A quick and Accurate Determination of Fresh Bound Water in Core Material Using

Conventional Techniques
By John Anton Rohan Sr

Abstract Papers by Waxman, Smits and Thomas1, 2 marked a change in shaly sand
evaluation. They gave a model based on a simplified physical concept, a solid electro-
chemical basis and a large set of careful experiments on various shaly samples. First
published in 1968 and again in 1974, this work introduced a dual water model for
explaining resistivity measurements in shaly media. Clavier, Coates and Dumanoir 3 used
the same data set more than a decade later to support their Dual Water model. In this
model a layer of water is bound to the clay and has a resistivity that is ‘nearly fresh’ and
different from the bulk water. This dual water extends to other core types it is an
experimentally measurable quantity. It has been hypothesized that bound water in a
formation is composed at least in part to a mono-layer of fresh water bound to the rock
surface by Van der Waal forces. It is possible to directly measure this value and to
calculate this irreducible water saturation directly from the mercury injection data since
it provides a surface area calculation. These techniques offer better estimates of initial
fluids in place as well as assisting in resistivity log interpretations. To measure this salinity
change between bound and mobile water laboratory testing can be done using a variety
of techniques. I will discuss; core flow, centrifuge, and MICP which provide fairly rapid
measurements.

Core Flow Core flow testing is the fastest of the techniques requiring only a few hours
to perform. It requires a core plug that has been cleaned and de-salted. It is necessary to
have an accurate measure of the pore volume of the plug to do the proper calculations.
The steps are as follows:
• Place the sample in a clean dry core holder with a simple micro resistivity cell
attached to the core holder outlet. Figure 1 shows a cell with an internal volume
of 0.05 cc made from 1” of 1/8” diameter peek tubing.
• Pull a quick partial vacuum. A simple 1,000 micron vacuum will remove 99.9% of
the air from the core plug.
• Begin injecting a degassed brine at a low rate of about a pore volume an hour.
• Once brine breaks through the core to the meter begin recording for at least two
pore volumes or until the injected brine and the produced brine achieve the same
salinity. Figure 1 shows the stability on a sandstone core plug. The fresh water
(bound water) saturation can be calculated from the increased salinity of the initial
brine through the core as fresh water is removed from the brine to form the bound
water layer on the plug. This 91 mD plug calculated 10.6% Swir.
Figure 1
Core Flow Resistivity Set-up and Real Time Data Set

From Core Holder Peek Peek to BPR

Relative Rw vs. Pore Volume Injection

Sandstone Plug

1.200

1.000

0.800
Relative Rw

0.600

0.400

0.200

0.000
0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0 16.0 18.0
Pore Volume injected
Centrifuge Measurement When the bound water in this experiment
becomes fresh or near fresh then the salt it carried into the core plug must
redistribute into the mobile brine increasing the salinity. Since this experiment
requires the measurement of this potential salinity change then a technique other
than air-brine must be used or the test must be conducted quickly. The reason for
this is that an air-brine centrifuge experiment suffers from evaporative water loss
which increases the salinity of the brine in the core plug while diluting the
produced fluid salinity. This is a phenomenon that is unique to air-brine centrifuge
capillary pressure and relative permeability tests. This is similar to a demonstrated
technique for achieving extremely low saturations in plugs that have been de-
saturated in the centrifuge called vapor desorption7 that involves putting plugs in
a sealed chamber and allowing the water to evaporate from the core until a low
saturation value is achieved. The centrifuge collection vial is a mini example of
that chamber. Figure 2 shows the results of placing a Berea core plug saturated
with brine in a sealed centrifuge holder and weighing it daily. The green line is a
1.5” diameter Berea plug sleeved in Teflon tape and Teflon heat shrink tubing to
seal the side walls and which sat on a lab bench for over a month. The blue line
represents 1.5” diameter 15 bar porous plate that was centrifuged for 2 days at
each of nine increasing speed steps used in the experiment. Since the highest
speed step only produced 3 bar then none of the production could have been
attributed to capillary production. At the end of the test the core holder was
placed on the lab bench and data was collected for about 2 weeks and is shown in
the red line. During centrifugation the evaporation rate increased over the static
Berea test, but when the cell became static the evaporation rate dropped to a rate
similar to the static Berea plug. This is due to the fact that in the static condition
water droplets can be seen forming in the chamber where the core material is
located thus causing a high humidity in that chamber reducing the evaporation
rate. While spinning this fluid would be moved to the lower chamber and the
lower humidity would cause an increased evaporation rate. This evaporation is
linear with time and can and must be used to correct the salinity of the collected
sample. This evaporation rate of 0.025 cc/day would mean a loss of 0.425 cc in the
17 days of this experiment. The use of Fluorinert FC-770 instead of air stops this
phenomena.
 Figure 2
Vapor De-saturation of core material in centrifuge collection vial vs time.

Fluorinert is a product of 3M nicknamed ‘liquid Teflon’ for its inert abilities. In the
presence of oil or brine it assumes the role of the non-wetting fluid. FC-770 was selected
out of all of the fluorinerts for several reasons seen in Table 1. First, it has a boiling point
near that of water making dean stark removal possible. Having a density greater than
brine and IFT lower than air-brine yields 3.6 times the equivalent air-brine capillary
pressure at the same rotational speed and 24 times that of air-brine if n-decane is the
wetting phase. This allows pressures equivalent to 27,000 psi air-mercury with FC-770-
brine and 118,000 psi air-mercury with FC-770-n-decane. These high pressures allow near
complete de-saturation of most core materials. Finally, by submerging the plugs in FC-
770 the problem of evaporation is avoided.
 Table 1
FC-770 key properties

Density Viscosity Boiling Brine n-decane

grams/cc cPoise Point IFT IFT
25°C 25°C °C dynes/cm dynes/cm
1.793 1.359 95 31.6 6.2

Centrifuge Procedures By following simple procedures accurate measurements

can be achieved. The sample should be clean, dry, and de-salted. It should have an
accurate pore volume measured and be sleeved in Teflon and Teflon heat shrink
tubing.

• Place the sample in a clean dry core holder with a both inlet and outlet ports
attached to a brine pump. Use a low NCS around 1,000 psi to insure near ambient
pore volume values.
• Pull a quick partial vacuum. A simple 1,000 micron vacuum will remove 99.9% of
the air from the core plug.
• Pressure the core plug to 500 psi with degassed brine and hold there for 16 – 24
hours. This should fully saturate the plug and prevent diffusion of altered salinity
brine out of it.
• Place the core plug in the centrifuge core holder and spin at a pressure at least 10
times the capillary entry pressure calculated for the core plug or at the highest
possible pressure of the centrifuge.
• Centrifuge until sufficient brine is produced for salinity measurements. Typical
meters require from 0.1 – 3.0 cc. If an air-brine experiment is conducted the
salinity must be corrected for evaporative dilution (0.025 cc/day for 1.5” diameter
or 0.0125 cc/day for 1” diameter plugs). If FC-770-brine tests were conducted no
correction is required. The measured increase in salinity over salinity of the
injected brine reflects the loss of bound water and can be used to calculate that
value.
MICP MICP capillary pressure measurements are the quickest of the capillary pressure
measurements to make taking hours to run, however, they are destructive to the core
material. They provide the capillary pressure curve of the dry core material and can even
use end trims or drill cuttings to make the measurements. 4,5,6 MICP data in itself gives a
very good representation of the dry material capillary pressure and pore size distribution
of the core material when properly corrected. The two corrections essential in MICP data
analysis are closure correction and material compressibility. Without compressibility
correction the data will produce false micro pore values increasing the surface area
calculations. Once proper pore size distributions are calculated a surface area for the
material can be calculated. In Table 2 you see a selection of sandstone and carbonate
core plugs used in both centrifuge and MICP tests to validate this technique. Using the
MICP calculation of the surface area in the core plug you can then calculate an estimated
mono-layer of water at 0.0269 cc/square meter (see table 3). Dividing this value by the
pore volume of the material results in the bound water value which is an irreducible value.
Table 2
Routine values of the Experimental Core Plugs
Sample Sample Sample Permeability, Pore
Sample Depth, Length, Diamter, millidarcys Porosity, Volume,
Number meter cm cm to Air Klinkenberg fraction cc
Bentheimer - 4.809 3.939 1541 1476 0.247 13.47
Bentheimer b - 3.589 3.920 1576 1510 0.250 10.36
Parker Limestone b - 3.593 3.879 18.4 14.9 0.172 6.87
Silurian Dolomite (v) - 3.772 3.864 276.1 254.1 0.160 6.62
Crab Orchard - 4.33 3.886 0.054 0.028 0.054 2.74
Berea - 5.106 3.869 470.4 439.6 0.208 11.71

Table 3
MICP Surface area calculations, Water Loss, and Centrifuge Measured Swir
Sample MICP MICP MICP Salinity Forbes
Identification Surface Area Mono-layer Water Water Loss Swir
m2 water, cc Fraction Fraction Fraction
Bentheimer 11.96 0.311 0.098 0.085 0.067
Bentheimer b 5.03 0.131 0.041 0.069 0.062
Parker b Limestone 13.11 0.341 0.158 0.149 0.163
Silurian Dolomite (v) 6.89 0.179 0.085 0.078 0.069
Crab Orchard 8.11 0.211 0.270 0.236 0.245
Berea 9.76 0.254 0.099 0.082 0.070
Once the bound water saturation is calculated it can be used to adjust the MICP data to
‘movable pore volume’ from the MICP capillary pressure curve. In Figures 3-5 you see that
this calculation agrees within measurement errors with the centrifuge values for the
majority of these core plugs.
Figure 3
Mercury Injection for Bentheimer & Bentheimer b Sandstone
MICP Capillary Pressure Comparison MICP Capillary Pressure Comparison
100000 100000

Dry Mercury Dry Mercury

10000 10000

Air-Mercury Capillary Pressure, psia

Air-Mercury Capillary Pressure, psia

Movable Mercury Movable Mercury

Movable Centrifuge Movable Centrifuge

1000 1000

100 100

10 10

1 1
1 0.8 0.6 0.4 0.2 0 -0.2 1 0.8 0.6 0.4 0.2 0 -0.2
Normalized Mercury Intrusion Normalized Mercury Intrusion

Figure 4
Mercury Injection for Berea Sandstone & Silurian Dolomite
MICP Capillary Pressure Comparison MICP Capillary Pressure Comparison
100000 100000

Dry Mercury Dry Mercury

10000 10000
Air-Mercury Capillary Pressure, psia

Air-Mercury Capillary Pressure, psia

Movable Mercury Movable Mercury

Movable Centrifuge Movable Centrifuge

1000 1000

100 100

10 10

1 1
1 0.8 0.6 0.4 0.2 0 -0.2 1 0.8 0.6 0.4 0.2 0 -0.2
Normalized Mercury Intrusion Normalized Mercury Intrusion
 Figure 5
Mercury Injection for Parker b Limestone & Crab Orchard Sandstone

MICP Capillary Pressure Comparison MICP Capillary Pressure Comparison

100000 100000
Dry Mercury

Dry Mercury Movable Mercury

10000 10000

Air-Mercury Capillary Pressure, psia

Air-Mercury Capillary Pressure, psia

Movable Mercury Movable Centrifuge

Movable Centrifuge 1000

1000

100 100

10 10

1 1
1 0.8 0.6 0.4 0.2 0 -0.2 1.000 0.800 0.600 0.400 0.200 0.000 -0.200
Normalized Mercury Intrusion Normalized Mercury Intrusion

Summary Measurement of the bound water saturation which appears to be fresh

water is possible using MICP, centrifuge, or core flow techniques. These measurements
are rapid and accurate and agree internally. This fresh water component affects electrical
property measurement as well as resistivity and NMR log comparisons.

References
1. Waxman, M.H. and Smits, L.J.M. 1968. Electrical Conductivities in Oil-Bearing
Shaly Sands. SPE J. 8 (2): 107–122. SPE-1863-PA.
2. Waxman, M.H. and Thomas, E.C. 1974. “Electrical Conductivities in Shaly Sands-
I. The Relation Between Hydrocarbon Saturation and Resistivity Index; II. The
Temperature Coefficient Of Electrical Conductivity.” J Pet Technol 26 (2): 213-
225. SPE-4094-PA.
3. Clavier, C., Coates, G., and Dumanoir, J. 1984. “Theoretical and Experimental
Bases for the Dual-Water Model for Interpretation of Shaly Sands.” SPE J. 24 (2):
153-168. SPE-6859-PA.
4. Purcell, W. R. 1949. Capillary pressure - their measurements using mercury and
the calculation of permeability therefrom: AIME Petroleum Trans., 186, 39-48.
5. Swanson, B.F., 1981, Simple correlation between permeabilities and mercury
capillary pressures: Journal of Petroleum Technology, v. 33/12, p. 2498-2504.
6. Pittman, E. D. 1992. Relationship of porosity and permeability to various
parameters derived from mercury injection - capillary pressure curves for
sandstones. American Association of Petroleum Geologists Bulletin, 51, 191-
198.