5.

1 APT Development and Testing

A two-phase project was designed to develop an APT to meet specified goals in regard
to water-permeability (Kw) reduction (Phase 1) and acid diversion (Phase 2). To meet
these goals, three series of tests were conducted: core flow tests to determine reduction
of brine and oil permeability, acid diversion tests, and rheological measurements.

Core Flow Tests for Brine- and Oil-Permeability Reduction.

All flow tests were conducted using multipressure-tap Hassler sleeves that allow the
core to be divided into four separate segments. For tests with sandstone cores, typical X-
ray diffraction analysis is shown in Table 1. For tests using carbonate cores (Bedford
limestone), typical X-ray diffraction analysis is shown in Table 2. Core lengths were
approximately 5 to 6 in., with a diameter of approximately 1 in. In all flow tests,
American Petroleum Inst. (API) brine (i.e., 9% NaCl and 1% CaCl2) was used as the
aqueous phase and kerosene was used as the oil phase. In all cases, 2% KCl was used as
the treatments mix water. Brine and oil initial permeabilities were determined in the
normal production direction with the flow from Segment 1 to Segment 4 (from reservoir
to well). The treatment was pumped in the reverse direction, from Segment 4 to Segment
1 (from well into reservoir). Final assessment of the treatments effect reverts to flow
from Segment 1 to Segment 4. All core tests were performed at residual-water saturation
or residual-oil saturation.

The following steps were followed to determine brine- and oil-permeability reduction:

1. Record core dimensions and place the core in the multitap Hassler sleeve
apparatus.
2. Place sufficient overburden pressure on the core to ensure that no fluid bypasses
the core. 3. Determine the viscosities (at temperature) of the brine and oil to be
used in the flow tests. Perform all flow series at the desired test temperature.
3. Stabilize the flow of brine through the core in the normal production direction.
 4. Stabilize the flow of oil through the core in the normal production direction.
5. Repeat Steps 4 and 5 until reproducible brine and oil permeabilities have been
achieved, ending with either brine or oil (depending on the test).
6. Pump the treatment through the core in the reverse-flow direction. For all flow
tests, use a limit of 30 pore volumes (PV) of treatment or a differential pressure
of 500 psi (whichever is reached first). Overdisplace the treatment through the
core with 6 PV of brine and 2 PV of kerosene, or until a differential pressure of
500 psi is reached (whichever comes first).
7. Repeat Step 4 or 5.
8. Use Eq. 1 to determine the shutoff percentage:

[ K pretreat K post treat ]

100 (5.1 )
K pretreat

K pretreat K posttreat
Where is the pretreatment permeability in md and post-

treatment permeability in md.

Acid Diversion Tests.

These tests were run using standard Hassler sleeves. For each test, one core each was
taken to residualoil saturation (water core) or residual-water saturation (oil core) and
initial permeabilities were measured as described in Steps 1 through 6 (previous
section). The cores were then connected so that the treatment sequence could be
bullheaded, allowing the treatment to flow through either core. An ammonium chloride
spacer was pumped between the APT treatment and the acid. For the APT treatment and
ammonium chloride spacer, a limit of 30 PV or 500-psi differential pressure was used,
and in all tests, the 500-psi limit was reached before pumping 30 PV. For the acid stage
(5% HCl), the limit was 13 PV or 500 psi; and in each case, 13 PV was pumped without
reaching the 500-psi limit. In the final stage, the cores were disconnected and final
permeabilities were measured.
 Rheological Measurements.

Rheological measurements (Fig. 3) were run on a Haake RS 150 rheostress rheometer,

using a cone-and-plate arrangement, at 73F. Rheological measurements (shown in Table
3) were run using a Brookfield LVT viscometer with a UL adapter at 60 rev/min, at
74F.

Phase 1Water-Permeability Reduction

Initial testing on this project focused on water-permeability reduction, with target goals
of a minimum 80% reduction in brine permeability and maximum 50% reduction in oil
permeability.

Polyacrylamide Modification.

HM polyacrylamide was the first type of polymer evaluated to determine whether

hydrophobic modification could improve RPM functionality. Polyacrylamide was
chosen because its use in bullhead operations has been well documented and because of
its ease of polymerization.2 Several variations were synthesized in an effort to determine
whether the hydrophobic modification had a positive effect on the brinepermeability
reduction. The polymers were synthesized with aqueous-solution polymerization with
azo initiators.5 The screeningtest method used for this phase of the project incorporated
a multitap-core flow test using Berea sandstone cores in a brine/oil/ brine/treatment
brine-flow sequence, at 175F. The multitap Hassler sleeve revealed the depth of
penetration of the treatment into the core.13,14 As mentioned, the multitap sleeve
divides the core into four segments. This system allows calculation of the permeability
reduction in each segment. In normal flow, the fluids enter the core at Segment 1 and
exit at Segment 4. In the treatment stage, polymer solution enters the core at Segment 4
and exits at Segment 1. For example, if the polymer molecular weight is too high and
restricts entry into the core, only Segment 4 will show damage.

A large number of modified polyacrylamides were tested, with polymers containing

variations in both the levels of hydrophobe and the hydrophobe-chain length.
Representative examples of the test results are shown in Fig. 4. The first entry in Fig. 4
is for an in-house synthesized, unmodified polyacrylamide. This polymer was not
extensively characterized, but was compared to a commercially available
polyacrylamide (used in previous core flow tests) having a molecular weight of
approximately 6 million.13 On the basis of solution viscosities, the in-house synthesized
sample has a molecular weight considerably less than 6 million. The remainder of the
data in Fig. 4 are for polyacrylamide modified with various levels of C18 hydrophobe
groups (a straight, unbranched alkyl chain, 18 carbon atoms in length). For these
samples, the synthesis conditions (temperature and initiator concentration) were the
same as those used for the unmodified polyacrylamide. Therefore, the molecular weights
of the unmodified and modified polymers should be somewhat similar, and any
differences in performance can be attributed to the hydrophobic modification.

As shown in Fig. 4, the hydrophobic modification increased levels of brine-permeability

reduction and also thermal stability. In these tests, the initial percentage of permeability
reduction (% Kw reduction) was calculated after flowing a minimum of 130 PV of brine
through the core after the treatment sequence. The cores were then shut in overnight at
temperature, and flow was re-established the following day. As seen previously, the
unmodified polyacrylamide was not thermally stable at 175F, and the level of
brinepermeability reduction dropped by almost 80% after the overnight shut-in.13
However, the hydrophobic modification resulted in an increase in thermal stability. The
polymer with 4% C18 hydrophobe shows only a slight decrease in effectiveness after the
shutin. The exact reasons for these improvements are not known, but it is speculated that
the superior retention of the brine-permeability reduction is caused by increased levels
of permanent adsorption resulting from hydrophobic associations.12
On the basis of the data generated during this phase of the project, a conclusion was
reached that the hydrophobic modification improved the level of brine-permeability
reduction. However, the target goal of 80% minimum reduction had not been met.
Hydrophobic modification also appeared to increase the temperature stability of the base
polymer (polyacrylamide) at the screening temperature (175F). The next development
stage sought a polymer base that would increase the level of brine-permeability
reduction and maintain better thermal stability than with the polyacrylamide.

Polydimethylaminoethyl Methacrylate (polyDMAEMA) Modification.

Polymers based on dimethylaminoethyl methacrylate were investigated,5 and several

variations were synthesized. Additions of C10, C16, and C18 hydrophobic groups were
tested (see Table 4). Total Reduction represents the overall permeability reduction for
the entire core. Segment 2 Reduction and Segment 3 Reduction represent Segments
2 and 3, respectively. Tests revealed that the C10 hydrophobe was not effective at
imparting brine-permeability reduction characteristics; the highest level of permeability
reduction was approximately 25%. Apparently, a minimum chain length is needed to
provide the associations between polymer chains that can impart an ability to reduce
core permeability. The highest level of permeability reduction occurred with the C16
hydrophobe. After extensive testing, polyDMAEMA modified with a C16 hydrophobe
was determined to meet the desired minimum requirements of at least 80% reduction in
brine permeability, with little or no damage to the effective permeability to oil. The next
section contains examples of flow tests run during the evaluation of this polymer.

Evaluating HM polyDMAEMA

In evaluating HM polyDMAEMA, Core 1 of Table 5 (a lowpermeability Berea core)

shows that the polymer brought about the desired permeability reduction to brine
throughout the core. For Tests 1 through 4 and Test 6, significant permeability reduction
was seen in Segments 2 and 3, indicating that the polymer penetrated into the core.
Continued testing showed that the polymer treatment resulted in excellent brine-
permeability reduction from 90 to 200F, even in high-permeability sandstone cores. In
Table 5, Cores 2 through 4 indicate that the target goal of 80% permeability reduction
was met in all of these tests. In addition, no decline in the effective brine-permeability
reduction has been seen with continued flow through the cores for 6 months at 210F.

The data presented to this stage relate only to water- and oilpermeability reduction and
were presented to show the development process of the APT technology. The laboratory
data can be related to actual field results for Kw reduction by the use of Darcys
equation for radial flow. Fig. 5 illustrates how this equation can be used to predict the
post-job water cut of a well, on the basis of the prejob water cut. In this case, it was
assumed that there were two layers: a 100% oil layer and a 100% water layer. It was also
assumed that the water layer was treated to a depth of 10 ft, with 95% permeability
reduction [residual-resistance factor (RRF)20], and the oil layer was treated to a depth of
5 ft, with 33% permeability reduction (RRF1.5). Therefore, Fig. 5 shows that in this
scenario, a polymer treatment takes a well from a prejob water cut of 80% to a post-job
water cut of 32%.

Testing at Residual-Water Saturation. In Table 5, Core 5 shows results of the treatment

of a Berea core at residual-water saturation. While there was some initial damage to the
oil permeability, continued flow resulted in minimal damage. This result was typical for
numerous tests.

Oxidizer Treatments.

The ability to remove water-shutoff treatments is a common topic of concern. In the case
of sealants (e.g., crosslinked polymers, monomer solutions, and silicates), the treatments
are essentially permanent. The gel in the rock matrix cannot be removed because fluid
cannot flow into the treated zone to contact the gel. However, with treatments of dilute,
nongelling polymers, flow through the treated zone can be achieved because the
treatment is not a total sealant. In Table 5, Core 6 shows the results of treating a core
with an oxidizer (5% sodium hypochlorite+1.8% NaOH) after a polymer treatment. In
this case, a highpermeability sandstone core was treated with 6,000 ppm polymer at
200F. After brine flow (to obtain the percentage of permeability reduction), the core
was treated with 2 PV of oxidizer. The core was shut in overnight, and brine flow
resumed the next day. As shown, the overall permeability reduction fell from 85 to 2%
after the oxidizer treatment.

Rheological Measurements

As discussed, hydrophobically modified polymers show unique rheological properties.

Fig. 3 shows viscosity measurements over a 30-minute period for 1% active solutions of
polyDMAEMA and two hydrophobically modified polyDMAEMA samples. The
polyDMAEMA test revealed essentially constant viscosity for 30 minutes at shear rates
ranging from 20 to 1,000 sec1. The HM polyDMAEMA samples initially showed
constant viscosity, but a rapid increase in viscosity was seen after a period. For the 5%
C16-modified polymer, the viscosity increase was observed at a shear rate of 200 sec1.
For the 7% C16-modified polymer, the increase occurred at 50 sec1. While a more-
extensive investigation of the rheological properties is not presented here, the hypothesis
is that this viscosity increase is caused by a change from intra- to intermolecular
hydrophobic associations. Under low shear conditions, intramolecular associations
dominate. However, under higher shear conditions, these associations break, allowing
the polymer chains to stretch and experience intermolecular associations. These
intermolecular associations are believed to result in the rapid increase in viscosity
observed. It should be noted that similar shear-thickening phenomena was not seen with
solutions less than 1% active (which covers typical treating solutions).

This rheological phenomenon could have implications in the use of this polymer system.
In some core flow tests at low treatment rates, no pressure increase was seen, even after
30 PV of treatment had been flowed into the core.5 One test has been run to investigate
the effect of the treatment flow rate. In this test, 16 PV of treatment was pumped at 2
mL/min, with no pressure increase. The flow rate was then increased to 4 mL/min, and
after pumping only 3 additional PV of treatment, the pressure had increased to 400 psi
(in this case, the treatment was stopped at 400 psi, rather than 500 psi). This
phenomenon is not new, and a recently published paper discusses a flow-induced
adsorption of polymers at various treatment flow rates.15

Viscosified or foamed fluids commonly used for acid diversion can result in high friction
pressure and require special manifolding and/or pumping equipment. The low viscosity
of the APT diverting system (shown in Table 3) results in ease of mixing, low friction
pressures, no special manifolding or pump requirement, etc. The diversion of aqueous
fluids occurs only after the material enters the porous media, whether it is naturally
fractured carbonate/dolomitic rock or sandstone matrix. It is theorized that the increased
shear encountered upon entering the rock matrix, coupled with polymer adsorption,
results in an apparent viscosity increase that may be responsible for the pressure
increases seen during the treatment.
Phase 2Acid Diversion

Testing to this point indicated that the APT could effectively reduce permeability to
water with little damage to oil permeability. Testing was then begun to determine
whether the APT would be effective in diverting acid treatments. Parallel core testing
was used; polymer and acid were bullheaded into both a watersaturated core and an oil-
saturated core simultaneously.

Test 1 Series: Sandstone Cores Treated Separately.

The initial experiments involved a relatively high-permeability sandstone core (at

residual-oil saturation to represent a water-bearing stratum) and a lower-permeability
Berea sandstone core (at residualwater saturation to represent an oil-bearing stratum). In
Table 5, Cores 7 and 8 show the results of control tests in which 13 PV of 5% HCl was
pumped through each of these cores separately. As shown, each test resulted in more
than a two-fold increase in permeability, demonstrating that these cores were stimulated
by the acid treatment.

Test 2 Series: Sandstone Cores Treated Simultaneously.

The second test again used a high-permeability core at residual-oil saturation and a
lower-permeability core at residual-water saturation. However, in this case, the cores
were connected in parallel so that the treatment fluid could be bullheaded into both cores
simultaneously. The test temperature was 175F. The treatment consisted of a 2,000-ppm
solution of APT. The volume of treatment entering the water core was 9 PV, and 0.8 PV
entered the oil core before the 500-psi pressure limitation was obtained. The APT fluid
was flushed out of the lines, and a spacer fluid of 5% ammonium chloride was pumped
into the parallel-core flow apparatus. All of the spacer fluid was observed to enter the oil
core (only 0.4 PV entered the core before reaching the 500-psi pressure limit). After
flushing the spacer from the lines, a 5% HCl solution was pumped into the parallel
treatment apparatus. From a total 13 PV of acid, 11 PV entered the oil core and 2 PV
entered the water core. As shown in Cores 9 and 10 (Table 5), water-core retained
permeability was only 3.5%, while oil-core retained permeability was 220% (essentially
the same as observed in the control test with the oil core). Thus, the APT not only
effectively diverted the acid from the water core to the oil core, it also very effectively
decreased the permeability of the water core while allowing stimulation of the oil core.

Test 3 Series: Berea Cores Treated Simultaneously.

A third test series used two Berea cores, one at residual-oil saturation and one at
residual-water saturation. Again, the cores were connected so that treatment fluids could
be bullheaded and the test temperature was 175F. A 2,000-ppm solution of APT was
bullheaded into the cores. The water core received 1 PV of the treatment, while 0.8 PV
entered the oil core before the 500-psi pressure limitation. After flushing the lines of the
APT fluid, a spacer of 5% ammonium chloride followed; 0.1 PV entered the water core
and 0.2 PV entered the oil core. From a total 13 PV of 5% HCl, 10 PV entered the oil
core and 3 PV entered the water core. As shown in Cores 11 and 12 (Table 5), the water
core gave a retained permeability of 44%, while the oil core gave a retained permeability
of 134%.
 Test 4 Series: Carbonate Cores Treated Simultaneously.

Previous testing focused on sandstone lithology; the fourth test series used two Bedford
limestone (carbonate) cores, one at residual-oil saturation and one at residual-water
saturation. Again, the cores were connected so that treatment fluids could be bullheaded
and the test temperature was 175F. A 2,000-ppm solution of APT was bullheaded into
the cores. Subsequently, 0.2 PV entered the water core and 1.6 PV entered the oil core
the opposite of that observed with the sandstone cores. On the 5% ammonium chloride
spacer, 0.5 PV entered the water core and 0.2 PV entered the oil core. From a total of 13
PV of 5% HCl, 2 PV entered the water core and 11 PV entered the oil core. These results
are tabulated in Table 5, Cores 13 and 14. The oil core had a large wormhole, while the
water core appeared completely intact (see Fig. 6).
Conclusions

On the basis of the laboratory investigation and subsequent field trials, the following
conclusions can be drawn:

Hydrophobic modification appears to improve brine-permeability reduction for

both polyacrylamide and polyDMAEMA in sandstone.
The target goals of 80% brine-permeability reduction and minimal damage to oil
permeability were met with the HM polyDMAEMA.
Laboratory and field tests have shown that APT can divert acid from
predominantly water-saturated zones to predominantly oilsaturated zones in both
sandstone and carbonate lithology.
In sandstone, APT can provide acid diversion and permanent Kw reduction.
In carbonate, APT can provide acid diversion. Further work is needed to
determine whether permanent Kw reduction will be seen.