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Application of NMR for Special Core Analysis

Mai Shimokawara1, Hiromi Kaido1, Yasuyuki Mino1


1
Japan Oil, Gas and Metals National Corporation
1-2-2 Hamada, Mihama-ku, Chiba-shi, Chiba, 261-0025, Japan
shimokawara-mai@jogmec.go.jp

Abstract
NMR (Nuclear Magnetic Resonance) technologies are widely used in the reservoir developments as
a logging tool which provides the porosity, fluid types in the reservoir. As it is known, the
laboratory's bench-top NMR is applying to evaluate the pore size distribution in the porous media.
Moreover NMR technologies provide several parameters of the rock properties; in particular T2
relaxation time provides the fluid type (brine, oil), boundary fluid, porosity and permeability in the
porous media.
In this paper, first we show the results for the comparison of the pore size distribution with Mercury
injection and NMR T2 relaxation time distribution. Then we introduce the new approach which
integrates the NMR measurement in Amott-Harvey test and the contact angle measurement for the
better understanding of the wettability of reservoir carbonate and sandstone rocks. The result
suggests the wettability alteration with change of fluid saturation and its effects on NMR signals.
And comparison of NMR signals in the case of different wettability rocks, it was confirmed that the
NMR signals showed the different trend. This study constitutes a first step for wettability evaluation
by using NMR technologies. Additional work is required to obtain the advantage of NMR
technologies for core analysis.

1. Introduction
In oil resource development, core analysis is very important technique to obtain various properties
of target reservoir. Through SCAL (Special Core Analysis), it is possible to obtain the physical
properties needed to predict flow behavior of reservoir fluid, such as relative permeability, capillary
pressure and wettability, etc. Wettability obtained through SCAL is one of the most important
factors that have large effect on flow behavior of reservoir fluids. Large amount of oil remains in a
reservoir that water flooding has already been operated. Therefore evaluation of wettability is very
important in operation of EOR for the purpose of additional recovery of this residual oil.
Wettability study of reservoir rocks was conducted by Craig in 1971. He defined wettability as, ‘the
tendency of one fluid to spread on or adhere to a solid surface in the presence of other immiscible
fluids’. Later, wettability has been recognized as an important factor in evaluating the fluid flow in

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porous media. There are a lot of methods for wettability evaluation (Anderson). In general, these
methods are consisting of 1.Amott method, 2. USBM method and 3.Contact angle measurement.
These methods, by using two or all three methods at the same time, could evaluate comprehensive
wettability. Moreover, NMR techniques have also been applied to wettability evaluation.
The first approach by NMR utilization in oil development filed was carried out by Brown and Fatt
in 1956. First, NMR measurements were conducted using artificial sample instead of rock core
sample. After obtaining the parameters of rock core samples, rock core samples recovered from oil
reservoir have been measured and the studies have conducted comparison between the distribution
of T2 relaxation time by NMR and pore diameter distribution by mercury injection method (Kenyon,
Borgia, Kleinberg). Because the results obtained by NMR have a lot of information which includes
the properties of the rocks and fluids in the pore space, many researchers have interpreted the
relationship between permeability and wettability by comparing various sample states, lithology and
so on (Hirasaki, Hsu, Ma, Guan, Al-Mahrooqi, Freedman, Chen).
This paper discusses about application of NMR for core analysis. We conducted Amott test and
contact angle measurement and attempted to apply NMR technology as a part of wettability
evaluation.

2. The principle of NMR


NMR could give a lot of information about proton existing in pores space, such as the amount of
proton and sensitivity to pore surface. NMR has the potential for wettability evaluation (in this case,
the proton means hydrogen, 1H). In NMR measurement, when the proton is put in magnetic field that
has some frequency, and forced into high energy state. Without magnetic wave, the proton returns to
the initial energy state. NMR measures the time to return to the state. This is defined as relaxation
time. The relaxation times depending on the magnetic direction are consisting of the longitudinal
relaxation time (T1) and the transverse relaxation time (T2). The relaxation times are the
combination of the relaxation mechanism based on the various phenomena. For example, T2
relaxation time expressed as a function of bulk relaxation, surface relaxation and diffusion relaxation
as shown in Eq.1 (Kenyon). In addition, using NMR data, it is possible to calculate permeability by
using surface relaxation rate and pore surface area (Seevers, Timur, Kenyon). NMR as logging tools
uses T2 relaxation time measured by the CPMG spin echo sequence (Taicher). This paper focuses on
T2 relaxation time by CPMG.

(Eq.1)

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3. Wettability
Wettability evaluation methods are three typical tests as described above. Amott method consists of
four basic measurements (Amott).
(i) The amount of brine spontaneously imbibed, Vwsp.
(ii) The amount of brine forcibly imbibed, Vwf.
(iii) The amount of oil spontaneously imbibed, Voilsp.
(iv) The amount of oil forcibly imbibed, Voilf.
Amott-Harvey Index is calculated by following equation (Eq.2).

(Eq.2)

In USBM method, we could obtain the relationship between water saturation and capillary pressure
by using a centrifuge machine and calculate USBM Index. These two methods are able to evaluate
wettability of core samples as a whole and require long time to measure. In contrast, the time
required for contact angle measurement of droplets formed on the core surface is short. Wettability
evaluation by this method is due to the property of only surface of core and is affected by surface
roughness.
In conventional wettability evaluation methods described above, it is impossible to obtain a
distribution of fluid in pore space. When X-ray CT scanner and NMR are used together with these
methods, it is possible to obtain the change of fluid distribution in pore space during Amott and
USBM methods. In this paper, we carried out NMR measurement as a part of wettability evaluation
and examined the distribution of fluid during Amott method.

4. Experiment
Two lithology rock core samples recovered from oil reservoir, carbonate (restored, Sample1 and 2)
and sandstone (fresh, Sample3) were used for the experiments. Restored carbonate samples were
flowed by 100PV of STO for 40 days aging. Physical properties of these samples are shown in
Table1and Table2.
NMR measurement was conducted at the end of each stage of the Amott test. In addition, NMR
measurement was also carried out in brine saturated condition and irreducible brine saturation one.
For convenience, we have numbered the following each step.
Step1: Before aging (Before replacing by STO), Sw=1.0
Step2: After aging (After replacing by STO), Sw=Swir
Step3: Spontaneous brine imbibition
Step4: Forced brine imbibition
Step5: Spontaneous oil imbibition

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Step6: Forced oil imbibition
After Step1, we carried out contact angle measurement. In order to confirm correlation between
distribution of T2 relaxation time by NMR and pore size distribution by mercury inject method, we
conducted mercury inject method. Preliminary experiments were also performed. Only liquids were
used as samples (brine and oil). When mix ration of liquids was changed, we carried out NMR
measurement.
Here, we treat the integrated area of NMR signal and T2 peak value to discuss about results of
NMR measurement. T2 peak value means a peak in distribution of T2 relaxation time. NMR area
means the integral value of the distribution of T2 relaxation time (Eq.3) and it is proportional to the
amount of proton existing in pore space.

(Eq.3)

We used NMR instrument (Oxford Instruments) irradiated 2MHz frequency as same as logging
tools. Contact angle measurement (First Ten Angstroms) was measured by placing a sample in
Decane in order to evaluate wettability under reservoir condition. In Amott method, STO and n-
Decane were used as oil. Synthetic brines were also used as brine. Synthetic brines were simulated to
oil reservoir’s one. Chemical components of brines are listed in Table3. BrineA was use for
Sample1and 2, brineB was used for Sample3.

5. Results and Discussion


 Amott method and contact angle measurement
Results of Amott method and contact angle measurement are shown in Tatble4. According to
Amott method, Sample1 and 2 are oil-wet because AHI are -0.54 and -0.70, respectively. AHI of
Sample3 is 0.002 and wettability is neutral.

 Comparison between NMR and mercury inject method


We compared the distribution of T2 relaxation time by NMR and the distribution of pore diameter
by mercury inject method to confirm the validity of the application of NMR results for pore size
distribution.
Result for Sample1 is shown in Fig.1. Here, ρe is effective relaxivity. This is introduced to account
for the fact that NMR responds to pore size whereas mercury injection capillary pressure. We
confirmed the correlation of these two methods. The data indicates that the peak value of pore
diameter distribution in Sample1 is 6.8µm. We could confirm the correlation in other samples.

 The effect of fluid existing in pore space on T2 relaxation time

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Fig.2 shows the relationship between water saturation and NMR area. Here, NMR area means a
relative value by dividing NMR area with the value of only brine used (Eq.4).

(Eq.4)

As water saturation decreases, NMR area increases in STO and it decreases in n-Decane. These
results suggest that it is necessary to consider the effect of liquid in the pore space on NMR signal.
In this study, we carried out preliminary experiments in order to consider the effect. As a result, we
were able to reduce the effect of proton depending on fluid chemical components and saturation of
fluid. This may indicate that it is possible to obtain saturation by NMR measurements of brine and
oil, even if saturation of samples is unknown.

 The change of T2 relaxation time during Amott method


We discuss about NMR spectrum due to change of water saturation during Amott method.
Comparison of NMR spectrum obtained for Step1 and Step2 in Sample1 is shown in Fig.3. T2 peak
values are about 30% smaller in Step2 compared with that of Step1 and NMR area is also reduced to
about 30% of that of Step1. In preliminary experiments of the same liquid ratio at this time, the value
of NMR area increases whereas T2 peak values decreased. The decrease of NMR area means that
drainage of brine was selectively promoted from large pores. The decrease of T2 peak value is
affected by brine imbibition and aging. Then, the comparison with Step2 and Step3 indicates that T2
peak value in Step3 increases to about 30% of one in Step2, although there is no change in water
saturation. These data suggest the change of brine distribution in pore space. In other words, when
sample core is immersed in brine at irreducible water saturation, the tendency that brine is easily
imbibed into pore space is shown.
In Amott method (Step3 to Step6), we confirmed that the change of fluid distribution in pore space
due to drainage and imbibition could be observed on the basis of the results by NMR measurement.
AS an example, the comparison of NMR spectrum in each step of Amott method is showed in Fig.4.
The shape of NMR spectrum changed at around 20ms of T2 peak value corresponding to 0.4µm of
pore diameter. This means that fluid existing in pore space larger than about 0.4µm selectively
migrated.
Next, we discuss about the result for Sample3 (sandstone). In the process from Step4 to Step5,
water saturation decreased to 6% by brine drainage. From the result, it was found that brine was
drained from the pore that had smaller peak in NMR spectrum corresponding to from 0.16 to 1.76µm
of pore diameter (Fig.5). In Step6, fluids were forced into this smaller one and another peak was
moved to larger size (from 19 to 27µm). Then, we compare between Step4 and Step6. These states
are after the injection of fluid (brine or oil). NMR intensity is different due to water saturation, its
shape is similar. This suggests that the pore distribution after the fluid injection is different compared

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with those of other operations.

 The change of NMR spectrum due to difference of wettability


We discuss about the change of NMR spectrum in the case of different wettability due to lithology.
Fig.6 shows the change of T2 peak value during Amott method in Sample1 and Sample3. In
Sample1, as water saturation decreases, T2 peak value also decreases. This sample is no magnetism.
So due to oil wet, rock particle surface is cover by oil and brine is existing in the center of pore space.
The factors of relaxation are diffusion relaxation and surface relaxation. Therefore, T2 peak value is
influenced by the amount of proton in pore space. On the other hand, in sample of sandstone, the
opposite trend was observed. This sample is magnetism. T2 relaxation time in magnetic rock is
promoted to be short, because surface relaxation increases in frequency. T2 relaxation time of
sandstone is shorter more than that of carbonate. We could confirm that results of sandstone were
different from that of carbonate. There is a need of further research to better understand the change
of NMR spectrum due to difference of wettability.

6. Conclusion
We attempted to apply of NMR technique as a part of wettability evaluation. NMR spectrum of
liquid existing in pore space suggests the possibility that water saturation could be estimated. The
change of pore distribution was confirmed during Amott method. And the same change could be
observed in carbonate. From comparison of result for carbonate and sandstone, we confirmed that
there were differences in the behavior of NMR spectrum during Amott method. NMR has proven to
be helpful in evaluating wettability and analyzing cores. In this study, we performed qualitative
evaluation of wettability. Further studies are needed to find out wettability evaluation by NMR
quantitatively.

Abbreviations
AbNMR Integral values of the distribution of T2 relaxation time measured by NMR instrument
when brine was used as a sample.
ANMR Integral values of the distribution of T2 relaxation time measured by NMR instrument.
ArNMR Relative integral values of the distribution of T2 relaxation time measured by NMR
instrument.
f(t2) Functions of T2 relaxation time.
T2 Transverse relaxation time of the pore fluid.
T2bulk T2 relaxation time of the bulk fluid.

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T2surf T2 relaxation time of the pore fluid due to surface relaxation.
T2diff T2 relaxation time of the pore fluid as induced by diffusion in the magnetic field
gradient.
Voilf Volume of drained water by forcibly oil imbibition.
Voilsp Volume of drained water by spontaneously oil imbibition.
Voiltotal Total volume of drained water by spontaneously and forcibly oil imbibition.
Vwf Volume of drained oil by forcibly oil imbibition.
Vwsp Volume of drained oil by spontaneously water imbibition.
Vwtotal Total volume of drained oil by spontaneously and forcibly water imbibition.

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Sample ID Sample 1 Sample 2 Sample 3
Rock type Carbonate Carbonate Sandstone
Sample state Restored Restored Fresh
Diameter mm 37.95 37.90 37.84
Length mm 65.93 70.00 63.61
Dry weight g 143.853 151.840 137.844
Pore volume mm3 21403 22744 19314
Porosity - 0.287 0.288 0.270
Air permeability md 96.34 66.15 754.48
Table1 Properties of rock core samples.

Sample 1 Sample 2 Sample 3


Calcite % 100 100 0
Quartz % 0 0 59.9
Anothite % 0 0 35.6
Microcline % 0 0 4.5
Table2 Mineral contents in samples by XRD analysis.

Brine A Brine B
3
Na g/m 67000 10648
3
K g/m 0 374
3
Ca g/m 20000 1658
3
Mg g/m 2500 117
3
Cl g/m 147000 19932
3
SO4 g/m 600 187
Table3 Chemical components of brines.

Sample 1 Sample 2 Sample 3


AHI -0.543 -0.697 0.0023
Contact angle 145.4° 142.44° 43.25°
Table4 Result of AHI and Contact angle measurement.

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Fig.1 Comparison of the distribution between T2 relaxation time by NMR (Step1) and pore
size measured by mercury injection.

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(a) Sample1 (used liquid is STO).

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(b) Sample3 (used liquid is n-Decane).
Fig.2 The effect of water saturation on ratio of NMR area.

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Fig.3 Comparison of NMR intensity between before aging and after aging (Step1 and Step2).

Fig.4 Comparison of T2 relaxation time during Amott method (Sample1).

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Fig.5 Comparison of T2 relaxation time during Amott method (Sample3).

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(a) Sample1

(b) Sample3
Fig.6 Relationship between NMR T2 peak and water saturation.

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