NMR Relaxation of Clay-Brine Mixtures

Abigail Matteson, Joseph Tomanic, Michael Herron, David Allen and William Kenyon
Schlumberger-Doll Research

Sandstone T2 Distribution
Signal distribution

0.03

0.3

3.0

33

3000

T2 (ms)
Small pore water Capillary bound water Producible fluids

Total CMR porosity 3-ms porosity Free-fluid porosity

2

Transverse Relaxation Equation 1 = 1 + 1 + 1 T2 T2S T2B T2D

1 = Surface relaxation T2S 1 = Bulk fluid relaxation T2B 1 = Diffusion in field gradient T2D relaxation

Surface Relaxation Equation S 1 = r2 Vp T2S

r
2

= Surface relaxivity

S = Surface area Vp = Pore volume

4

T2 Response of Clay-Bound Water

Air

Clay particles

Bound water

Signal distribution

T2 (ms)

T2 Response of Clay-Bound Water and Brine

Brine

Clay particles

Bound water

slow Signal distribution

Molecular diffusion

fast

T2 (ms)

T2 (ms)

Objective of Study
Can a T2 distribution be used to measure l clay-bound water
l clay type and l pore-size distribution?

Experimental Setup
l Maximize the amount of clay-bound water l Use various clay types

Kaolinite, smectite, illite and glauconite

l Vary pore volume

Compact clay-brine mixtures (max 16,000 psi)

l Measure T2 distributions

Clays, clay-brine mixtures

Clay Types and Properties

Clay CEC
(meq/100 g)

Surface area
(m2/g)

Magnetic susceptibility
(micro cgs, 10-6)

Fe2O3
(wt%)

Smectite
Texas

82.6 21.4 16.0 10.9

62.2 72.3 97.8 17.3

1.8 21.7 8.6 0.5

1.2 22.2 9.2 1.0

Glauconite
Birmingham, New Jersey

Illite
Fithian, Illinois

Kaolinite
Warren Co., Georgia
9

T2 Response of Clay-Bound Water

Air

Clay particles

Bound water

Signal distribution

10

T2 (ms)

Clay T2 Distributions at Room Humidity Conditions

0.08 0.06 0.04 0.02 0
11

Smectite Illite Glauconite Kaolinite

0.1

1.0

10

100

1,000

10,000

T2 (ms)

Smectite
14 0 2 0 2 0 2 0 3 0 2.5 0 1.2 0 1.0 0 0.7 0 0.5 0 0.1 1.0 10 100 T2 (ms) Slurry 8 psi 27 psi 89 psi) 500 psi 1,000 psi 2,000 psi 4,000 psi 8,000 psi 16,000 psi 1,000 10,000

12

Illite
30 0 8 0 8 0 8 0 6 0 6 0 4 0 2 0 1 0 0.5
13

Slurry 8 psi 23 psi 78 psi) 500 psi 1,000 psi 2,000 psi 4,000 psi 8,000 psi 16,000 psi 1.0 10 100 T2 (ms) 1,000 10,000

0 0.1

T2 Peak Positions
8-11 psi

500 psi

16,000 psi 0.1 1.0 10 100 T2 (ms) 1,000 10,000

Kaolinite Smectite Illiite Glauconite

14

Surface Relaxation Equation S 1 = r2 Vp T2S

r
2

= Surface relaxivity

S = Surface area Vp = Pore volume

15

Kaolinite
4 3

Pressure Versus Surface Relaxivity (r2)

r2 (mm/s)

2 1 0 0 5000 10,000 15,000 20,000

Pressure (psi)
16

Iron Concentration Versus Surface Relaxivity (r2)

4 3

Smectite Illite
Kaolinite Kaolinite

Glauconite

r2 (mm/s)

2 1 0 0 5

10

15

20

25

17

Fe2O3 (wt%)

CEC Versus Log-Mean T2

10

Kaolinite Log-mean T2 (ms)

Glauconite Illite
0 0
18

Smectite

50

100

Cation exchange capacity (meq/g)

Shale 1
6 4
3 ms

40% Illite 0% Smectite 21% Kaolinite 0% Chlorite 4% Glauconite

2 0 0.1
19

1.0

10 T2 (ms)

100

1000

10,000

Shale 2
35
3 ms

25 15 5 0.1
20

40% Illite 7% Smectite 14% Kaolinite 0% Chlorite 0% Glauconite

1.0

10 100 T2 (ms)

1000

10,000

Objective of Study
Can a T2 distribution be used to measure l clay-bound water
l clay type and l pore-size distribution?

21

Conclusions
l T2 distributions have a single peak.

Cannot measure clay-bound water

Implies fast diffusion between clay-bound and pore waters
l T2 peak position is a function of Clay type Compaction and clay concentration (S/Vp) Surface relaxivity (varies with iron content).

Cannot identify clays l T2 peak position is not a function of CEC.

22