Effect of divalent ions on solid-fluid

interface, as observed by NMR

transverse relaxation time


Leonardo Meireles
MSc Petroleum Engineering
DTU - Danmarks Tekniske Universitet


SPE student paper contest
Imperial College of London
2
nd
June 2014

Contents
31/07/2014 Pre-thesis project - Leonardo Meireles 2
Motivation
Theory
Experiments
Results
Conclusions
Danmarks Tekniske Universitet
Motivation:
Can divalent ions in seawater change chalk
wettability?

Generally water flooding of carbonate reservoirs
seen as a challenge.
Ekofisk: Approaching 50% recovery (year) against a
17% prediction.
oil recovery increased when using seawater
compared to formation brine as displacing uid.
31/07/2014 Pre-thesis project - Leonardo Meireles 3
Danmarks Tekniske Universitet
Theory:
How does NMR measure solid-fluid
interaction?



31/07/2014 Pre-thesis project - Leonardo Meireles 4
1

2
=
1

2,
+

()
2
12

= (0)

/
2

=1

Danmarks Tekniske Universitet
Experiments:
Breaking down seawater
31/07/2014 Pre-thesis project - Leonardo Meireles 5
Ca
2+
, Na
2+
, Mg
2+
, and SO
4
2-

are the
predominant ions in seawater.
An outcrop chalk (Stevns Chalk) was
used in SSA of 2, 5 and 10m
2
.

Acquisition parameters:


TAU SNR* Recycle Delay NECH
(s) n/a (s) n/a
200 300 30 32768
Acquisition parameters
Danmarks Tekniske Universitet
Results:
Comparison of T
2surf
in distinct
brines/concentrations
31/07/2014 Pre-thesis project - Leonardo Meireles 6
0.0E+00
5.0E-08
1.0E-07
1.5E-07
2.0E-07
2.5E-07
3.0E-07
3.5E-07
4.0E-07
10000 100000 1000000 10000000
Calcium chloride brine - 10m2
CaL10
CaM10
CaH10
DW10
Time (s)
D
i
s
t
r
i
b
u
t
i
o
n

a
m
p
l
i
t
u
d
e

(
u
n
i
t
l
e
s
s
)

Danmarks Tekniske Universitet
Results:
Comparison of T
2surf
in distinct
brines/concentrations
31/07/2014 Pre-thesis project - Leonardo Meireles 7
0.0E+00
5.0E-08
1.0E-07
1.5E-07
2.0E-07
2.5E-07
3.0E-07
3.5E-07
4.0E-07
10000 100000 1000000 10000000
Sodium Sulfate brine - 10m2
SO4L10
SO4M10
SO4H10
DW10
Time (s)
D
i
s
t
r
i
b
u
t
i
o
n

a
m
p
l
i
t
u
d
e

(
u
n
i
t
l
e
s
s
)

Danmarks Tekniske Universitet
Results:
Comparison of T
2surf
in distinct
brines/concentrations
31/07/2014 Pre-thesis project - Leonardo Meireles 8
0.0E+00
5.0E-08
1.0E-07
1.5E-07
2.0E-07
2.5E-07
3.0E-07
3.5E-07
4.0E-07
10000 100000 1000000 10000000
Sodium Chloride brine - 10m2
NaL10
NaM10
NaH10
DW10
Time (s)
D
i
s
t
r
i
b
u
t
i
o
n

a
m
p
l
i
t
u
d
e

(
u
n
i
t
l
e
s
s
)

Danmarks Tekniske Universitet
Results:
Comparison of T
2surf
in distinct
brines/concentrations
31/07/2014 Pre-thesis project - Leonardo Meireles 9
0.0E+00
5.0E-08
1.0E-07
1.5E-07
2.0E-07
2.5E-07
3.0E-07
3.5E-07
4.0E-07
10000 100000 1000000 10000000
Magnesium Chloride brine - 10m2
MgL10
MgM10
MgH10
DW10
Time (s)
D
i
s
t
r
i
b
u
t
i
o
n

a
m
p
l
i
t
u
d
e

(
u
n
i
t
l
e
s
s
)

Time (s)
Danmarks Tekniske Universitet
Results:
Comparison of T
2surf
in distinct
brines/concentrations
31/07/2014 Pre-thesis project - Leonardo Meireles 10
0.0E+00
5.0E-08
1.0E-07
1.5E-07
2.0E-07
2.5E-07
3.0E-07
3.5E-07
4.0E-07
10000 100000 1000000 10000000
Magnesium Chloride brine - 5m2
MgL05
MgM05
MgH05
DW05
Time (s)
D
i
s
t
r
i
b
u
t
i
o
n

a
m
p
l
i
t
u
d
e

(
u
n
i
t
l
e
s
s
)

Danmarks Tekniske Universitet
Results:
Comparison of T
2surf
in distinct
brines/concentrations
31/07/2014 Pre-thesis project - Leonardo Meireles 11
0.0E+00
5.0E-08
1.0E-07
1.5E-07
2.0E-07
2.5E-07
3.0E-07
3.5E-07
4.0E-07
10000 100000 1000000 10000000
Magnesium Chloride brine - 2m2
MgL02
MgM02
MgH02
DW02
Time (s)
D
i
s
t
r
i
b
u
t
i
o
n

a
m
p
l
i
t
u
d
e

(
u
n
i
t
l
e
s
s
)

Danmarks Tekniske Universitet
Results:
Bound fluid calculations
31/07/2014 Pre-thesis project - Leonardo Meireles 12
0.0E+0
5.0E-3
1.0E-2
1.5E-2
2.0E-2
2.5E-2
3.0E-2
3.5E-2
4.0E-2
4.5E-2
5.0E-2
0 2 4 6 8 10 12
B
o
u
n
d

f
l
u
i
d

(
u
n
i
t
l
e
s
s
)

Solid Surface area (m2)
Bound Fluid - Low concentration brines
Dw
Ca_L
Mg_L
Na_L
SO4_L
Danmarks Tekniske Universitet
Results:
Bound fluid calculations
31/07/2014 Pre-thesis project - Leonardo Meireles 13
0.0E+0
5.0E-3
1.0E-2
1.5E-2
2.0E-2
2.5E-2
3.0E-2
3.5E-2
4.0E-2
4.5E-2
5.0E-2
0 2 4 6 8 10 12
B
o
u
n
d

f
l
u
i
d

(
u
n
i
t
l
e
s
s
)

Solid Surface area (m2)
Bound Fluid - Medium concentration brines
Dw
Ca_M
Mg_M
Na_M
SO4_M
Danmarks Tekniske Universitet
Results:
Bound fluid calculations
31/07/2014 Pre-thesis project - Leonardo Meireles 14
0.0E+0
5.0E-3
1.0E-2
1.5E-2
2.0E-2
2.5E-2
3.0E-2
3.5E-2
4.0E-2
4.5E-2
5.0E-2
0 2 4 6 8 10 12
B
o
u
n
d

f
l
u
i
d

(
u
n
i
t
l
e
s
s
)

Solid Surface area (m2)
Bound Fluid - High concentration brines
Ca_H
Mg_H
Na_H
SO4_H
Dw
Danmarks Tekniske Universitet
Results:
Porosity measurements corroborates
bound fluid calculations
31/07/2014 Pre-thesis project - Leonardo Meireles 15
0.02
0.025
0.03
0.035
0.04
0.045
0.58
0.59
0.60
0.61
0.62
0.63
0.64
1000 10000 100000
B
o
u
n
d

w
a
t
e
r

(
u
n
i
t
l
e
s
s
)


P
o
r
o
s
i
t
y

(
V
/
V
)

Solution concentration (NaCl equivalent) (ppm)
Porosity vs Bound water- 10m2 surface samples
Ca_H Mg_H Na_H SO4_H
Bw Ca Bw Mg Bw Na Bw SO4
Danmarks Tekniske Universitet
Conclusions:

31/07/2014 Pre-thesis project - Leonardo Meireles 16

All brines influenced to some degree the relaxation
times in bound water.
Magnesium chloride brine effectively increased
relaxivity, even at very low concentrations.
Faster relaxation times translated in a lower amount
of adsorbed fluid.
Porosity measurements seem to validate bound fluid
calculated through NMR.