Jomu~.

LO~

ELSEVIER Journal of Petroleum Science and Engineering 17 (1997) 197-209

Laboratory evaluation of phenol-formaldehyde/polymer gelants

for high-temperature applications
Steven L. Bryant a,b, Martin Bartosek a, Thomas P. L o c k h a r t a,,
a Eniricerche S.p.A., L,ia F. Maritano, 26. 1-20097 San Donato Milanese, Italy
b TICAM, Unit,ersio' o f Texas atAustin, Austin, TX 78712, USA

Received 9 October 1995; accepted 11 December 1996

Abstract

Polymer gels are attractive tools for stopping unwanted fluid production from oil and gas wells, but conventional gelant
formulations become increasingly difficult to apply at higher formation temperatures. In contrast phenol-formaldehyde
cross-linked polymer gelants remain viable to at least 140°C. Choice of polymer composition permits control of the gelation
delay, and the gelants display good injectivity even when the residence time approaches the gelation time. Cross-linking
occurs over a wide range of pH and is insensitive to lithology. Although retention of the gelant components on formation
rock is negligible, phenol strongly partitions into oil phases contacted by the gelant. Experiments and numerical modelling
show that a preflush of phenol is an effective method of compensating for phenol partitioning in the formation. © 1997
Elsevier Science B.V. All rights reserved.

1. Introduction The desirable characteristics of a gelant (i.e. gel-

forming solution) for these applications may be sum-
Recent successful applications of cross-linked
marised as follows: (1) programmable gelation de-
polymer gels for reducing produced water have led
lay; (2) good injectivity; (3) good polymer and
to strongly renewed interest in this technology within
cross-linker propagation; (4) insensitivity of the
the oil industry. In matrix formations a treatment
cross-linking chemistry, to fluid-rock and fluid-fluid
placed in the near-wellbore region can completely
interactions; (5) good gel stability under reservoir
shut off both water and gas production from selected
conditions. The first two characteristics ensure that
intervals. Near-wellbore treatments can also be used
the desired treatment volume can be placed in the
to modify the conformance of injected fluids where
formation, while the third and fourth lend confidence
crossflow is not a consideration (Seright, 1988).
that gel will form throughout the treated volume. The
Other impressive results have been achieved in wa-
last characteristic provides assurance that the treat-
ter-flooded formations, where polymer gels have been
ment will last long enough to achieve the required
used to close conductive fractures (Sydansk and
economic benefit. Although we list these character-
Moore, 1992; Boding, 1994).
istics individually, they are not mutually indepen-
dent. For example, gel stability and gelation delay
* Corresponding author. are different manifestations of the cross-linking reac-

0920-4105/97/$17.00 Copyright © 1997 Elsevier Science B.V. All rights reserved.

PH S0920-4105(96)00079-4
198 S.L. Bryant et al. / Journal of Petroleum Science and Engineering 17 (1997) 19~209
tion. Thus finding a gelant that satisfies all the
criteria may be difficult.
As temperature increases, the difficulty in meet-
ing any of these characteristics increases. For exam-
ple, the principal gelants currently employed in the
industry [formed with polyacrylamide and Cr(III)-
acetate cross-linker (Sydansk and Moore, 1992;
Sydansk, 1993)] undergo gelation in a few hours or
less at 70°C and within a few minutes at 100°C
(Albonico et al., 1994). Moreover, Cr(III)-acetate is
strongly driven to precipitation and retention in
porous media at elevated temperature (Albonico et
al., 1994; Bartosek et al., 1994). Thus the placement
of Cr(III)-acetate/polymer gels a significant distance
into matrix rock (e.g., > 1 m from the wellbore, as
some applications might require) will be difficult to
achieve in higher-temperature formations. Various
methods have been developed to address these draw-
backs. These include cooling the formation with a
pre-flush (Sanders et al., 1994) and employing
chelating ligands to delay gelation at high tempera-
ture and strongly reduce Cr(III) retention (Lockhart
and Albonico, 1992; Albonico et al., 1993, 1994;
Bartosek et al., 1994). Although these techniques
provide some useful extensions of the applicability
of Cr(III)-polymer systems, these gelants do not
presently appear to provide a general solution to the
problem of water shut-off in formations above 100°C.
With regard to gel stability (characteristic 5 above),
on the other hand, it is possible to formulate bulk
gels with commercial polymers which exhibit long-
term stability in hard brines (Albonico and Lockhart,
1993). More importantly, persistent permeability re-
duction of gel-treated porous media can be achieved
to at least 140°C (Bryant et al., 1996).
Among the several other polymer gelants de-
scribed in the literature, those formed with acryl-
amide polymers or copolymers using a combination
of phenol and formaldehyde as cross-linkers (Falk,
1984; Moradi-Araghi et al., 1988) are reported to
undergo relatively slow gelation (from several days
to a week or more) at 90-100°C. These long gelation
delays, coupled with the reasonable expectation that
the phenol and formaldehyde cross-linkers will not
interact strongly with formation rock, suggested to us
that these gelants might be good candidates for some
high-temperature applications. We report here stud-
ies that provide new insight into the factors that
influence cross-linking of p h e n o l - f o r m a l -
dehyde/polymer gelants, and characterize their in-
jectivity and propagation in porous media. These
gelants emerge from these tests as attractive candi-
dates for high-temperature field applications.
2. Methods and materials
2.1. Materials
The commercial polymers employed in these stud-
ies were a low-molecular-weight (500,000 g/tool)
hydrolyzed PAAm, a p o l y ( a c r y l a m i d e - c o -
acrylamido-3-propane sulfonic acid) copolymer
( P A A m - A M P S ) , and an acrylamide/N-vinyl
pyrrolidone/acrylamido-3-propane sulfonic acid ter-
polymer (PAAm-VP-AMPS). The freshwater (FW)
gelants were prepared with distilled water. The syn-
thetic seawater (SSW) employed contained 10,818
ppm Na +, 448 ppm Ca -'+, and 1,288 ppm Mg 2+, all
furnished as their chloride salts. Standard reagent-
grade phenol and formaldehyde, the latter furnished
as a 35% aqueous solution, were employed.
2.2. Bulk gelation experiments
Gelants were prepared as described previously
(Albonico et al., 1993), the phenol and formaldehyde
being added last, followed by adjustment of the pH
by addition of diluted solutions of HC1 and NaOH
(0.01-1 M). Gelants were aged either in screw-cap
vials, in which case they were initially air-saturated,
or in sealed glass ampoules after careful degassing to
remove oxygen.
The influence of pH on gelation was studied by
preparing gelants covering the pH range of interest.
These were periodically removed from the oven
(every 1-2 h the first day, then gradually less fre-
quently as the pH stabilized) and the pH readjusted
using a minimum of acid or base solution. By this
method the pH of the gelants was maintained to
within 0.5 pH unit of the initial value. An effort was
made to minimize dilution of the samples during the
adjustment of their pH; the variation in their final
concentrations was less than 5%. The pH of the fluid
solutions and gels was monitored using a Metrohm
EA 125 microelectrode.
 S.L. Bryant et al. / Journal of Petroleum Science and Engineering 17 (1997) 197-209
Filtration experiments on the partially gelled solu-
tions were carried out by forcing the gelant through a
5-1xm Millipore or l-lxm Nuclepore filter at a con-
stant flow rate and monitoring for the rise in the
injection pressure. Filtration of the gelants through
the 1-~zm filter resulted in a noticeable decrease in
turbidity. The gelant solutions used in these experi-
ments were filtered through 5-1xm Millipore filters
prior to being placed in the oven to cross-link.
2.3. Partitioning experiments
To study the partitioning of phenol into crude oil,
a 1000 ppm SSW solution of phenol and an equal
weight of oil was mixed on a vortex mixer at ambi-
ent temperature until a fine emulsion was formed.
The resulting emulsion was allowed to stand for
several minutes to an hour followed by centrifuga-
tion to separate the phases. Control experiments
showed that the equilibration of phenol between the
two phases was essentially complete within the mini-
mum time required for mixing and separating the
two phases. A similar procedure was employed for
equilibrating 1000 ppm formaldehyde between SSW
and the crude oils. Three light-to-medium crude oils
stored at ambient conditions were used.
The quantity of phenol remaining in the aqueous
phase after equilibration was determined by a UV
spectroscopic method, monitoring at 268 nm. Con-
trol experiments showed that no components in the
crude oils contributed to the wavelength monitored.
Formaldehyde analysis was carried out using a col-
orimetric method based on chromotropic acid (Hauser
and Cummings, 1964). The detection limit of formal-
dehyde was better than 1 ppm.
2.4. Porous media experiments
General details of the equipment and procedures
used in the porous media experiments have been
given previously (Bartosek et al., 1994). Experi-
ments at elevated temperature were run with a back
pressure regulator at 2.5 atm.
Gelant injectivity was measured at ambient tem-
perature in Clashach sandstone cores (4-cm length
× 2.5-cm diameter) of 1 D permeability and in a
Portland limestone core (10 cm × 2.5 cm, 160 mD)
using a constant flow rate of 30 ml/h. The gelant
199
solution was pre-filtered through a 5-1xm Millipore
filter, aged to 50% of its gelation time in bulk (24 h)
at 120°C and then cooled before injection.
One slim-tube experiment was carried out with a
3 m × 0.8-cm i.d. stainless-steel tube dry-packed
with clean quartz sand (75-125 p~m) and fitted with
nylon endcap screens. After packing with sand, the
slim-tube was coiled and saturated with SSW under
vacuum and placed in a forced air oven. The initial
permeability was 3300 roD. Phenol propagation in
the brine-saturated slim-tube was characterized at
120°C by injecting brine containing 1000 ppm phe-
nol and 100 ppm of I tracer as KI. The phenol and
I tracer were monitored simultaneously by UV at
268 and 234 nm, respectively. The I absorption at
234 nm was corrected for the modest contribution of
phenol at this wavelength.
The slim-tube was oil-saturated by flooding at a
differential pressure of 50 bar with 1 1 (16 PV) of a
light, paraffinic crude oil at ambient temperature.
This was followed by flooding with 1 1 of SSW at 50
bar and 120°C to establish residual oil saturation.
The p h e n o l / I - tracer flood was then repeated at
120°C in order to determine both the water saturation
and the phenol retention by the residual oil. Finally,
the slim-tube was flooded with a phenol-formal-
dehyde/PAAm gelant at 120°C at an initial flow rate
of 30 ml/h. From the recorded pressure history, the
change in the apparent viscosity of the in-situ gelant
with time was calculated from Darcy's law.
A second experiment was carried out with a
6.6-m brine-saturated slim-tube. The gelant was in-
jected at 0.08 ml/min at 140°C until the maximum
injection pressure was reached (150 bar). At this
point the slim-tube was shut-in for 24 h and then
cooled to ambient temperature. The slim-tube was
cut into pieces 10 cm in length, and their resistance
to flow was tested by applying a constant flow rate
of brine (0.05 ml/min) for a few minutes.
2.5. Numerical modeling
The effect of phenol partitioning into the residual
oil phase during injection of gelant into the reservoir
was modeled using SQUEEZE~V (Sorbie, 1990; Sorbie
et al., 1991). It was convenient to transform mathe-
matically the phenol equilibrium with the immobile
oil phase into an equivalent adsorption onto the
200 S.L. Br?,'ant et al. / Journal of Petroleum Science and Engineering 17 (1997) 197-209
reservoir rock. Partitioning of polymer and formal-
dehyde into the oil phase and their adsorption onto
reservoir rock were taken to be zero. Physical disper-
sion was simulated by numerical dispersion (1-2
ft2/day).
3. Results and discussion
3.1. Bulk studies
Bulk chemical studies on gelants serve to define
the range of compositions and the conditions under
which gelation occurs. Appropriately designed exper-
iments can also yield insights into the factors that
control gelation delay, gel stability and the sensitiv-
ity of the gelation chemistry to interference by
fluid-fluid and fluid-rock interactions. In this part
of the paper we report on experiments carried out in
order to characterize the influence of pH on the
gelation reaction and to identify parameters that in-
fluence the rate of gelation at elevated temperature.
The reader is directed elsewhere (Albonico et al.,
1995) for studies defining the optimum phenol and
formaldehyde concentrations for the polymers em-
ployed in the present studies. Those tests also estab-
lished that the phenol-formaldehyde cross-linking
system is relatively insensitive to the salinity of the
aqueous medium, and showed that the gel properties
do not depend strongly on the weight ratio of
phenol:formaldehyde; unless otherwise noted, a 1:1
weight ratio is employed in the studies reported
below,
3.1.1. Gelation sensitir'i~ to pH
Many formation brines are buffered by the forma-
tion rock to a neutral or weakly acidic pH (Seright,
1992). It is reasonable to expect that the pH of a
gelant introduced into such a formation will ap-
proach the pH of the resident formation fluids unless
the gelant is strongly buffered or the formation has
been modified by an appropriate pre-flush. The re-
ported requirement of an alkaline pH for gelation
(Falk, 1984) was therefore perceived as a potential
limitation of phenol-formaldehyde gelants. Surpris-
ingly, however, measurements on several phenol-
formaldehyde gelants near the gel point revealed a
marked tendency of the solutions to evolve to a pH
of ~ 6 during the gelation process, independent of
their initial pH. The pH range over which these gels
form was better defined by preparing a number of
phenol-formaldehyde/PAAm-AMPS gelants cov-
eting the interval from pH 1 to pH 8.5. By means of
frequent monitoring and correction of the pH with
acid or base, it was possible to maintain the gelants
to within 0.5 pH unit of the initial value through the
gelation point. Gelation occurred over the entire
interval examined, indicating that this cross-linking
chemistry is functional over a wide range of pH.
The constant-pH experiments also yielded infor-
mation on the influence of pH on the gelation delay.
Polymer cross-linking was slowest at neutral pH and
accelerated sharply at pH 1. The limited experimen-
tation at alkaline pH suggests that cross-linking may
also accelerate above pH 8. Most significantly, how-
ever, the gelation delay varied by less than a factor
of 2 over the pH range of interest for field applica-
tions, pH 4.5-8. This means that the inherent rate of
the polymer cross-linking reaction should be rela-
tively insensitive to acid-base interactions that occur
within the formation, a most desirable property in a
gelant. We speculate that the slower gelation kinetics
below pH 8 might be responsible for the earlier
conclusion (Falk, 1984) that gelation requires an
alkaline pH (preferably pH 8-9). Rheological mea-
surements (Albonico et al., 1995) confirmed that the
final mechanical properties of the gels were insensi-
tive to pH.
3.1.2. Gelation delay
It has been suggested (Falk, 1984; Moradi-Araghi
et al., 1993) that the gelation time of phenol-formal-
dehyde gelants can be conveniently modified by
varying the phenol and formaldehyde concentrations.
We find, instead, that the gelation times of PAAm-
AMPS solutions vary by less than three-fold for
phenol and formaldehyde concentrations from 800 to
8000 ppm. The PAAm and PAAm-VP-AMPS
polymers behaved similarly. Considering the re-
stricted range of cross-linker concentrations that yield
gels of good strength and stability for a given poly-
mer solution, these results suggest that the possibili-
ties of programming the gelation time of phenol-for-
maldehyde/polymer gelants by adjusting the cross-
linker concentration are, in fact, quite limited.
Temperature, on the other hand, influences the
 S.L. Bo,ant et al. / Journal of Petroleum Science and Engineering 17 (1997) 197-209 201

gelation time quite strongly. The results for the three
acrylamide polymers plotted in Fig. 1 show that for a
given composition, the gelation times decrease by a
factor of 5-20 on passing from 90 ° to 120°C (see
also Moradi-Araghi et al., 1993). Except for the 5%
PAAm solution, cross-linking proceeds extremely
slowly at 60°C. This observation is consistent with
earlier indications that the lower useful temperature
limit for this cross-linking system is 70-80°C (Falk,
1984; Moradi-Araghi et al., 1993).
Importantly, the results presented in Fig. 1 show
that the gelation time is strongly dependent on the
type and concentration of polymer employed. The
low-molecular-weight PAAm compositions gel an
order of magnitude more rapidly than the acrylamide
copolymer gelants; gelation of the 5% PAAm solu-
tions takes place readily even at 60°C. While the
gelation delay of a given gelant will largely be
determined by the formation temperature, the marked
difference in the gelation delays obtained with differ-
ent polymer compositions increases the possibilities
of finding a suitable gelant for a given reservoir
treatment. Between the fast-gelling, low-molecular-
weight PAAm and slower-gelling P A A m - V P -
AMPS compositions, phenol-formal-
dehyde/polymer gelants can be formulated to satisfy
the requirements of most near-wellbore treatments
from 60° to 140°C and beyond. The variation in
gelation delay for the systems in Fig. l correlates
with several factors that would be expected to accel-
erate the cross-linking reaction: increasing acryl-
amide comonomer content of the polymer, increasing
polymer concentration, and increasing concentration
of phenol and formaldehyde, although our previous
results suggest that the latter factor has only a lim-
ited impact.
3.2. Gelant propagation and injectiL,i~ in porous
media
The experimentation on bulk solutions confirmed
that phenol-formaldehyde/polymer compositions
possess many of the attributes required of a gelant
for application at high temperature: the gelation de-
lays are technologically useful and, to a reasonable
degree, programmable to at least 140°C; the cross-
linking chemistry is relatively insensitive to pH over
a wide pH range. The movement of a gelant through
porous media, however, introduces a number of
complex factors such as fluid-rock interactions,
which can progressively modify the chemical com-
position of the gelant by adding ionic species to it,
by changing its pH, or by retaining polymer or
cross-linker. There will also be intimate contact be-
tween the propagating gelant and the crude oil in
matrix rock. Filtration of partially cross-linked poly-

~5o l

", F--.o---PAAm 5% 1
~x - - - ~ - - - P A A m 3°1o I
~
o 125 ', - -,D - Terpolymer 1% I
Terpolymer 2 ~J
4

~ 100~

E
75

50
0.01 0,1 1 10 100 1000

gelation time, days

Fig. 1. Gelation times for phenol-formaldehyde/polymer gelants are strongly dependent upon temperature and polymer type and
concentration, but are insensitive to pH and cross-linker concentration (data shown here for initial pH 6). The dependence upon polymer
type permits tuning the gelation delay across a wide range of times, even at high temperatures.
202 S.L. Bryant et al. / Journal of Petroleum Science and Engineering 17 (1997) 197 209
mer from the gelant by the pore throats of the rock
could affect the injectivity and placement of the
gelant. It is possible to evaluate the importance of
such phenomena by means of porous media experi-
ments coupled with numerical simulation. In this part
of the paper we will report on sandpack and core-
floods carried out in order to characterize the propa-
gation and injectivity of phenol-formaldehyde
cross-linked polymer gelants.
3.2.1. Gelant turbidity
While carrying out the studies reported in the first
part of this paper, we observed that the phenol-for-
maldehyde gelants quickly became turbid, and had
turned opaque by their gel point. Surprisingly, the
earlier literature does not refer clearly to this phase
separation process. Experiments on simple phenol-
formaldehyde solutions showed that the separating
phase was formed by reaction between the two
cross-linkers. In the absence of polymer, the initial
milky dispersion gave way to a viscous oil that
settled to the bottom of the container and later
solidified, presumably yielding a Bakelite-like mate-
rial (Moradi-Araghi et al., 1993). Evidently, the pres-
ence of polymer in the gelant solution inhibits coagu-
lation and settling of the dispersion before gelation
occurs. It remains unclear whether the condensed
phenol-formaldehyde oil phase plays a role in poly-
mer cross-linking or whether it is an inert side
product.
The presence of phase-separated material in the
phenol-formaldehyde/polymer gelants has potential
implications for the injectivity and propagation of
these compositions in a rock matrix: if the dispersed
phase were stripped from the propagating gelant, its
accumulation could prematurely reduce the perme-
ability of the formation. If the separated phase were
important for polymer cross-linking, then its filtra-
tion from the propagating solution would compro-
mise the gelation at the leading front of the gelant.
In order to determine the impact of the phase-sep-
arated material on injectivity, experiments were car-
ried out with phenol-formaldehyde/polymer gelants
that had been heated for some fraction of their
gelation time. These highly turbid, partially cross-
linked solutions were cooled to room temperature to
stop further reaction and then pumped through porous
media of varying characteristics. Results of one such
experiment using a 1 D Clashach sandstone core and
a P A A m - A M P S gelant (1% in polymer, 1000 ppm
each, phenol and formaldehyde) heated to 50% of its
gelation time are shown in Fig. 2. Whereas the
injection pressure at constant flow was steady for the
uncross-linked gelant, it increased slowly but contin-
uously for the turbid gelant, suggesting a small
degree of filtration. A similar experiment was run
using a P A A m - V P - A M P S gelant (l% in polymer,
4000 ppm each, phenol and formaldehyde) with a
160 mD Portland limestone core. Once again, only a
very slight rise in the injection pressure with injected
volume was observed for solutions that had been
aged either to 25% or to 50% of their gelation time.
Measurement of the turbidity of the gelant aged to
25% of its gelation time indicated less than a 10%
decrease after passage through the limestone core.
Complementary results were obtained in filtration
experiments with Millipore filters. These experi-
ments showed that a P A A m - A M P S gelant heated at
120°C to beyond 50% of its gelation time in bulk
passed through a 5-1xm filter without evidence of
filtration. Some filtration was observed with a l q x m
filter, which provides an indication of the dimensions
of the phase-separated material or cross-linked ag-
gregates that were present in the partially cross-lin-
1 Gelant aged at 120°C Ibr
~08- Gelant freshly prepare(]
~ 06T
Flow rate = 31} m L / h
~ o4T T=25°(:
c __4
02
°o- ,; ;; ; ; 3; 20 .
P o r e v o l u m e i n j e c t e d (1 P V = 4 . 5 rnL)
Fig. 2. lnjectivity at constant flow rate and ambient temperature in
a 1000 mD sandstone core of an uncross-linked phenol-formal-
dehyde/PAAm-AMPS gelant and the same gelant after aging at
120°C for 50% of its gelation time. The freshly prepared solution
is completely uncross-linked and does not alter injectivity at all.
The aged solution is very turbid, but neither the turbidity nor the
partial cross-linking impair injectivity significantly; after 40 PV
the injection pressure has increased only 15%. Similar results
were observed in a 160 mD limestone, indicating that this system
exhibits good injectivity regardless of lithology.
 S.L. Bryant et al./ Journal of Petroleum Science and Engineering 17 (1997) 197-209 203

ked solution. Together these experiments suggest flow t ' = dXfD/dto, where x~ is the dimensionless
that separation of the phenol-formaldehyde reaction position of the phenol concentration front. Since K
products by filtration in formation rock is not likely and Sor are constant, v is also constant, and the time
to be important, at least up to a significant fraction of at which the phenol front arrives at some position x o
the gelation time in bulk. in the porous medium is simply:
arrival XD
. = -- (3)
3.2.2. Cross-linker propagation U

A series of experiments in a 3-m sandpack illus-

3.2.2.1. The influence of phenol partitioning. Previ-
trates these concepts. An aqueous solution of phenol
ous studies have shown that phenol, phenol deriva-
propagated through the brine-saturated slim-tube
tives, and formaldehyde propagate through brine-
without detectable separation of the phenol from the
saturated porous media without retention (Seright
tracer (Fig. 3, upper part). After establishing residual
and Martin, 1991; Moradi-Araghi et al., 1993). How-
oil saturation (So~ = 0.2) with a light crude oil ( K =
ever, in view of the organic nature of these cross-lin-
0.52), the slim-tube was again flooded with aqueous
kers, we were concerned that they might possess
phenol (1000 ppm). This time the phenol exited 7 ml
sufficient solubility in crude oil to be stripped out of
(0.15 aqueous-phase pore volumes) after the tracer
the propagating gelant by partitioning into the resid-
(Fig. 3, lower part). The observed arrival time of
ual oil phase. Indeed, when aqueous solutions of
phenol (1000 ppm) were exposed to equal weights of
three light-to-medium crude oils, between 40% and
70% of the phenol passed into the oil phase. The
corresponding values of the partitioning coefficient 08
!1 I f
K ranged between 0.5 and 2, where K is defined as
the ratio of equilibrium phenol concentrations in the
r:
two phases: ~4 • tracer ,

Co E
K- (1) • J
Cw m i

Analogous experiments showed no partitioning of 4() 45 50 g~ 0{] 65 70

formaldehyde into the oil phase. Injected volume, mL

The immediate field implication of phenol parti-

tioning is that the volume of gel formed in the
reservoir will be less than the volume of gelant
injected. This effect can be quantified by adapting S" OIq' I:
the theory of chromatography so that the immobile (18

residual oil phase acts as the adsorbent, and the 22

: phenol ]
phase equilibrium expression of Eq. (1) replaces the
adsorption isotherm. Assuming a constant partition- 04 * tracer i
t
ing coefficient yields a simple expression for the rate
~- n 2
at which the phenol concentration front advances Z
f
into the porous medium:
411 45 z'll 55 (~ll 65 70 7~
1
v - S,,~ (2) Injected volume, m L

l + K - - Fig. 3. Phenol propagates together with the tracer through a 3-m

l - Sor sandpack at 100%brine saturation (upper plot). In the presenceof
residual oil, the arrival of the phenol concentration front is
The velocity c is relative to the velocity vt at which delayed due to phenol partitioning into the oil (lower plot). Both
an inert aqueous tracer would propagate. For linear floods were carried out at 120°C.
204 S.L. Bo,ant et al./ Journal of Petroleum Science and Engineering 17 (1997) 197 209

1.15 PV agrees well with the value of 1.13 PV
calculated from Eqs. (2) and (3). The rapid rise of
the phenol curve to the injected level, once it began
to exit from the core, indicates that the partitioning
of phenol into the light crude oil was an equilibrium
process. Phenol was recovered quantitatively during
a brine post-flush, establishing the complete re-
versibility of the phenomenon.
3.2.2.2. The influence of dispersion. Dispersion
causes significant dilution at the leading edge of the
injected gelant. Qualitatively this has the same effect
as phenol partitioning: the volume of gel formed will
be less than the volume of gelant injected. Moreover,
an absorption process governed by a linear relation-
ship such as Eq. (1) will be dispersive in the same
way that a tracer concentration front is dispersive.
Thus dispersion will spread the slower-moving phe-
nol front as well as the formaldehyde and polymer
fronts, exacerbating the problem of phenol retention
discussed above.
To illustrate the magnitude of these effects, con-
sider a treatment for a target interval that is 10 ft
thick, has 20% porosity and contains a medium
crude oil ( K = 2.2) at a residual saturation of So~ =
0.3. Suppose that a gelant volume of 320 bbl (51 m 3)
is injected. This is sufficient to fill the reservoir
aqueous phase volume around the well to a radius of
20 ft. A numerical simulation of this treatment is
shown in Fig. 4. Dispersion has spread the concen-
tration fronts substantially during their advance into
the reservoir. The phenol front lags those of formal-
dehyde and polymer, due to absorption of phenol
into the residual crude oil.
Suppose now that gelation occurs only where the
gelant contains at least 80% of the injected concen-
trations of the polymer and of each of the two
cross-linkers. This threshold concentration for
formaldehyde and the polymer is at a distance of
16.5 ft from the wellbore (Fig. 4). Thus the 35% of
the injected gelant volume that lies beyond this
distance would not form gel, even in the absence of
phenol partitioning. In this example phenol falls
below the 80% threshold concentration just 8.3 ft
from the wellbore. The gelant solution lying within
this distance of the wellbore, i.e., that which would
go on to gel during shut-in, is only 17% of the
volume injected.

100000

1 0 0 0 0 ~- - . _
- - ~ Polymer

0 \

I- " - Phenol
0
= ~
"13
[ Formaldehyde

tO [ 8 0 % of ~njected ] ' u ~ 8 0 % Of injected - "\\\

100 L concentration : I concentration

l ",-,,! \

10 - - , '
' r , " ........ .... I ~
0 5 !0 15 20 25

Distance from wellbore, ft

Fig. 4. Simulated concentration profiles of phenol, formaldehyde and polymer in injected gelant as a function of radial distance from the
wellbore. The injected volume is equal to the brine-filled pore volume of the formation within 20 ft of the wellbore. Gel will not form in this
entire volume, however. Dispersion reduces the concentrations of all the gelant components at the leading edge of the injected slug. The
phenol cross-linker penetration is further reduced by partitioning into residual oil in the formation.
 S.L. Brn'ant et al. / Journal of Petroleum Science and Engineering 17 (1997) 197-209
3.2.3. Methods to improve propagation
Dispersion and phenol partitioning obviously re-
sult in wasted chemical. A more serious problem is
that gel will not form to the desired distance in the
formation. One way to avoid the latter problem is
simply to inject more gelant, While over-sizing the
treatment addresses the issue of depth of penetration,
it increases the economic penalty of production
downtime. Over-sizing also complicates the job de-
sign. A greater volume of viscous fluid must be
pushed into the formation within the time window
imposed by the gelation time,
A better solution is to inject a preflush of phenol.
Suppose the preflush has the same phenol concentra-
tion as the gelant. Then the injected gelant will
encounter oil with a phenol concentration already in
equilibrium with the gelant composition. Thus no
stripping of phenol from the gelant will occur, and
the gelant components will propagate together until
they reach the penetration depth of the preflush.
Since the preflush will have water-like viscosity and
cannot form gel on its own, this option is opera-
tionally simpler than the option of oversizing the
gelant volume. It also means that much more of the
injected gelant will form gel, reducing wasted chemi-
cals.
Increasing the phenol concentration in the gelant
is also a viable means of pushing the desired phenol
concentration deeper into the reservoir. This is not
because a front of high phenol concentration travels
more rapidly than a front of low concentration; Eq.
(2) shows that the velocity is independent of concen-
tration. Rather, a higher injected concentration im-
poses a higher concentration gradient and thus in-
creases the dispersive/diffusive flux.
Numerical simulation was again used to evaluate
these alternatives. The target was to achieve 800
ppm phenol in the gelant at a distance of 16.5 fl from
the wellbore (this corresponds to the concentration
that phenol would have had at this distance if there
were no partitioning). For the increased-concentra-
tion alternative, this requirement is met with a phe-
nol concentration of 2.55% in the gelant. The possi-
ble solutions for the preflush alternative are defined
by two variables, the concentration and volume of
the phenol pre-flush. Assuming that a short pre-flush
and moderate phenol concentration would be pre-
ferred in the field, we find that a 2.5-m 3 slug 10% in
205
phenol would conveniently achieve the target con-
centration in the gelant at the desired depth in the
formation. The polymer, formaldehyde and phenol
profiles for the two alternatives are shown in Fig. 5.
Given the low cost of phenol, both alternatives
appear to be economically sensible ways of achiev-
ing a four-fold increase in the volume of gel formed.
From Fig. 5, however, we see that both of these
approaches will generate high phenol concentrations
in the gelant: with the pre-flush the phenol concen-
tration will be as high as 5000 ppm, while in the
other case the gelant nearest the wellbore will con-
tain 2.55% phenol. Experiments were therefore run
in order to determine whether gelation is affected by
such high concentrations of phenol. FW and SSW
solutions of PAAm (3%) and formaldehyde (1000
ppm) gelled at 120°C in the presence of up to, but
not beyond, 10,000 ppm of phenol. This suggests
that the formaldehyde is tied up unproductively by
phenol at high phenol concentrations, which is rea-
sonable in light of the hypotheses that have been
offered on the cross-linking mechanism (Moradi-
Araghi et al., 1993). Other experiments showed that
the maximum amount of phenol for which gelation
occurs rises with increasing formaldehyde concentra-
tion.
These results rule out the use of a high phenol
concentration in the gelant to compensate for the loss
of phenol into the immobile oil phase. The use of a
phenol pre-flush, on the other hand, appears to be a
viable means for maximizing the conversion of the
gelant to gel within the formation.
This analysis assumes that the viscous (of order
10-100 cP) gelant does not mobilise any residual
oil. Any oil swept out of the treated zone ahead of
the gelant would no longer act as a phenol sink, thus
increasing phenol penetration. The possibility of mo-
bilisation depends upon the producing conditions for
the well and the treatment design, so it is not consid-
ered further here.
3.2.4. Gelant injecticiO'
The gelation reaction changes an ordinary viscous
solution into an elastic solid which cannot be pumped
through porous media at practical pressures. The
evolution of the effective viscosity of the gelant
during this reaction imposes obvious constraints on
the placement of a treatment. To assess its injectiv-
206 S.L. B ~ a n t et al. / Journal of Petroleum Science and Engineering 17 ( 1997) 197-209

ity, a gelant 1000 ppm each in phenol and formal-
dehyde and 3% in PAAm (MW 5 X 105) was pumped
continuously but at different flow rates through a
3-m slim-tube packed with quartz sand and contain-
ing 20% of residual oil at 120°C. At the initial
injection rate (30 m l / h ) the residence time of the
gelant in the sand pack (1.6 h) was much less than
the gelation time measured in bulk at this tempera-
ture (11 h). As shown in Fig. 6 the apparent viscosity
increased as the gelant displaced the brine from the
slim-tube, reaching a steady value of just under 20
cP. (The apparent viscosity is calculated directly
from Darcy's law and the observed pressure drop,
ignoring the presence of the oil phase. It thus in-
cludes the effect of any permeability reduction due
to filtration or blockage.) Reducing the flow rate to
12 m l / h and then to 6 m l / h increased the residence
time to 37% and 75% of the gelation time, respec-
tively, yet the gelant remained pumpable, with no
significant change in the apparent viscosity. How-
ever, when the injection rate was reduced to 1.2
ml/h, the residence time of the gelant in the sand
pack was much longer than the gelation time. After
6-h injection at this rate the pressure limit of the
equipment was reached and injection was halted• At
this point, gelant in the last quarter of the slim-tube
had been in the sand pack for at least 11 h, the
gelation time in bulk. The steady increase in the
apparent viscosity during this stage of the experi-
ment reflects the increasing volume of gelant in the
slim-tube approaching the gel point.
A second slim-tube experiment was carried out in
order to confirm that gel forms at the leading front of
the gelant. This was accomplished using a 2%
PAAm-VP-AMPS SSW gelant (containing 4000
ppm each of phenol and formaldehyde) with a bulk
gelation time of 17 h at 140°C. The flow rate was
chosen so that after 17 h of injection the gelant
would have arrived approximately half-way through
the 6.6-m brine-saturated slim-tube. The experiment
was terminated after 9.5 h of injection when the
injection pressure had reached 150 bar. At this point,
the calculated gelant front (neglecting dispersion)
had penetrated to a depth of 2.33 m. The 10-cm
lengths of the slim-tube (see Section 2.4) between
the inlet and 2.3 m from the inlet resisted flow at
pressure drops up to 200 bar. Gelled sand was
extruded from the sections between 2.3 and 2.4 in
from the inlet at 55 bar. Free-flowing sand was
extruded from the sections beyond 2.4 m at low

100000 ~-

J Phenol (concentrated gelant)

0-4 . . . . "0 - o - • 0-

E
Q.
t-
10000

1
t Phenol (prefiush then . . "
normal gelant) n"
"I --

" ' - E l ".

",'.:.
"~olymer

.O
i
1000 ~ " "
¢
0
¢
0 ",', Formaldehyde
\
100 q
-,-Q \

,i! :, -,-..-~
5 10 15 20 25

Distance from wellbore, ft

Fig. 5. Simulated concentration profiles of phenol, tormaldehyde and polymer for two methods of increasing phenol penetration. Increasing
the concentration of phenol in the gelant to 2.55% gives the same depth of effective phenol penetration as in a formation with no residual
oil. Another way to achieve the same penetration is to precede the placement of normal gelant with a small volume of concentrated phenol
solution (in the example depicted here, 2.5 m 3 of 10% solution).
 S.L Br>,ant et al. / Journal of Petroleum Science and Engineering 17 (1997) 197-209
too T
i
9o
l
go
30
A
e~ ' mL/t
o 70 16 t
60
0
U
"g 50.-
40.
0 s ~0
Fig. 6. Apparent viscosity (as defined in text) of phenol-formaldehyde/PAAm gelant injected continuouslyinto a 3-m sandpack at 120°C at
decreasing flow rates. The labels for each section give the flow rate and correspondingresidence times. The apparent viscosity of the gelant
does not increase from its initial value until the residence time of the gelant in the sandpack exceeds the gelation time, which is 11 h for this
formulation.
pressure. Thus the maximum depth of effective gel
formation corresponds to the calculated depth of
gelant penetration. This desirable feature of the phe-
nol-formaldehyde system is not restricted to sand-
packs. Gelant injected into a Portland limestone core
formed gel throughout the core length. The insensi-
tivity to lithology is a significant advantage, as it
simplifies treatment design and reduces the chances
that unknown or unexpected variations in formation
mineralogy could compromise the treatment.
The above slim-tube experiment also demon-
strates how effectively these gels reduce permeabil-
ity. Typical post-gelation permeabilities are tens of
microdarcies, regardless of the lithology or the initial
permeability of the medium. These values are com-
parable to those found for other strong gels (Seright,
1993). Hence the phenol-formaldehyde system
should have the same capacity for stopping fluid
flow in high-temperature formations that other sys-
tems offer in less harsh environments.
4. Conclusions
Phenol-formaldehyde/polymer gelants are an at-
tractive system for fluid shut-off in high-temperature
207
12 mL/h 6 mL/h 12 mL/h
41h 82h 41 h
~s 2o 25 30 3s 40
Time (hours)
formations. Cross-linking occurs over a broad pH
range, and the gelation delay is relatively insensitive
to this parameter. In contrast, gelation delay depends
strongly upon temperature and the nature and con-
centration of the polymer used. By selecting between
different polymer compositions, reasonable flexibil-
ity in the gelation time can be achieved over the
temperature range from 60 ° to at least 140°C. The
turbidity that results from reaction between the phe-
nol and formaldehyde cross-linkers has limited or
negligible effects on gelation, gelant propagation or
gelant injectivity. Indeed, the gelants can be injected
through 3-m sand packs at 140°C even for residence
times approaching the gelation time. Porous media
studies show that the propagation and the gel perfor-
mance of this system are not sensitive to lithology.
The solubility of phenol in crude oil is the primary
disadvantage of this system. Simulations show that
the simplest method to overcome this problem is to
inject a slug of phenol before the gelant.
5. Notation
C~, = concentration of phenol in crude oil
(mol/l)
208 S.L Bryant et al. / Journal of Petroleum Science and Engineering 17 (1997) 197-209
Cw = concentration of phenol in brine (mol/1)
K = phenol partitioning coefficient between
brine and crude oil (dimensionless)
Sot = residual oil saturation (dimensionless)
r = velocity of phenol concentration front
relative to velocity of inert aqueous tracer
t,~ = velocity of inert aqueous tracer through a
porous medium
xD = dimensionless distance within porous
medium
x~ = dimensionless position of phenol concen-
tration front within porous medium
tD = dimensionless time (pore volumes in-
jected)
t~rri,,~
D = dimensionless time at which phenol con-
centration front reaches given position
within a porous medium
Acknowledgements
It is a pleasure to acknowledge Giuseppe Calloni
for his contributions to several of the experiments
described in this paper, Alberto Malandrino for the
numerical simulations and Paola Albonico for the
bulk gelation experiments. This research was sup-
ported by Agip SpA. Parts of this paper were pre-
sented at the 1995 SPE Oilfield Chemistry Sympo-
sium, San Antonio, Texas, as SPE 28983.
References
Albonico, P. and Lockhart, T.P., 1993. Divalent ion-resistant
polymer gets for high temperature applications: syneresis in-
hibiting additives. Presented at Soc. Pet. Eng. Int. Symp. on
Oilfield Chemistry, New Orleans, LA, Mar. 2-5, Pap. SPE
25220.
Albonico, P., Burrafato, G., Di Lullo, A. and Lockhart, T.P.,
1993. Effective gelation-delaying additives for Cr+3/polymer
gels. Presented at Soc. Pet. Eng. Int. Symp. on Oilfield
Chemistry, New Orleans, LA, Mar. 2-5, Pap. SPE 25221.
Albonico, P., Bartosek, M., Lockhart, T.P,, Causin, E. and Rossi,
E., 1994. New polymer gels for reducing water production in
high temperature reservoirs. Presented at Eur. Prod. Oper.
Conf. Exhibit., Aberdeen, Mar. 15-17, Pap. SPE 27609.
Albonico, P., Bartosek, M., Malandrino, A., Bryant, S. and Lock-
hart, T.P., 1995. Studies on phenol-formaldehyde crosslinked
polymer gels in bulk and in porous media. Presented at Soc.
Pet. Eng. Int. Symp. on Oilfield Chemistry, San Antonio, TX,
Feb. 14 17, Pap. SPE 28983.
Bartosek, M., Mennella, A., Lockhart, T.P., Causin, E., Rossi, E.
and Passucci, C., 1994. Polymer gels for conformance treat-
ments: propagation of Cr(III) cross-linking complexes in
porous media. Presented at the Soc. Pet. Eng./U.S. Dep.
Energy 9th Syrup. on Improved Oil Recovery, Tulsa, OK,
Apr. 17-20. Pap. SPE/DOE 27828.
Borling, D.C., 1994. Injection conformance control case histories
using gels at the Wertz Field CO 2 tertiary flood in Wyoming.
Presented at Soc. Pet. Eng./U.S. Dep. Energy 9th Symp. on
Improved Oil Recovery, Tulsa, OK, Apr. 17-20, Pap.
SPE/DOE 27825.
Bryant, S.L., Rabaioli, M.R and Lockhart, T.P., 1996. Influence
of syneresis on permeability reduction by polymer gels. SPE
Production and Facilities, (Nov. 1996), pp. 209-215.
Falk, D.O., 1984. Process for selectively plugging permeable
zones in a subterranean formation. U.S. Patent 4,485,875
(Dec. 4, 1984).
Hauser. T.R. and Cummings, R.L., 1964. Increasing sensitivity of
3-methyl-2-benzothiazolone hydrazone test for analysis of
aliphatic aldehydes in air. Anal. Chem., 36: 179.
Lockha~, T.P. and Albonico, P., 1992. A new gelation technology
for in-depth placement of Cr + 3/polymer gels in high-temper-
ature reservoirs. Presented at Soc. Pet. Eng./U.S. Dep. Energy
8th Symp. on Enhanced Oil Recovery, Tulsa, OK, Apr. 22-24,
Pap. SPE/DOE 24194.
Moradi-Araghi, A., Beardmore, D.H. and Stahl, G.A., 1988. The
application of gels in enhanced oil recovery: theory, polymers
and cross-linker systems. In: G.A. Stahl and D.N. Schulz
(Editors), Water-Soluble Polymers for Petroleum Recovery.
Plenum, New York, NY, pp. 299-312.
Moradi-Araghi, A., Bjornson, G. and Doe, P.H., 1993. Thermally
stable gels for near-wellbore permeability contrast corrections.
Soc. Pet. Eng. Adv. Technol. Ser., 1: 140-145.
Sanders. G., Chambers, M. and Lane, R., 1994. Successful gas
shutoff with polymer gel using temperature modeling and
selective placement in the Prudhoe Bay field. Presented at
69th Soc. Pet. Eng. Annu. Tech. Conf. Exhibit., New Orleans,
LA, Sept. 25-28, Pap. SPE 28502.
Seright, R.S., 1988. Placement of gels to modify injection profiles.
Presented at Soc. Pet. Eng./U.S. Dep. Energy 6th Enhanced
Oil Recovery Syrup., Tulsa, OK, Apr. 17-20, Pap. SPE/DOE
17332.
Seright, R.S., 1992. Impact of permeability and lithology on gel
performance. Presented at Soc. Pet. Eng./U.S. Dep. Energy
8th Symp. on Enhanced Oil Recovery, Tulsa, OK, Apr. 22-24,
SPE/DOE 24190.
Seright, R.S., 1993. Effect of rock permeability on gel perfor-
mance in fluid-diversion applications. In Situ, 17: 363-386.
Seright, R.S. and Martin, F.D., 1991. Impact of gelation pH, rock
permeability, and lithology on the performance of a
monomer-based gel. Presented at Soc. Pet. Eng Int. Syrup. on
Oilfield Chemistry, Anaheim, CA, Feb. 20-22, Pap. SPE
20999.
Sorbie. K.S., 1990. The SQUEEZE IV User Manual. Dep. Pet.
Eng., Heriot-Watt Univ., Edinburgh.
 S.L. Bryant et al. / Journal of Petroleum Science and Engineering 17 (1997) 197-209 209

Sorbie, K,S., Yuan, M.D., Todd, A.C. and Wat, R.M.S., 1991.
The modelling and design of scale inhibitor squeeze treat-
ments in complex reservoirs, Presented at Soc. Pet. Eng. Int.
Symp. on Oilfield Chemistry, Anaheim, CA, Feb. 20-22, Pap.
SPE 21024.
Sydansk, R.D., 1993. Acrylamide-polymer/chromium(llI)-
carboxylate gels for near wellbore matrix treatments. Soc. Pet.
Eng. Adv. Technol. Set,, 1: 146-152.
Sydansk, R.D. and Moore, P., 1992. Gel conformance treatments
increase oil production in Wyoming. Oil Gas J. (Jan.), 20:
40-45.