nanocapsules for oil detection and extended-reach ph modification james m. tour rice university

Nanocapsules for Oil Detection and Extended-Reach pH Modification

James M. TourRice University

www.jmtour.com

http://www.jmtour.com/

Schematic of Oil Detection by Nanoreporters(a) Nanoparticles (NPs) with

hydrophobic signaling cargo (red rectangles) are injected into the subsurface.

(b) The nanoreporters encounter oil and release their hydrophobic signaling cargo into the oil.

(c) The nanoreporters are recovered and analyzed for the signaling cargo for the existence of saturated oil residual (SOR).

• Core material: functionalized carbon black (“fCB”) • Cargo molecules: triheptylamine (TPA) or 14C-labeled triphenylamine (TPA*)• Batch desorption studies were conducted to understand the partition behavior of TPA

Early Work: Carbon Black-based FormulationA heavily oxidized and

carboxylated carbon coreSEM image of 50 nm

carbon black (CB)

H2SO4, H3PO4

KMnO4, 50 ºC

100 nm

O O

OH

O

HO

HO OH

EDC, H2O

PVA

O O

OPVA

O

PVAO

HO OH

CB powder PVA-OCB

powder

PVA-OCB NPs

Cabot (MA, USA)

PVA

DCC, DMAP, DMF

OPVA

CH3

CNO

n

HON

N

O

H3C

H3C CNOH

O

THF, 60°C, 48hrsfCB

(CB)

(PVA-fCB) TEM of 15 nm fCB

Zeta potential of PVA-fCB is 3.84x10-1 mV

PVA-fCB is almost neutral and it will not bind to charged porous media

3

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1

1.1

0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54 56 58 60

Nor

mal

ized

Con

cent

ratio

n C/

Co

Inj PV

Gen#1 NPs - 20ppm Gen#2 NPs - 20ppm Gen#3 NPs - 20ppm

Gen#3 NPs - 100ppm Ideal Tracer

Transport Studies in Berea Sandstone – HCCs-PEG (Gen#1), OCB-PVA (Gen#2), CB-PVA (Gen#3)

Experimental DetailsSample: NPs in 31 kppm seabrineCore size: 1” (D) x 1.5” (L)Core type: Berea SandstoneCore Permeability: 300mDT = 28 oCOutlet P = 1 atmInjection rate: ~0.1 cc/min Linear velocity: 0.113 cm/min (5.3 ft/day)

Gen#1 – Poor Performer

Gen#3 – Acceptable Performer

Retention of Gen#3 particles: 10 micrograms/g of Berea Sandstone

25 °C

45 °C

55 °C

70 °C

Size distribution of PVA-OCB became broader as temperature was increased

The cloud point of 2000 Mn PVA is ~70 °C

The diameter of OCB is in the range of 30 to 40 nm

Early work: 2000 Mn PVA coated OCB

Stability of Sulfated PVA Coated CB

PVA (50 K)-fCB (left) vs. LsPVA (50 K)-fCB (right) in API standard brine at 100°C

API brine (Ionic Strength 3.77 M): NaCl (1.4 M), CaCl2 (0.19 M)

Synthetic seawater (Ionic Strength 0.55 M): CaCl2 (3.5 mM), MgCl2 (5.5 mM), KCl (19.8

mM), NaCl (0.5 M), Na2SO4 (0.5 mM), NaHCO3 (2.0 mM)

PVA (50 K)

DCC, DMAP, DMSO

OsPVA

CH3

CNO

n

HON

N

O

H3C

H3C CNOH

O

THF, 60°C, 48hrsfCB

(CB)

sPVA (50 K)-fCB

ClSO3H/CH3COOH

60 °C or 75 °C

NaOH (1 M)

sPVA:OH

nOSO3Na

m

• HsPVA: Highly sulfated PVA 4.5 mL 1 M ClSO3H/CH3COOH, 75 °C• LsPVA: Lightly sulfated PVA 3.0 mL 1 M ClSO3H/CH3COOH, 60 °C

Awaiting XPS data

Nanoparticles Transport in API Solution at 70 ºC

More than 90% of sPVA-fCB can flow through calcite and sandstone columns at 70 ºC in API brine

sPVA(50 K)-fCB was dispersed in API brine (8 wt% NaCl, 2 wt% CaCl2) The concentration of nanoparticles was 20 mg/L

0 2 4 6 8 10

0

20

40

60

80

100

0 2 4 6 8 10 12

0

20

40

60

80

100

C/C

0(%

)

No. of pore volume

H sPVA-fCB L sPVA-fCB PVA-fCB

Sandstone

No. of pore Volume

Calcite

HsPVA-fCB

LsPVA-fCB

PVA-fCB

LsPVA-fCB

PVA-fCB HsPVA-fCB

Calcite columns

Sandstone columns

No. of pore volume No. of pore volume

0 2 4 6 8 10 12 14 16

0

20

40

60

80

100

0 2 4 6 8 10 12 14 16

0

20

40

60

80

100

0 2 4 6 8 10 12 14 16

0

20

40

60

80

100

0 10 20 30 40 50 60

30

40

50

60

70

80

90

100

C/C

0 (%

)

No. of pore volume

a)

C/C

0 (%

)

No. of pore volume

sPVA-fCB TPA

c)

C/C

0 (%

)

No. of pore volume

b)

TP

A C

/C0 (%

)

Oil saturation (%)

d)

Breakthrough Studies in Different Oil Content Columns

Breakthrough of TPA/sPVA-fCB in sandstone-packed columns at 25 °C (a) without isoparL; (b) with 29% isoparL in column and (c) with 58% isoparL in the column

Flow rate is 8 mL/h (linear velocity 12.2 m/d)

x is the oil saturation in the column and kp is the partition coefficient (1.03*10-4 kg-NP/L).

TPA NP

p

100f (%)

xk 1

c(100 x)

Correlation Studies under More Realistic Conditions

Nanoparticles were dispersed in API brine, the concentration of sPVA-CB was 30 mg/L Columns were packed with ground calcite with oil saturation 0.58 (the volume of isoparL/PV) The release of probe molecules only slightly depends on the flow rate

0 2 4 6 8 10 12

0

20

40

60

80

100

0 2 4 6 8 10 12 14 16

0

20

40

60

80

100

0 2 4 6

0

20

40

60

80

100

0 2 4 6 8 10 12 140

20

40

60

80

100

C/C

0 (%

)

No. of pore volume

6.5 cm column1 mL/h, 1.53 m/d

1)

C/C

0 (%

)

No. of pore volume

sPVA-fCB TPA

6.5 cm column8 mL/h, 12.2 m/d

3)

C/C

0 (%

)

No. of pore volume

12.2 cm column 8 mL/h, 5.2 m/d

2)

TP

A C

/C0 (%

)

Linear velocity (m/d)

Residual TPA on the NP vs. the linear velocity; hence release of the probe molecule does not depend on the flow rate

Dissolve

in H2O

Surfactants

1. Load tracer

2. cross-link

Step 1:Formation of micelle

Step 2: Cross-linking & tracer loading

Micelles NPs

Tracer: Cross-linker:

10

C9H19 O(CH2CH2O)nSO3NH4

n = 20

Hitenol Nile Red Divinylbenzene

Surfactant:

O

NN

O

Second generation nanoreporters: cross-linked micelle

TEM image(NP radius ~10-15 nm)

Hitenol-DVB/Nile red NPs remain the similar size at 25 -100 ºC

Hitenol/Nile red micelles decrease in size at high temperature

25 50 75 100

0

10

20

30 Hitenol-DVB/Nile red NPs Hitenol micelle/Nile red

Hyd

rodyn

am

ic s

ize (

nm

)

Temperature (°C)

11

Size of Hitenol-DVB/Nile red NPs in API brine

400 450 500 550 600 650 700

623

Nile Red (Ex:550 nm)

Inte

nsity

(A

.U.)

Wavelength (nm)

Detection conditions: Nanoparticle: UV-Vis at 215 nmNile red: fluorescence at 623 nm (excitation at 550 nm)

200 300 400 500 600

Inte

nsity

(A

. U

.)

Wavelength (nm)

NPs215

Fluorescence spectrum UV-Vis spectrum

C9H19 O(EO)nSO3NH4 +

Initiator NPs+ O

NN

O

Nile redNanoparticles

Detection methods

Both show good breakthrough

Breakthrough of Nile red is above 98% in no oil sandstone column Breakthrough of Nile red is about 80% in 50% oil sandstone column

0 3 6 9 12 15

0

20

40

60

80

100

C/C

0 (

%)

Number of pore volume

NPs Nile red

Switch to blank

0 3 6 9 12 15

0

20

40

60

80

100

C/C

0 (

%)


NPs Nile red

Switch to blank

50% oil sandstone column (SOR=50%)

No oil sandstone column (SOR=0%)

13

Breakthrough behavior study (DVB/Hitenol = 2)

0 3 6 9 12 15

0

20

40

60

80

100


Hitenol Nile red

Switch to API

0 3 6 9 12 15

0

20

40

60

80

100

C/C

0 (

%)

Number of pore volumes

Hitenol Nile red

Switch to API

50% oil sandstone column (SOR=50%)

No oil sandstone column (SOR=0%)

Both show poor breakthrough

Migration of Nile red into oil phase

Instability of the Hitenol micelle structure

Physical adsorption of Nile red onto rock surface

Instability of the Hitenol micelle structure

Physical adsorption of Nile red onto rock surface

14

Control experiment: no cross-linker

Breakthrough Apparatus Setup

Syringe pump

Packed column

Effluent collection

7 cm length with 0.3421 cm2 cross

sectional areaPacked with cleaned

crushed Berea sandstone (106-250

mesh)

The sandstone was washed 3 x using 1 wt

% acetic acid and deionized water, dried and packed into the

column.

15

Column Preparation• The XLM with DVB:Hitenol=4:1 was used• Ambient temperature• Dry column was flushed with API brine (linear velocity at

33.6 m/day) for around 200 pore volumes (PV) to remove the air bubble

• A non-reactive tracer (tritiated water or 2 M NaBr solution) was intorduced into the column to measure the porosity and dispersion coefficient of the column

• The column was flushed with 10 PV API brine to remove the non-reactive tracer

• XLM solution was injected into the column at flowrate of 8 mL/h (13.44 m/day or 7.5 min residence time)

• Effluent was collected and measured for the XLM concentration

16

Breakthrough of XLM at Different Concentration

Two different concentrations of XLMs were used (1000 ppm and 38.5 ppm), 7.5 min residence time (13.44 m/day)

0 2 4 6 8 10 12 14

0

20

40

60

80

100

1000 ppm XLM with DVB/Hitenol=4

C/C

0 (%

)


NaBr XLM

Switch to API

0 2 4 6 8 10 12 14

0

20

40

60

80

100

38.5 ppm XLM with DVB/Hitenol=4

C/C

0 (%

)


NaBr XLM

Switch to API brine

Low concentration XLM has poor breakthrough due to the adsorption onto sandstone

Retardation factor: 4.4Dispersion coefficient: 0.0015 cm2/sPorosity: 0.419

17

0 2 4 6 8 10 12 14

0

20

40

60

80

100 Hitenol : DVB = 1 : 1 Hitenol : DVB = 1 : 2 Hitenol : DVB = 1 : 4

switch to blank

C/C

0 (

%)

Number of Pore Volume

Breakthrough Profiles Summary for Hitenol/DVB

18

C9H19 O(CH2CH2O)20SO3-NH4

+

Hitenol BC-20

+ AIBN, N2

sonicate for 24 hHitenol-DVB/Nile red NPs+ O

NN

ONile reddivinylbenzene

(DVB)

NPs with a Hitenol/DVB ratio of 1:4 show the best breakthrough at ~ 70 %.

Breakthrough Profiles for Hitenol-Noigen-DVB

19

C9H19 (OCH2CH2)10-OH +

AIBN, N2

sonicate for 24 hHitenol-Noigen-DVB/Nile red NPs

C9H19 O(CH2CH2O)20SO3NH4

Hitenol BC-20

+ O

NN

ONile red

+

DVBNoigen RN-30

0 2 4 6 8 10 12 14

0

20

40

60

80

100

120 Noigen : Hitenol = 8 : 2

switch to blank

C/C

0 (%

)


Noigen : Hitenol = 8 : 2 (molar ratio)

Breakthrough of NPs is 45 % at 2.5 PVs and the rapidly reaches 94 % at 3.3 PVs.

The zeta potential of the NPs is -28.49±2.42 mV.

0 2 4 6 8 10 12 14

0

20

40

60

80

100

120 Noigen : Hitenol = 9 : 1

switch to blank

C/C

0 (

%)



20

C9H19 (OCH2CH2)10-OH +

AIBN, N2

sonicate for 24 hHitenol-Noigen-DVB/Nile red NPs

C9H19 O(CH2CH2O)20SO3NH4

Hitenol BC-20

+ O

NN

ONile red

+

DVBNoigen RN-30

Noigen : Hitenol = 9 :1 (molar ratio)

NP breakthrough reaches 53 % by 2.5 PVs and rapidly increases to 98 % at 3.3 PVs.

The zeta potential of the NPs is -15.19±1.84 mV.


21

0 2 4 6 8 10 12 14

0

20

40

60

80

100

120 Noigen : Hitenol = 9 : 1 Noigen : Hitenol = 8 : 2 Hitenol

switch to blank


C/C

0 (

%)

Noigen/Hitenol

Zeta potential (mV)

0 -44.70±4.05 4 -28.49±2.42 9 -15.19±1.84

Dissolve

in H2O

Surfactants

1. Load tracer

2. cross-link

Step 1:Formation of micelle

Step 2: Cross-linking & tracer loading

Micelles NPs

Tracer: Temperature responsive cross-linker:

22

C9H19 O(CH2CH2O)nSO3NH4

n = 20

Hitenol Nile Red

1,6-hexanediol diacrylate(HDDA)

Surfactant:

O

NN

O OO

O

O

Future work: time-releasing nanoreporters

Nanocapsules for Well Acidization

Delivery of acids to hydraulic fractures forming during the fracturing process

Nanoreporter for H2S Detection in the Subsurface

FP-PVA-FCB

=

1st Gen. nanoreporter:

2nd Gen. nanoreporter:

=

naphthalimide-based molecule

=

(A)

2 EWG: in a pull-pull way ICT is forbidden Non-fluorescent

3-nitro-1,8-naphthalic anhydride

1 EDG + 1 EWG: in a push-pull way ICT is allowed Fluorescent

H2S

PVA(50k)-fCB FP-PVA(50k)-fCB

Preparation of the Gen. 2 Nanoreporter for H2S Detection

(B)

ICT: intramolecular charge transfer

NO O

HN

HO

O

O

OH

i j

Ground core materials: sandstone (provided by AEC) Flow rate: 0.6 mL/h for each syringe, retention time 2 h Nanoparticles were dispersed in synthetic seawater Temperature: 25 °C

Syringe pump

GC glassvials

NPs

Fluorescent probes

Syringe pump

Nanoreporters

Na2S solution spectrometerFluorescence

UV-visspectrometer

Apparatus for Breakthrough Study

FP-PVA-fCB Nanoreporter for H2S Detection

480 520 560 600 640 680 7200.0

5.0x104

1.0x105

1.5x105

2.0x105

2.5x105

0 20 40 60 160 2000.0

5.0x104

1.0x105

1.5x105

2.0x105

Flu

ore

sce

nce

inte

nsi

ty (

a.u

.)

Na2S concentration (M)

[Na2S]

Flu

ore

sce

nce

inte

nsi

ty (

a.u

.)

Wavelength (nm)

50 μM FP-PVA(50k)-FCB and various concentrations of Na2S(aq) (0~170 μM) were injected to the column simultaneously.

The fluorescence increase showed a linear correlation with the injected Na2S(aq), and reached 11-fold enhancement as 70 μM Na2S(aq) reacted with the nanoreporter.

H2S Detection in Kuwaiti oil field Berea sandstone

Kuwaiti oil field and Berea sandstone in order to simulate the oilfield environment. The dolomite had crude oil trapped on the surface; the total organic carbon content of the dolomite was 4.97%. The FP-PVA(50k)-CB and 65 μM Na2S in the synthetic seawater were simultaneous injected into the oil-dolomite column. Figure left shows the relative breakthrough performance when the nanoreporter was pumped through the column. The FP-PVA(50k)-CB not only had >95% breakthrough efficiency in 6 PV, but also exhibited an obvious change in fluorescent enhancement before and after reacting with the H2S (right).

0 2 4 6 8 10 12

0

20

40

60

80

100

C/C

0

Pore volume

480 520 560 600 640 6800.0

5.0x104

1.0x105

1.5x105

2.0x105

Flu

ore

scen

ce in

ten

sity (a.u

.)

Wavelength (nm)

Nanoreporter Project Team Members, Supported by the Advanced Energy Consortium

Steven

Mike MasonJim Amy

Macy Varun YinhongClaire

Fei Ben

nanocapsules for oil detection and extended-reach ph modification james m. tour rice university

Documents