Article

Cite This: Energy Fuels 2018, 32, 4959−4968 pubs.acs.org/EF

Mechanism Study of Disproportionate Permeability Reduction Using

Nuclear Magnetic Resonance T2
Bin Liang,*,†,‡ Hanqiao Jiang,†,‡ Junjian Li,*,†,‡ Fuzhen Chen,†,‡,§ Wenpei Miao,∥ Hanxu Yang,†,‡
Yan Qiao,†,‡ and Wenbin Chen†,‡
†
State Key Laboratory of Petroleum Resources and Prospecting, Beijing, 102249 PR China
‡
China University of Petroleum, Beijing, 102249 PR China
§
School of Petroleum Engineering, China University of Petroleum, Qingdao, 266580 PR China
∥
Department of Earth, Environmental and Planetary Sciences, Rice University, Houston, Texas 77005, United States

ABSTRACT: Excessive water production is an enduring problem in the oil industry that has always been an unbearable burden
on the environment and a great damage to the ultimate oil recovery. Gel treatment has been routinely used for decreasing water
production. Disproportionate permeability reduction (DPR) is a natural phenomenon in some polymer gels that can reduce the
permeability to water more than to oil. The conformance improvement treatments with DPR can effectively reduce the water cut
without substantially reducing the oil productivity in fractured reservoirs. At present, there are no widely accepted mechanisms of
oil-phase permeability development and DPR. In this paper, nuclear magnetic resonance is applied to study the mechanisms of
oil-phase permeability development, DPR, and permeability influence by scanning different core samples treated with Cr(III)−
acetate−hydrolyzed polyacrylamide polymer gels. Results show that the permeability difference leads to a certain alteration in
NMR T2 curves, but final conclusions for the mechanisms are consistent. For the mechanism of oil-phase permeability
development, initially, gel displacement in large pores accounts for the oil permeability development, after which the gel
dehydration becomes the main mechanism. The mechanisms for DPR include the blocking of flow channels by gel rehydration
and residual oil and the low permeability of gel relative to water. The results can be used to optimize the utility of polymer gels
with a DPR property.

1. INTRODUCTION economic oil productivity. However, horizontal wells are more

Global energy demand and consumption is forecasted to keep
growing in the next 20 years,1 and fossil fuels supply more than
85% of the world’s energy with oil production of 32 billion
barrels per year. Most of the conventional resource was
discovered between 1946 and 1980, and since then, annual
production has exceeded annual discoveries.2 The decline in the
oil supply is supposed to be offset by the production from
conventional fields through enhanced oil recovery (EOR) and
oil and gas supplies from unconventional reservoirs, such as
shale gas, shale oil, tight gas, and other complex fractured
reservoirs.3,4 EOR is oil recovery by the injection of materials
not normally present in petroleum reservoirs, such as water-
soluble polymer, steam, solvents, surfactants, and carbon
dioxide,5−8 among which the cross-linked polymer is an
important kind of EOR agent for the profile control and
water shutoff. Because the matrix of unconventional reservoirs
is usually of low permeability, these kinds of reservoirs generally
call for both natural and hydraulic fracture networks to acquire
an economic recovery of hydrocarbon.9 However, in complex
fractured reservoirs, when the injector or producer is connected
to faults or fractures, injected water can rapidly break through
into the producers. For reservoirs with bottom water, water
coning is severe because the bottom water may travel through
high-permeability fractures. The situation can be especially
common if the fracture system is extensively developed. A
horizontal well can enhance the reservoir contact and increase
the possibility of meeting more fractures, thereby ensuring the
easily subjected to water-breakthrough problems due to more
fracture network connections. The coning water production
reduces the oil production significantly, which has become a
serious problem in many oil field applications. As of 2000, oil
companies produced an average of 3 barrels of water for each
barrel of oil from the depleting reservoirs, and more than $40
billion was spent dealing with unwanted water per year.10 The
production of water was reported to be 249 million barrels per
day in 2005.11 Therefore, it is necessary to delay and minimize
water coning for both technical and economic considera-
tions.12−14
Many different methods and materials are available to solve
excessive-water-production problems. These methods can be
broadly categorized as chemical or mechanical. Polymer, foam,
and gels are typical chemical plugging agents;15,16 packers,
bridge plugs, and patches are examples of mechanical
techniques. Each of these methods works well for certain
types of water-coning problems.17 Therefore, to achieve an
effective treatment when dealing with the water production
problem, the nature of the problem should be understood
correctly.18 Based on the conceptual consideration related to
the treatment difficulty, the water production problems are
summarized into four categories, among which the linear-flow
Received: February 1, 2018
Revised: March 15, 2018
Published: March 21, 2018

© 2018 American Chemical Society 4959 DOI: 10.1021/acs.energyfuels.8b00420

Energy Fuels 2018, 32, 4959−4968
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problems are water-coning problems caused by linear-flow
features (e.g., fracture, fracture-like structures, narrow channels
behind pipe, or vug pathways). Problems such as casing leaks,
flow behind pipes, 2D coning, and natural fracture systems
leading to an aquifer are normally effectively solved with gelants
(i.e., the fluid gel formulation before significant cross-linking
occurs). For the other problems, fully or partially formed gels
(i.e., cross-linking products that will not flow into or damage
porous media) are the best solution.17 However, the approach
to solving linear flow problems is fundamentally different from
those for solving radial flow problems in reservoirs without
fractures. Especially for gel treatment, the gel properties,
placement procedures, and the optimum volume of gel placed
differs greatly from those in radial flow treatment. Hydrocarbon
zones must be protected during gelant placement for radial flow
problems.19 Therefore, it is critical to decide whether the flow
around the wellbore is linear or radial. Several methods are
available to judge whether the flow near the wellbore is linear
(with fracture-like features) or radial (in an unfractured matrix
or rock), such as the Darcy equation method, core and log
analysis, interwell tracer tests, and pressure transient anal-
ysis.20−23 Compared with cement and carbonates, gelant can
easily flow into the porous media and seal the hydrocarbon-
bearing zone sufficiently. The shut-off function of gelant and gel
is to deeply penetrate into a reservoir and plug the narrow
channels or microfractures near the zone to be shut off.24
Therefore, gels involving gelant injection are frequently used to
treat excess-water-production problems in unfractured reser-
voirs.25,26 However, when the water zone is located at the
bottom or above the oil zone, cross-flow occurs between the
hydrocarbon strata and water zone, and gelant will cross-flow
and damage the oil-producing zones without effectively
plugging water production zone. Therefore, the gel treatment
will be meaningless no matter how much gelant is injected.27
Gel treatment can be applied in both production and injection
wells to treat water production problems in unfractured
reservoirs with effective barriers to cross-flow.28−30 Many
polymers and gels can reduce the relative permeability to water
to a greater extent than that to oil and gas. This property is
called disproportionate permeability reduction (DPR).31,32 The
DPR property is critical to the success of gel treatments in
production wells located in hydrocarbon zones that are not
effectively protected during gelant placement.33,34 The DPR
property is of value only when high-hydrocarbon-saturation
zones are distinct from the offending excess-water-producing
zones. In other words, DPR will not alleviate water production
in unfractured reservoirs that effectively have only one zone.35
There are two technical obstacles preventing this gel treatment
being successful in unfractured reservoirs without zone
isolation. First, the residual resistance factor to oil (Frro) must
be less than 2, while the residual resistance factor to water must
be greater than 10.17 Second, a Frro of less than 2 is hard to
achieve because low Frro values indicate incomplete gelation
that is severely subjected to pH, salinity, temperature, and other
factors. It is difficult to predict and control the gelation stage to
obtain the desired Frro in consideration of the complex reservoir
conditions.36
The performance of DPR property in fractured reservoirs is
different from that in unfractured reservoirs. DPR conformance
improvement treatments can be easily applied in hydraulically
or naturally fractured reservoirs. Basic engineering calcula-
tions37 reveal that currently gel treatments with a DPR property
are far more practical when treating linear flow problems (e.g.,
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fractures) than radial flow problems (e.g., wells without
fractures). When treating with fractures, the successful
application of gel treatment only has two requirements. First,
the reduction of permeability to water is more than that to oil.
In other words, the residual resistance factor of oil is smaller
than that of water. Second, the distance of gelant leak-off from
the fracture surface controllable. These requirements ensure the
timely recovery of oil productivity. The gel is placed and
functions within the matrix rocks adjacent to fractures.38 If
gelant penetration distances are too large, the pressure gradient
may be too small to allow oil to initiate the flow through the
gel. The block ability of gel to water is determined by the
product of leak-off distance and the residual resistance factor
provided by the gel.17 The caused resistance to water and oil is
a critical issue for both linear and radial flow problems during
DPR application. Therefore, it is necessary to investigate the
mechanism of DPR. Understanding the mechanism enables us
to figure out the right technique to improve the gel treatment
performance and make full use of DPR.
The general DPR process can be described as follows: after
porous media is treated with cross-linked gels, the permeability
will drop to a low level. Afterward, the oil flow channels
develop as the oil penetrates into the gel-filled pore spaces.
However, the permeability to subsequent water will be
exceptionally low; even the oil permeability has increased to
a great value. There are a number of works focusing on the
mechanisms of oil permeability development and DPR.39−49
Dawe and Zhang’s visual microscale studies reveal that oil and
water pass through the gels by different mechanisms.50 Oil
passes the gel by fingering from the center of the pores and
widens the pathway by taking away some water from inside the
gel and dehydrating the gel, whereas water passes a gel by
diffusing into and swelling the gel.50 Liang et al.51 examine
several possible explanations about DPR, demonstrating that
gel shrinking and swelling is not likely to be responsible for
DPR. Wettability plays a role in DPR but with limited
influence, and Liang et al. suggest that the segregation of oil and
water pathways may instead play the domination role in DPR.
Nillson et al.52 put forward a mechanism with segregated
pathways for oil and water and the preferential pathways for oil
and water are controlled by wettability and partially by pore
size. Liang and Seright53 came up with a new point that if the
gelant matches the wetting phase, the wall-effect model results
in the DPR. If the gelant matches the nonwetting phase, the
droplet model accounts for the DPR. Willhite et al.54 held that
the gel-dehydration mechanism creates new oil-flow channels,
and the brine flows primarily in the same flow path as oil. The
trapping of oil leads to the DPR. Nguyen et al.55 studied DPR
mechanism in sand packs treated with Cr(III)−acetate−HPAM
gels. They claim that oil restores permeability by dehydrating
and displacing of gels and reconnection of residual oil ganglia.
The trapping of residual oil is the main reason leading to DPR.
Using X-rays, Seright et al.56,57 showed that dehydration is the
primary reason for the oil permeability increase. The
permeability to water is extremely low because gel and oil
primarily flow in the same path, but the gel rehydration and
swelling partially close the path; thus, the water must flow
through the gel itself.
With respect to the oil permeability development mecha-
nism, researchers mainly focus on the displacement mecha-
nism40,57,58 and dehydration mechanism.49,50 No explanation is
fully convincing, and more work should be done to further
verify the mechanism. As for the mechanism of DPR, possible
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Figure 1. Apparatus schematic of NMR T2 scanning for DPR experiments. Reprinted with permission from ref 71. Copyright 2017 American
Chemical Society.
explanations, such as pathway segregation, residual oil blocking,
the wall-effect model, restricted pore-throat model, and flowing
through gel itself because of gel swelling, are always able to find
their own basis. However, none of these proposed mechanisms
have been widely accepted to be the primary cause for DPR.
Therefore, more investigations should be conducted to figure
out the mechanism of DPR and the primary cause.
To visualize DPR at the pore level, the nuclear magnetic
resonance (NMR) scanning technique is adopted in this work.
NMR, as a nondestructive technique, has been applied to
monitor the properties of petroleum reservoir fluids.59
Specifically, it can be used to determine the components
group abundances in liquids derived from petroleum and coal
using selected multiplet 13C NMR spectroscopy.60 It can also
be applied to investigate fluid properties (i.e., wettability,
saturation, and viscosity)61,62 and several rock properties (i.e.,
rock permeability, pore structure distribution, producible
porosity, and the capillary pressure).63−66 Also, NMR is widely
used in well logging.67 NMR shows good application value in
the petroleum industry. Several works investigate spontaneous
imbibition using nuclear magnetic resonance; 68−70 we
previously studied the oil saturation development behind
spontaneous imbibition front using NMR T2. NMR T2 can
reflect the oil and water saturation changes in different pore
sizes in the permeable medium.71
The main purpose of this paper is to study the dominant
mechanisms of oil permeability development and DPR using
core flooding and NMR. The oil and water core-flooding
processes are scanned by NMR. This scanning reflects the
change of phase saturation, which enables us to have an insight
into the change behaviors of oil and water flow pathways.
Thereby, NMR results of core samples with different
permeability are discussed to investigate the mechanisms of
oil permeability development and DPR. In a companion paper,
we studied the mechanisms by combining core flooding, NMR,
and microscopic glass-etched model.72 Our work will focus on
the NMR scanned results of core samples with different
permeabilities. This helps us to further explore the effect of
permeability on the gel-phase change. Also, this helps further
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demonstrate the superiority of NMR scanning as a technique
for studying phase interaction and flow behaviors associated
with gel treatment. All of the above cognition practice will
deepen the understanding of DPR mechanisms and potentially
improve the utility of polymer gels with a DPR property.
2. EXPERIMENT
2.1. Experimental Materials. Polyacrylamide polymers
have been used for years to reduce the water production in
producers and mobility control in injectors. What makes
polyacrylamides distinctive for water shutoff is their ability to
reduce the permeability to water more than to oil.32 Sydansk
(1990) developed the aqueous gels by cross-linking poly-
acrylamide polymer with a Cr (III)−carboxylate−complex
cross-linking agent. By the addition of trivalent cations to form
a solid-like gel structure, the cross-linked polymer provides
greater reductions in permeability than uncross-linked poly-
mers.8 The gel technology has been tested in numerous oil
fields and yields effective conformance control.73−75 Our work
is based on the cross-linked polyacrylamide gels.
In the experiments, the gel contains 0.3% HPAM, 0.4% Cr
(III) acetate, and 0.3% NaCl. The hydrolyzed polyacrylamide
polymer (HPAM) has a molecular weight of approximately
12 000 kDa with a 25% hydrolysis degree and 98 wt % purity.
The sandstone cores are 7.1 cm long and 2.51 cm in diameter;
the two core samples have absolute permeabilities of 2.3 and
0.8 Darcy, respectively.
2.2. Experimental Procedure. Before the gelant injection,
the cores were fully saturated with water. Later, six pore
volumes (PVs) of Cr (III)−acetate−HPAM gelant were
injected with a constant pressure gradient of 48.6 psi/ft, and
the cores were shut in at 50 °C for 24 h to allow gelation.
As shown in Figure 1, the first part of the experimental
system is the core-flooding system. The ISCO pump provides
constant injection rates during the oil and brine injection. The
pressure sensor detects the pressure gradient. In every 10 or 20
PVs liquid injection, the flooding process is suspended for T2
scanning. The second part is the nuclear magnetic resonance
system. The core samples are inserted into the NMR probe for
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Figure 2. Schematic diagram of nuclear magnetic resonance. Reprinted with permission from ref 71. Copyright 2017 American Chemical Society.
Figure 3. Permeability curves to oil and water after gel placement. The left image is the core with a permeability of 2.3 Darcy. The right image is the
core with a permeability of 0.8 Darcy. Reprinted with permission from ref 72. Copyright 2017 Society of Petroleum Engineers.
T2 scanning and then will be reset in core holder for the
subsequent flooding. The experimental procedures of the NMR
T2 scanning for DPR experiments include the following phases:
(1) injection of the fully fluorinated oil with a constant
speed;
(2) stopping of the oil injection for T2 scanning in every 10
PVs injection;
(3) stopping of the oil injection and T2 scanning at a
different time;
(4) injection of the brine after 110 PVs oil injection; and
(5) stopping of the water injection for T2 scanning in every
20 PVs injection.
2.3. Nuclear Magnetic Resonance T2 Test. The
mechanisms of NMR have been detailed in our previous
work.71 Here, we make a simple description again for a better
understanding of NMR scanning. In the oil industry, hydrogen
nuclei (1H) are popular in most fluids, which makes them ideal
nuclei for NMR measurement. Therefore, “nuclear” refers to
hydrogen nuclei (1H), which have a magnetic moment (similar
to a tiny bar magnet). “Magnetic” means the instrument
provides the magnetic field. Under certain conditions, a strong
interaction between the hydrogen atom and the magnetic field
will be generated. This characteristic is called “nuclear magnetic
resonance”. It is known that water and oil are rich in 1H and
that 1H will display different distribution patterns under
different conditions (Figure 2)76.
When a core sample, saturated with oil or water, is placed
under natural conditions, the “tiny bar magnets” of hydrogen
nuclei will show a random distribution. The sample thus has no
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magnetic property. However, if the sample is placed in the
static magnetic field, the tiny bar magnets will align in the same
orientation. The magnetic moment synthesis of each hydrogen
nucleus is presented as a macroscopic magnetization vector.
The magnitude of the magnetization vector is proportional to
the number of the free hydrogen nuclei that can interact with
the magnetic field, which is proportional to the fluid volume. In
the NMR T2 spectrum, the signal amplitude is a representative
of the macroscopic magnetization vector. Therefore, the larger
the signal amplitude is, the larger the free fluid volume is. The
signal amplitude is the ordinate of the T2 spectrum, and
relaxation time is the transverse coordinate of NMR T2
spectrum. The magnitude of relaxation time reflects the force
that the fluid is subjected to. For a single-phase system, the
magnitude of relaxation time reflects fluid volume with respect
to the relaxation time. Generally, the longer the relaxation time
is, the larger the pore size, and the relaxation time and pore
radius are positively correlated.77 In our experiments, what we
are concerned with is not the exact value of pore size but the oil
saturation change, so we take the relaxation time roughly as the
pore size.
Because both oil and water contain hydrogen nuclei, it is
difficult to separate them from the magnetic signal directly. A
pair of approaches can be adopted to solve this. The first is to
block the water signal by adding paramagnetic MnCl2 to the
water. The second is to block the oil signal by replacing oil with
fully fluorinated oil, in which the hydrogen nuclei have been
fully replaced by fluorine. In this study, we employ the second
method to block the oil signal because the Cr(III)−acetate−
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Figure 4. NMR T2 scanning curves at different PV of oil injection. The left image is the core with a permeability of 2.3 Darcy. The right image is the
core with a permeability of 0.8 Darcy. Reprinted with permission from ref 72. Copyright 2017 Society of Petroleum Engineers.
HPAM gelant is sensitive to MnCl2. Gelation will be stopped
by MnCl2 with the concentration of over 20 000g/L.78
3. RESULTS AND DISCUSSION
3.1. Disproportionate Permeability Reduction Behav-
iors. The red curve for the 2.3 Darcy case (Figure 3) shows
that the oil permeability increased gradually from 90 to 505
millidarcy (mD) during the 110 PVs oil injection mD) during
the 110 PVs oil injection. Meanwhile, the change rate of oil
permeability decreased as the oil flooding continued. After the
oil injection, subsequent water was injected and the
permeability to water dropped sharply from 500 to 40 md, as
the blue curve shows. The permeability to water maintained a
constant value during the next 90 PVs water injection.
Compared to the 2.3 Darcy case, the oil permeability curve
in the 0.8 Darcy case displays a similar pattern of change during
the 100 PVs oil injection. The oil permeability increased
gradually and the oil permeability gradient decreased as the oil
flooding proceeded. During subsequent water injection, the
permeability to water also decreased sharply from 130 md to an
extremely small value and maintained a constant value.
In the 2.3 Darcy case, the mechanism change leads to the oil
permeability gradient decline at about 7 PVs. In the literature
review, oil-pathway evolution is attributed to either the gel-
displacement mechanism or the gel-dehydration mechanism.58
Before a 7 PVs oil injection, the gel displacement mechanism
dominates in the oil permeability development; later, the gel-
dehydration mechanism overtakes it.72 More evidence for the
domination of the gel-displacement mechanism is gel
production at the outlet. Compared to the 2.3 Darcy case,
the oil permeability gradient in the 0.8 Darcy case also shows a
similar trend, so we assume that the decline is also caused by
the same reason as the 2.3 Darcy case. However, more work
should be done to verify this assumption and to see the
difference in NMR results.
For the 2.3 Darcy case, when the oil injection reached 100
PVs, we paused the oil injection and carried out the NMR
scanning at a different shut-in time. When we resumed the oil
injection, a noticeable drop in oil permeability was observed
with a 3 PVs oil injection. Gel rehydration is proven to account
for the slight reduction of permeability to oil.58,72 For the 0.8
Darcy case, when oil injection reached 50 PV, we stopped oil
injection for 14 h, after which a slight fall in oil permeability
occurred similarly. We still assume that the gel rehydration is
the primary cause of the decrease of oil permeability. However,
as the permeability of the two cases is different, further
comparison of their NMR T2 curves should be considered.
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3.2. Mechanisms of Oil Permeability Development. In
this section, we compare the NMR results of the core samples
with different permeabilities to study the mechanisms of oil
permeability development and DPR. All of the NMR data have
been processed using Medellin’s NMR inversion method79 to
eliminate the ringing effect of primary NMR data.
Take the NMR T2 curves after gelation as an example. There
are two high peaks in the 2.3 Darcy case where the high left
peak indicates a large amount of fluid existing in small pores
and there is a wide range distribution of small pores. However,
in the 0.8 Darcy case, the left peak is negligible. The ratio of
small pores is related to the separation of rocks. When the
relaxation time is larger than 400 ms, the signal amplitude in
the 0.8 Darcy case shows no value, while there is a certain value
in 2.3 Darcy case. Because the relaxation time roughly
represents the pore size, we can approximately conclude that
the maximum pore in 2.3 Darcy case is larger. Signal amplitude
represents the volume ratio with respect to the relaxation time.
For the comparison at 100 ms, the peak signal amplitude in 0.8
Darcy case is twice of that in 2.3 Darcy case. What is more, the
area under the T2 distribution curve with a relaxation time
larger than 100 ms in the 0.8 Darcy case is larger than that of
the 2.3 Darcy case. This does not mean that there are more
large pores in the 0.8 Darcy case because different core samples
have different correlations between relaxation time and pore
size.
The left panel in Figure 4 shows the NMR T2 scanning
curves for the 2.3 Darcy case at different PV of oil injected. A
sharp signal decrease in large pores happened when oil
injection reached 7 PVs, at which there is a noticeable decline
of oil permeability gradient. However, no more noticeable
signal amplitude decrease in large pores was detected during
further oil injection. It has been proved that a gel-displacement
mechanism in large pores is the primary reason for the initial
oil-pathway development.72 Because the signal amplitude is
proportional to the fluid volume, this signal decrease in large
pores means that the replacement of gel by fully fluorinated oil,
which has no signal during NMR T2 scanning. The production
of some gel at the outlet supports this conclusion further. With
the proceeding of oil flooding, there is an obvious increase in
signal amplitude in small pores, while the change in large pores
is inconspicuous. Because paramagnetic Cr(III) can greatly
shorten the relaxation time, the relaxation time of the Cr (III)−
acetate−HPAM gel is shorter than that of free water. During
NMR tests, if the echo time is too long, a portion of the signal
with short relaxation time relaxes so quickly that the instrument
cannot detect them. Therefore, for the same volume of gel and
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Figure 5. NMR T2 scanning curves at different PV of oil injection. The left image is the core with a permeability of 2.3 Darcy. The right image is the
core with a permeability of 0.8 Darcy. Reprinted with permission from ref 72. Copyright 2017 Society of Petroleum Engineers.

Figure 6. NMR T2 scanning curves at different shut-in time duration. The left image is the core with a permeability of 2.3 Darcy. The right image is
the core with a permeability of 0.8 Darcy. Reprinted with permission from ref 72. Copyright 2017 Society of Petroleum Engineers.

water in small pores, the detectable NMR signal of water can
possibly be larger than gel. When free water is pushed out of
the gel in small pores, the total NMR signal can increase.
Because the Cr (III)−acetate−HPAM gel can dehydrate under
oil-phase pressure, more water will be pushed out of the gel and
be trapped in small pores with the going on of oil flooding.
Therefore, the increase of free water in small pores is
responsible for the gradual increasing of signal in small pores.
For the 0.8 Darcy case, signal plummeted in large pores
during the first 10 PVs of oil injection, while no obvious change
occurred in small pores. During this process, some gel was also
produced at the outlet. Based on the discussion in the 2.3 Darcy
case, we have acknowledged that the gel displacement
mechanism is the primary mechanism for oil permeability
development initially. However, as the oil injection continued,
signal drop still occurred in large pores during another 40 PVs
of oil injection with no change in small pores. The signal-
amplitude behavior is different from that in the 2.3 Darcy case,
in which signal amplitude jumps in small pores while the
change in large pores is inconspicuous. In the 2.3 Darcy case,
the decline of oil permeability gradient results from the
mechanism change. The displacement mechanism entails a high
oil permeability gradient, while the subsequent dehydration
mechanism leads to a smaller oil permeability gradient. The oil
pressure gradient decreased at about 10 PVs of oil injection; if
the dehydration mechanism is also the primary mechanism
causing oil permeability development after 10 PVs of oil
injection, the T2 curve pattern change during another 40 PVs
of oil injection should be different from that during the first 10
PVs. Note that in the 0.8 Darcy case, the amplitude peak
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dropped from 85 to 55 during the first 10 PV of oil injection,
while the peak value decreased from 55 to 42 during another 40
PV of oil injection, indicating a slower decline speed of the
signal. This is consistent with the smaller oil permeability
gradient during another 40 PVs of oil injection. Therefore, we
conclude that the gel-dehydration mechanism is the main
mechanism in this phase. In terms of the obvious decrease in
large pores, because small pores are in the minority in the 0.8
Darcy core, the dehydration mainly happened in large and
moderate pores, and it was difficult for the water dehydrated
from the gel to stay in the oil-flow channels created by oil-phase
pressure. The water dehydrated from the gel was displaced out,
and the nonsignal fully fluorinated oil took the pore space
previously occupied by the dehydrated water, so the signal
amplitude in large pores kept falling. It is possible that a small
portion of dehydrated water is left in the flow channels, whereas
its volume is too small to offset the signal decrease. The signal
change in small pores is too inconspicuous to mention.
Figure 5 is another set of NMR T2 scanning curves during
further oil injection. From the discussion in Figure 4, the
dehydration mechanism was responsible for the oil permeability
development in both cores at this stage. As the oil flooding
proceeded, the permeability to oil kept growing. For the 2.3
Darcy case, the signal amplitude in small pores increased
gradually, while no distinct change occurs in large pores. For
the 0.8 Darcy case, the signal in large pores kept decreasing at a
very low speed. The peak value declined from 40 to 37 during
the 30 PV oil injection. However, the signal change in small
pores is too inconspicuous to mention. In conclusion, gel
dehydration mainly occurs in small pores for the 2.3 Darcy case,
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Figure 7. NMR T2 scanning curves at different PV of water injected. The left image is the core with a permeability of 2.3 Darcy. The right image is
the core with a permeability of 0.8 Darcy. Reprinted with permission from ref 72. Copyright 2017 Society of Petroleum Engineers.
while gel dehydration mainly happens in large and moderate
pores for the 0.8 Darcy case, indicating that the gel dehydration
becomes more and more difficult.
When 100 PVs of oil was injected, we paused the oil flooding
and scanned the core samples at a different shut-in time. Figure
6 plots a series of NMR T2 curves that demonstrate gel
rehydration versus shut-in time. For the 2.3 Darcy case, the
signal amplitude decreased as the time went by, which is caused
by the gel rehydration.72 The dehydrated gel absorbed free
water and rehydrated, and the detectable NMR signal
accordingly decreased. For a given equal volume in small
pores, the detectable signal amplitude of free water is much
larger than the mature gel, which accounts for the signal decline
in gel rehydration. For the 0.8 Darcy case, the signal amplitude
also dropped gradually. The gel rehydration in this case also
suggests that some free water was left in the oil flow pathways
because the rehydration happens only when the dehydrated gel
meets free water.
For both cores, when the oil flooding restarted, a noticeable
decrease in oil permeability occurred. However, the perme-
ability quickly recovered during another 3 PVs of oil injection.
Thus, we conclude that for both cores, the gel rehydration can
only partially reduce the permeability, and the rehydrated gel
can be easily extruded by the oil phase. For the 2.3 Darcy case,
the signal amplitude started increasing after 10 PVs of oil
injection, suggesting that the gel dehydrated again. However,
for the 0.8 Darcy case, the rise in signal amplitude occurred in
large and moderate pores, which is inconsistent with our
conclusion from Figures 4 and 5 that when the dehydration
happens, the signal amplitude in large pores decreases. A
possible explanation for this is that after the gel rehydration
happened, the oil-flow channels in large pores would deform.
The distribution of oil, gel, and free water would turn more
complex, so the free water dehydrated from the gel could not
be displaced out immediately and completely, contributing to
the slight increase in signal amplitude. As the oil injection
continued, the signal amplitude in large pores gradually
descended as shown in Figure 5, demonstrating that the free
water dehydrated from the gel was displaced out from the flow
pathways.
3.3. DPR Mechanism. After the oil flooding process was
completed, subsequent water was injected into the core
samples. The corresponding NMR T2 curves are shown in
Figure 7.
For the 2.3 Darcy case, compared to the NMR T2 curve
when oil injection just reached 110 PVs, the signal of water
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Article
flooding in both large and small pores show a clear increase,
especially in large pores. Compared to the NMR T2 curve just
after gelation, when 20 PV of water was injected, the signal
amplitude in large pores would immediately recover to the
approximate value as that after gel gelation. The signal
amplitude in large pores rose because the gel rehydrated, and
the fully fluorinated oil previously occupying the large pore
space was largely replaced by the rehydrated gel or free water.
There is a large portion of residual oil left in the large pores. In
fact, for a given equal volume, the relaxation time of free water
is much larger than matured gel; therefore, only a little fully
fluorinated oil was displaced out because the increase of signal
in large pores is approximate to that after gelation. Figure 3
shows that the permeability plumped from 500 to 40 md as the
water flooding started. The gel rehydration and high residual oil
saturation are two important mechanisms for the DPR to water.
Some water has to flow through the gel body and gel films.72
Seright previously mentioned that the permeability to water
through the gel is extremely low,58 so the low flow capacity of
water through the gel is also a reason for DPR. With the
increase of water injection, the signal amplitude in large and
small pores remained unchanged. The permeability to water
maintained a relatively constant value during the subsequent
water flooding, indicating the termination of gel rehydration.
For the 0.8 Darcy case, a gradual signal increase in large
pores occurred as the first 30 PVs of water injection. This
phenomenon is different from the signal change in the 2.3
Darcy case, in which signal increased in both large and small
pores. Moreover, the signal amplitude in large pores rebounded
to the level close to the 2.3 Darcy case after gelation, while the
signal amplitude in 0.8 Darcy case recovered to a value that is
far less than the signal amplitude after gelation. A possible
explanation is that because the oil pathways are narrower than
that in the 2.3 Darcy case, the pathways would be further
compressed when the gel rehydration happened where much
residual oil was left. Thus the ability of flow pathways to trap
free water in this case is lower than the 2.3 Darcy case.
Consequently, the gel rehydration and the trapping of free
water only lead to a limit increase in signal amplitude in large
pores. Besides, plenty of the residual oil was trapped in the flow
channels, which, together with the expansion of rehydrated gel,
will significantly block the flow pathways. Most water had to
flow through the gel and gel films. Figure 3 shows the
permeability dropped from 130 to 4 md when the water
flooding began, and the permeability was maintained as the
water was steadily injected. In this case, high residual oil
DOI: 10.1021/acs.energyfuels.8b00420
Energy Fuels 2018, 32, 4959−4968
Energy & Fuels
saturation, gel rehydration, and the low permeability of gel
relative to water are the main mechanisms of DPR. As water
was injected, the signal amplitude in large pores slightly
decreased after 30 PVs of oil injection. There are possible
explanations for this phenomenon. First is the increase of fully
fluorinated oil in large pores. However, because no more oil
was injected during this phase, this assumption is incorrect.
Second is the decrease of the free water. The free-water
reduction resulted from the deepening of gel rehydration,
which led to gel swelling and pushed more free water out of the
pore space. Because the detectable NMR signal amplitude of
free water is larger than that of mature gel in relatively small
pores, further gel rehydration cannot offset the free water loss,
decreasing the signal amplitude. The speed of gel rehydration,
in this case, is slower than that in the 2.3 Darcy case.
4. CONCLUSIONS
(1) Gel displacement in large pores is the primary reason for
the oil permeability development initially. As oil flooding
proceeds, the gel-dehydration mechanism becomes
dominant. For the porous medium of very high
permeability, gel dehydration occurs in all pores, while
for the porous medium with lower permeability, gel
dehydration mainly occurs in large pores.
(2) Some free-water dehydration products from the gel will
be trapped in the pore space, which is more difficult to
resolve for the porous medium with lower permeability.
Gel rehydrates when there is no oil-phase pressure
gradient. The rehydrated gel can reduce the permeability
to a limited extent, and the oil pathways can be easily
extruded by the subsequent oil injection.
(3) The gel rehydrates abruptly when meeting water, and the
permeability to water will be significantly reduced. The
reasons for DPR include the gel rehydration that blocks
the flow channel available to water, the high residual-oil
saturation (which greatly blocks the available flow
channels), and the low permeability of the gel relative
to water. A large portion of water has to flow through the
gel or gel films because of gel rehydration and residual oil
retention. As for the low-permeability porous medium,
gel rehydration mainly happens in large pores, while gel
rehydration occurs in all space for the porous medium of
high permeability when contacting water.
(4) NMR T2 is an effective way to study phase interaction
and flow behaviors associated with the gel treatment.
Although the certain change in NMR T2 curves may
happen because of the permeability difference, final
conclusions for the mechanisms of oil permeability
development and DPR are consistent.
■
AUTHOR INFORMATION
Corresponding Authors
*E-mail (B.L.): liangbin_petro@163.com.
*E-mail (J.L.): lijunjian2015@126.com.
ORCID
Bin Liang: 0000-0003-4476-4128
Notes
The authors declare no competing financial interest.
4966
Article
■ ACKNOWLEDGMENTS
Financial support from National Natural Science Foundation of
China (grant no. 51404280) and the Foundation of the State
Key Laboratory of Petroleum Resources and Prospecting,
China University of Petroleum, Beijing (grant no. PRP/open-
1707) is acknowledged. The NMR inversion code used in this
study was provided by Dr. David Medellin and Dr. Carlos
Torres-Verdin at UT Austin’s Research Consortium on
Formation Evaluation. The authors greatly thank Dr. Han
Jiang at the University of Texas at Austin for performing the
NMR inversion.
■
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