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Shale eera fleury
- 1. Renewable energies | Eco-friendly production | Innovative transport | Eco-efficient processes | Sustainable resources
© 2010 - IFP Energies nouvelles, Rueil-Malmaison, France
Characterization of shales
with low field NMR.
M. Fleury
SCA symposium, 8-11 September 2014, Avignon, France
- 2. © 2010 - IFP Energies nouvelles, Rueil-Malmaison, France
Low permeability media and nanoporous materials
From characterisation to modelling:
can we do it better?
Rueil-Malmaison, France, 9-11 June 2015
2
http://www.rs-lowperm2015.com/
End of Call For Papers: 28 Nov. 2014
LowPerm2015: platform for exchange and interaction between research and
industry players from a variety of different disciplines such as geological
formations (shale, tight sandstone or carbonates, etc.), concrete engineering,
polymer sheaths for pipelines, nanofiltration for produced water treatment,
heterogeneous catalysis, etc.
These very different applications all face the same challenges: the
characterisation and modelling of these media and materials and the
associated transport mechanisms at different scales and potentially enhanced
by the confinement.
- 3. © 2010 - IFP Energies nouvelles, Rueil-Malmaison, France
Characterization issues
Pore sizes down to 1 nanometer
Medium to low porosity (5-15%)
Presence of organic matter and associated porosity
Liquid permeability down to 1nD, gas flow dominated
by Klinkenberg effect
Simple measurements such as porosity or
cementation exponent m difficult
M. Fleury et al., Caprock and gas shale characterization: 3 appropriate petrophyscial methods
- 4. © 2010 - IFP Energies nouvelles, Rueil-Malmaison, France
NMR issues
Does NMR measure total porosity ?
Typical relaxation time of nanopores ?
Does T2 distribution indicate pore size distribution ?
Pore coupling effect
Fluid typing
Methane signature: adsorbed / free gas
Organic matter signature
T2 distribution alone insufficient
2 approaches:
Use diffusion contrast: T2-D maps
Use T1-T2 contrast: T1-T2 map
4
- 5. © 2010 - IFP Energies nouvelles, Rueil-Malmaison, France
5
NMR logging examples: caprock
Callovo-Oxfordian formation
Ketzin caprock
- 6. © 2010 - IFP Energies nouvelles, Rueil-Malmaison, France
6
NMR logging examples: gas shales
Ramirez et al., 2011, SPE144062
- 7. © 2010 - IFP Energies nouvelles, Rueil-Malmaison, France
NMR conventionnal approach
M. Fleury, Characterization 7 of shales with low field NMR
- 8. © 2010 - IFP Energies nouvelles, Rueil-Malmaison, France
Fluid typing ?
From Glorioso et al. SPE 167785, 2014
Advanced techniques needed !
NMR signal
M. Fleury, Characterization 8 of shales with low field NMR
- 9. © 2010 - IFP Energies nouvelles, Rueil-Malmaison, France
Outline
Relaxation of water in nanopores
Diffusion properties (cementation exponent m)
Relaxation of methane in porous media
Relaxation of solid or pseudo-solid components
Conclusion: fluid typing from T1-T2 map
9
- 10. © 2010 - IFP Energies nouvelles, Rueil-Malmaison, France
10
-1
2
10
1
10
0
10
-1
10
-2
10
-3
10
-4
10
10
0
1
10
10
2
3
10
10
4
10
Pore size V/S (micron)
Measured T
2
(ms)
Fast diffusion limit 4
2
V/S << D
2
=10 m/s
2
=1 m/s
T
2b
Relaxation in nanopores
S
1 1
T 2
V T Bulk
2
2
1 nm pore sizes
between
0.1 and 1ms
- 11. © 2010 - IFP Energies nouvelles, Rueil-Malmaison, France
11
Example: caprock sample (COx)
T
2
(ms)
(ms)
T
1
12
-2
1
10
0
10
-1
10
-2
10
-1
Hydroxyls
10
0
10
1
10
10
1
2
Mobile water
(23 MHz NMR instrument
18 mm probe)
- 12. © 2010 - IFP Energies nouvelles, Rueil-Malmaison, France
Study of nanopores in clays
Cristal with
hydroxyls
Counter-ions
and water
d001
(SAXS)
from Porion et al. J. Phys. Chem. 2007
interlayer spacing
<1nm
M. Fleury et al., Characterization of interlayer water in clays using low 12 field relaxation and nutation experiments
- 13. © 2010 - IFP Energies nouvelles, Rueil-Malmaison, France
13
Example: smectite powder at RH=50%
T
2
T2 below 0.1 ms should not
be included in porosity
(ms)
(ms)
T
1
10
-2
10
-1
10
0
10
1
10
-1
10
0
10
1
T1/T2=1
2.5
10
Hydroxyls
Mobile water
Mobile water
(23 MHz NMR instrument
10 mm probe)
Fleury et al., J. Phys. Chem. 2013
- 14. © 2010 - IFP Energies nouvelles, Rueil-Malmaison, France
T2 in nanopores (smectite powders)
Fleury et al., J. Phys. Chem. 2013
M. Fleury, Characterization 14 of shales with low field NMR
- 15. © 2010 - IFP Energies nouvelles, Rueil-Malmaison, France
Results: gas shale sample at Sw=1
M. Fleury, Characterization 15 of shales with low field NMR
- 16. © 2010 - IFP Energies nouvelles, Rueil-Malmaison, France
Measurement of cementation m
Tortuosity from
resistivity (Archie) diffusivity
16
1 m
eff
D
m
D
m
R
0
w R
Classical method
Need knowledge of
water salinity
From NMR diffusion
Experiments at Sw=1
No specific knowledge
Some potential issues related to
clay conductivity
- 17. © 2010 - IFP Energies nouvelles, Rueil-Malmaison, France
17
NMR method: deuterium diffusion
Example: Kw=50 nD, : 6.4 %, size: D=L=15mm
-2
100
80
60
40
20
10
-1
10
2.6 hr
0
10
1
10
H2 outside
sample
2
10
3
10
0
t=0
T
2
(ms)
) (a.u.)
2
A(T
16 hr
H2 not exchanged with D2
D2O
=2.48e-006 cm2/s
6 1
f
C C
* exp
2 2
k D t
H2O saturated
sample at t=0
0 5 10 15 20
0.8
0.6
0.4
0.2
0
-0.2
Time (hr)
C*
D
p
Diffusion coefficient
m=1.87
1
2
2 2
k
p
i f
r
C C k
C
Fleury et al., Energy Procedia 2009
Berne et al. , OGST, 2009
- 18. )
i
-C
f
)/(C
© 2010 - IFP Energies nouvelles, Rueil-Malmaison, France
Example: gas shale samples
18
0.12
0.1
0.08
0.06
0.04
0.02
0
0 0.02 0.04 0.06 0.08 0.1 0.12
Porosity
Deff/Dm
m=2
m=2.5
RM9-14 D=0.62 10-10 m2/s
2 nD
0 20 40 60 80 100 120 140 160 180
1.2
1
0.8
0.6
0.4
0.2
0
-0.2
Time (hr)
i
(C-C
RM3-14 D=1.1 10-10 m2/s
The less porous sample has the highest Deff !!
Measurements
Results
100% water saturated
0.12 nD
m=2.45, 2 nD
m=1.9, 0.12 nD
- 19. © 2010 - IFP Energies nouvelles, Rueil-Malmaison, France
Water diffusivity: consequences
Diffusion length much larger than pore size :
D 10-10 m2/s, LD=(6Dt)1/2 800 nm at t=1ms
Pore sizes <500 nm are in a pore coupling regime
19
MICP
Difficult to reconcile MICP and NMR !!
- 20. © 2010 - IFP Energies nouvelles, Rueil-Malmaison, France
Relaxation of methane in porous media
Fundamental mechanisms known
Bulk properties (Oosting et al. 1971): spin rotation
Riehl et al. 1972, NMR relaxation of adsorbed methane:
anisotropic rotationnal motions at the solid surface
large T1/T2 ratio
Existing work in petroleum sciences
Straley, 1997 T1/T2 ratio >> 1 even in partially saturated
samples
Recent work: Kausik et al. 2011, Rylander et al. 2013, Tinni et
al. 2014….
20
- 21. © 2010 - IFP Energies nouvelles, Rueil-Malmaison, France
Results for methane
Bulk CH4
200 bar
CH4 in
Shale
Sand
M. Fleury, Characterization 21 of shales with low field NMR
- 22. © 2010 - IFP Energies nouvelles, Rueil-Malmaison, France
Results for methane in organic matter
100 bar 200 bar
M. Fleury, Characterization 22 of shales with low field NMR
- 23. © 2010 - IFP Energies nouvelles, Rueil-Malmaison, France
Relaxation of solids or pseudo-solid
components
BPP theory
23
2 2 2 2
1
4
1
8
1
2
2
1
C
T
2 2 2 2
1
4
2
4
1
10
6
1
C
T
Liquids
Example:
Ice: T2=0.008 ms
T1=70 s at 30 MHz
- 24. Amplitude (a.u.)
© 2010 - IFP Energies nouvelles, Rueil-Malmaison, France
Détection and quantification of hydroxyls
300
250
200
150
100
50
0
-50
10
-2
10
-1
10
Cristal with
hydroxyls
0
Time (ms)
Smectite 200°C
Water
(removed
at 200°C)
86% hydroxyls compared to XRD formulae:
Fleury et al., J. Phys. Chem. 2013
M. Fleury, Characterization 24 of shales with low field NMR
- 25. © 2010 - IFP Energies nouvelles, Rueil-Malmaison, France
Detection of organic matter in coal
British coal
Anthracite
Vitrinite reflectance: 2.41
Specific density: 1.35
German coal
High volatile bituminous
Vitrinite reflectance: 0.79
Specific density: 1.71
M. Fleury, Characterization 25 of shales with low field NMR
- 26. © 2010 - IFP Energies nouvelles, Rueil-Malmaison, France
Results: organic matter from shales (1/2)
Immature Oil window Gas window
Hydrogen content:
59 mg/g 30 mg/g 21 mg/g
M. Fleury, Characterization 26 of shales with low field NMR
- 27. © 2010 - IFP Energies nouvelles, Rueil-Malmaison, France
Results: organic matter in shales (2/2)
« Dry » samples
Oil window Gas window
?
M. Fleury, Characterization 27 of shales with low field NMR
- 28. © 2010 - IFP Energies nouvelles, Rueil-Malmaison, France
Principle of T1-T2 maps
T1/T2~2
liquids in porous media
T
2
(ms)
(ms)
T
1
10
-2
10
-1
10
0
1
10
28 Réunion du 15 novembre 2012
10
2
10
3
10
-2
10
-1
10
0
10
1
10
2
10
3
T1/T2=1
bulk liquid
T1/T2~100
solid protons
limit of confinement effect
resolution
limit
Pore size
protons mobility
low
high
small (1 nm) large
- 29. © 2010 - IFP Energies nouvelles, Rueil-Malmaison, France
Fluids typing from T1-T2 map
M. Fleury, Characterization 29 of shales with low field NMR
- 30. © 2010 - IFP Energies nouvelles, Rueil-Malmaison, France
30
Conclusions
Fluid typing from T1-T2 maps
T2 not smaller than 0.1 ms for water in nanopores
Hydroxyls are below 0.1 ms, should be removed for porosity
calculation
Methane has a large T1 signature (1s)
Weak overlapping of the different protons populations
in a T1-T2 map
T1-T2 signatures well understood from existing work
and NMR theory