro-Porous Pore Volume

(cc/g)

Average Pore

Diameter (nm)

Anhydrite Percentage

(%)Other Notes

purified calcite 1.318 1.222 5.008E-5 1.820 0.07

(99.5 wt% CaCO3)Alfa Aesar

[Lot # C270009]

industrial calcite 1.608 1.297 1.617E-5 1.780 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

sandstone2.6750 2.6730 3.341E-4 1.149 NA Kocurek Industries

7

Polyacrylate vs. Sodium Carbonate for Reducing Adsorption of NI-Blend on Different Rocks/Minerals

Carlpool Dolomite

Franklin In-dustrial Calcite

Kaolinite Indiana LimeStone

Powderized Berea

Sandstone

0

1

2

3

4

5

6

7

8 W/O Sacrificial Agent

After Addition of 1 wt % Na2CO3

After Addition of 2500 ppm of Sodium Polyacrylate (4500 Da)

Ads

orpt

ion

(mg/

g)

Room Temperature, 24 h Equilibrium time

Initial Concentration of NI-Blend = 0.5 wt%

Rotary Mixer (4-5 rpm)

up to

18

Almost Zero Adsorption after addition of 2500 ppm

Na-Polyacrylate

8

Reducing Adsorption of Two Different Surfactants using Polyacrylate on Carlpool Dolomite

0 500 1000 1500 2000 2500 30000

0.5

1

1.5

2

2.5

NI-Blend

S13B

Initial Concentration of Sodium Polyacrylate (Mw=4500 Da) (ppm)

Ads

orpt

ion

(mg/

g)

NI-Blend S13B0

0.5

1

1.5

2

2.5

Without Sacrificial Agent

After adding 2500 ppm Sodium Polyacrylate (Mw=4500 Da)

Ads

orpt

ion

(mg/

g)

9

Conclusions

Results and Discussions

Materials and Methods

Introduction and Problem Definition

Why Sodium Polyacrylate? Any role for Mw of polyacrylate?

Does polyacrylate reduce adsorption of different anionic surfactants on

different rocks and minerals?

Effect of salinity and divalent ions on application of polyacrylate as

sacrificial agent.

What is the adsorption of polyacrylate in comparison with anionic surfactant?

Experimental Evidence for the effect of anhydrite on adsorption of anionic

surfactants?

How does application of polyacrylate affect the total material cost?

How dynamic and static adsorption tests compares?

Reducing Adsorption of NI-Blend on Carlpool Dolomite: Polyacrylate vs. Different Chemicals

10

Glyceri

c acid

Glycolic

acid

Sodium carbonate

Sodium EDTA

Pectin

Mw=2

MDa

Sodium alginate

Mw=2

MDa

Sigma Na-p

olyacry

late M

w=210

...

Dow Na-polya

crylat

e Mw=2

100 D

a

Sigma Na-p

olyacry

late M

w=510

...

Dow Na-polya

crylat

e Mw=4

100 D

a0.0

0.4

0.8

1.2

1.6

2.0A

dsor

ptio

n of

NI-B

lend

(mg/

g) Monomer Sacrificial Agents Polymeric Sacrificial Agents

Sodium polyacrylates with different Mw from different

vendors

Sodium Polyacrylate vs. Other Sacrificial Agents in the Literature

11

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 10.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

1.8

2.0Poly(EthyleneGlycol) Methyl Ether (Mw=5000 Da)

Sodium Metaborate

sodium carbonate

Sodium Polyacrylate (Mw=4500 Da)

Concentration of added Sacrificial Agent (wt %)

Adso

rptio

n of

NI-B

lend

on

Carlp

ool d

olom

ite

(mg/

g)

Conclusions

Results and Discussions

Materials and Methods

Introduction and Problem Definition

Why Sodium Polyacrylate? What is role for Mw of polyacrylate?

Does polyacrylate reduce adsorption of different anionic surfactants on

different rocks and minerals?

Effect of salinity and divalent ions on application of polyacrylate as

sacrificial agent.

What is the adsorption of polyacrylate in comparison with anionic surfactant?

Experimental Evidence for the effect of anhydrite on adsorption of anionic

surfactants?

How does application of polyacrylate affect the total material cost?

How dynamic and static adsorption tests compares?

Effect of Molecular Weight of Polyacrylate on adsorption of anionic surfactant

12

0 500 1000 1500 2000 25000.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

1.8

Sodium Propionate (Repeating Unit of Sodium Polyacrylate)

SNF FLOSPERSE 1000 (Sodium Polyacrylate Mw=2200 Da)

SNF FLOSPERSE 3000 (Sodium Polyacrylate Mw=4500 Da)

SNF FLOSPERSE 15000 (Sodium Polyacrylate Mw=150,000 Da)

SNF FLOPAM AN 995 BPM (Sodium Polyacrylate Mw=2.5-3.5 M Da)

Initial Concentration of Sacrificial Agents Added (ppm)

Adso

rptio

n of

NI-B

lend

(mg/

g)

Conclusions

Results and Discussions

Materials and Methods

Introduction and Problem Definition

Why Sodium Polyacrylate? What is role for Mw of polyacrylate?

Does polyacrylate reduce adsorption of different anionic surfactants on

different rocks and minerals?

Effect of salinity and divalent ions on application of polyacrylate as

sacrificial agent.

What is the adsorption of polyacrylate in comparison with anionic surfactant?

Experimental Evidence for the effect of anhydrite on adsorption of anionic

surfactants?

How does application of polyacrylate affect the total material cost?

How dynamic and static adsorption tests compares?

Adsorption of Polyacrylate (Mw=4500Da) on Carlpool Dolomite

0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

1.8

Adso

rptio

n (m

g/g)

Initial Concentration of Polymer = 0.5 %wtInitial Concentration of Surfactant VariesAll solution @ 3.5 % NaCl, Room TemperatureDolomite (from Carlpool) 20% Ca, 10% Mg

Compare Adsorption of NI-Blend and that of Sodium Polyacrylate

(Mw=4500Da) on the same Adsor-bent (Carlpool Dolomite)

Polyacrylate Adsorption

NI-Blend Adsorption

13

Conclusions

Results and Discussions

Materials and Methods

Introduction and Problem Definition

Why Sodium Polyacrylate? What is role for Mw of polyacrylate?

Does polyacrylate reduce adsorption of different anionic surfactants on

different rocks and minerals?

Effect of salinity and divalent ions on application of polyacrylate as

sacrificial agent.

What is the adsorption of polyacrylate in comparison with anionic surfactant?

Experimental Evidence for the effect of anhydrite on adsorption of anionic

surfactants?

How does application of polyacrylate affect the total material cost?

How dynamic and static adsorption tests compares?

Effect of salinity

NI-Blend AdsorptionPowdered Berea Sandstone

NI-Blend Adsorption Carlpool Dolomite

0 1 2 3 40.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

1.8

No sacrificial agent added

After addition of 2500 ppm sodium polyacrylate (Mw=4500 Da)

NaCl Salinity (wt %)

Ads

orpt

ion

of N

I-Ble

nd o

n C

arlp

ool

Dol

omite

(mg/

g)0.5 1 1.5 2 2.5 3 3.5 4

0

0.5

1

1.5

2

2.5

No sacrificial agent added

After addition of 2500 ppm sodium polyacrylate (Mw=4500 Da)

NaCl Salinity (wt %)

Adso

rptio

n of

NI-B

lend

on

Pow

dere

d Be

rea

Sand

ston

e (m

g/g)

14

Effect of divalent ions

NI-Blend Adsorption Kaolinite

NI-Blend Adsorption Pure Calcite

0 1000 2000 30000.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

5.0

On Pure Calcite W/O Sacrificial Agent On Pure Calcite W/ 2500 ppm Sodium Polyacry-late (4500 Da)

Concentration of Added CaCl2 (ppm)

NI-B

lend

Ads

orpt

ion

(mg/

g)

Initi

al S

olut

ion

Bec

omes

Haz

y

15

0 500 1000 1500 2000 2500 3000 35000

5

10

15

20

25

30 On Pure Kaolinite W/O Sacrificial Agent On Pure Kaolonite W/ 2500 ppm Sodium Polyacrylate (4500 Da)

Concentration of added CaCl2 (ppm)

NI-B

lend

Ads

orpt

ion

(mg/

g)

Initi

al S

olut

ion

beco

mes

Haz

y

Effect of divalent ions

NI-Blend Adsorption on Powdered Berea Sandstone

NI-Blend Adsorption on Carlpool Dolomite

0 1000 2000 30000

1

2

3

4

5On Powdered Berea Sandstone W/O Sacrificial Agent

On Powdered Berea Sandstone W/ 2500 ppm Sodium Polyacrylate (4500 Da)

Concentration of Added CaCl2 (ppm)

NI-B

lend

Ads

orpt

ion

(mg/

g)

Initi

al S

olut

ion

Bec

omes

Haz

y

0 1000 2000 30000.0

0.5

1.0

1.5

2.0

2.5

3.0On Carlpool Dolomite W/O Sacri-ficial Agent On Carlpool Dolomite W/ 2500 ppm Sodium Polyacrylate (4500 Da)

Concentration of Added CaCl2 (ppm)

NI-B

lend

Ads

orpt

ion

(mg/

g)

Initi

al S

olut

ion

Bec

omes

Haz

y

16

Conclusions

Results and Discussions

Materials and Methods

Introduction and Problem Definition

Why Sodium Polyacrylate? What is role for Mw of polyacrylate?

Does polyacrylate reduce adsorption of different anionic surfactants on

different rocks and minerals?

Effect of salinity and divalent ions on application of polyacrylate as

sacrificial agent.

What is the adsorption of polyacrylate in comparison with anionic surfactant?

Experimental Evidence for the effect of anhydrite on adsorption of anionic

surfactants?

How does application of polyacrylate affect the total material cost?

How dynamic and static adsorption tests compares?

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

*

** * * * * *

**

Conclusions

Results and Discussions

Materials and Methods

Introduction and Problem Definition

Why Sodium Polyacrylate? What is role for Mw of polyacrylate?

Does polyacrylate reduce adsorption of different anionic surfactants on

different rocks and minerals?

Effect of salinity and divalent ions on application of polyacrylate as

sacrificial agent.

What is the adsorption of polyacrylate in comparison with anionic surfactant?

Experimental Evidence for the effect of anhydrite on adsorption of anionic

surfactants?

How does application of polyacrylate affect the total material cost?

How dynamic and static adsorption tests compares?

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

0 ppm sodium polyacrylate

1000 ppm sodium polyacrylate

2500 ppm sodium polyacrylate

00.20.40.60.8

11.21.41.61.8

dynamic test static test

NI-B

lend

Ads

orpt

ion

(mg/

g)

0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45 0.5-0.10.40.91.41.92.42.93.43.94.4

Pure Calcite + 5% Anhydrite without Sacrificial Agent

Various PAR

Polyacrylate on Calcite no an-hydrite

Equilibrium Concentration of NI-blend (wt%)

NI-b

lend

Ads

orpt

ion

(m

g/g)

22

PAR = (# of repeating units in polyacrylate) / (# of moles of anhydrite)

Decrease in PAR

Conclusions

Results and Discussions

Materials and Methods

Introduction and Problem Definition

Why Sodium Polyacrylate? What is role for Mw of polyacrylate?

Does polyacrylate reduce adsorption of different anionic surfactants on

different rocks and minerals?

Effect of salinity and divalent ions on application of polyacrylate as

sacrificial agent.

What is the adsorption of polyacrylate in comparison with anionic surfactant?

Experimental Evidence for the effect of anhydrite on adsorption of anionic

surfactants?

How does application of polyacrylate affect the total material cost?

How dynamic and static adsorption tests compares?

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

Conclusion

THANK YOU

25

Back-Up Slides

26

Sodium Polyacrylate has negative charge in neutral pH

Surfactant has negative charge in neutral pH

Does this mean that Sodium Polyacrylate can interfere with

measuring concentration of anionic (sulfate-based)

surfactant?

Is Polyacrylate Affecting the titration of Surfactant?

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.

-0.399999999999999 0.100000000000001 0.6000000000000010

1

2

3

4

5

6

7

f(x) = 10.9850243889184 xR² = 0.999426383953348

W/O PolymerLinear (W/O Polymer)W/ Polyacrylate

Sample Size (cc)

Volu

me

of ti

trant

use

d fo

r EP

(cc)

The surfactant used is S13B.Concentration of Surfactant = 0.75 %Concentration of Polymer Added =

0.56 %pH 3 was provided in the titration ex-

periment using HCl solution.The source of Polyacrylate is Acumer

1100.two solutions were made. The first

one has ~0.75% of surfactant at 3.5 % 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 mea-sured to be about 3. Then, titration

was done by potentiometric titration.

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