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Novel Gel with Controllable Strength for In-Depth


Conformance Control: Bulk Gelation Performance and
Propagation Properties in Porous Media
a a b c
Hong He , Yefei Wang & Jian Zhang
a
College of Petroleum Engineering , China University of Petroleum (East China) , Qingdao ,
Shandong , P. R. China
b
State Key Laboratory of Offshore Oil Exploitation , Beijing , P. R. China
c
CNOOC Research Institute , Beijing , P. R. China
Accepted author version posted online: 16 Jun 2014.Published online: 20 Dec 2014.

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To cite this article: Hong He , Yefei Wang & Jian Zhang (2015) Novel Gel with Controllable Strength for In-Depth Conformance
Control: Bulk Gelation Performance and Propagation Properties in Porous Media, Journal of Dispersion Science and Technology,
36:5, 626-633, DOI: 10.1080/01932691.2014.933436

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Journal of Dispersion Science and Technology, 36:626–633, 2015
Copyright # Taylor & Francis Group, LLC
ISSN: 0193-2691 print=1532-2351 online
DOI: 10.1080/01932691.2014.933436

Novel Gel with Controllable Strength for In-Depth


Conformance Control: Bulk Gelation Performance and
Propagation Properties in Porous Media
Hong He,1 Yefei Wang,1 and Jian Zhang2,3
1
College of Petroleum Engineering, China University of Petroleum (East China), Qingdao,
Shandong, P. R. China
2
State Key Laboratory of Offshore Oil Exploitation, Beijing, P. R. China
3
CNOOC Research Institute, Beijing, P. R. China

GRAPHICAL ABSTRACT
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Polymer gel has been widely used to control excessive water production in mature oilfields.
However, in view of reservoir conditions characterized by serious heterogeneous thick oil layers,
high strength and in-depth propagation are required of polymer gel to achieve good treatment
efficiency. Based on the concept of in-depth conformance control, a novel gel with controllable
strength composed of polymer, resorcinol/hexamethylenetetramine (HMTA), acetic acid and
gel strength modifier was developed. The effects of component concentrations on bulk gelation
properties were investigated. The microstructures of conventional gel and novel gel at different
aging time were studied by scanning electron microscopy (SEM), which can provide insight into
the mechanism of controllable gel strength. Moreover, sandpack flow experiments were carried
out on sandpacks (U2.5  100 cm) with multi-point pressure taps to investigate whether the novel
gel can propagate in porous media. Compared with the conventional gel, SEM results showed that
the three-dimensional network structure of novel gel was weakened more seriously, resulting in
the decrease of gel strength. Due to decreased gel strength at different aging time, the novel
gel can propagate in porous media to achieve in-depth conformance control.
Keywords Controllable gel strength, in-depth conformance control, microstructure, polymer
gel, propagation properties, scanning electron microscopy (SEM)

1. INTRODUCTION
Polymer flooding has been proved as an effective
Received 13 May 2014; accepted 8 June 2014. method to improve oil recovery in the offshore oilfield of
Address correspondence to Hong He, No. 66, West Bohai Bay in China.[1,2] However, due to reservoir hetero-
Changjiang Road, Huangdao, 266580, Qingdao, P. R. China. geneity and long-term flushing by polymer solution,
E-mail: hehong1103@gmail.com breakthrough of injected polymer solution along the high
Color versions of one or more of the figures in the article can
permeability channel occurs, resulting in poor sweep
be found online at www.tandfonline.com/ldis.

626
NOVEL GEL FOR IN-DEPTH CONFORMANCE CONTROL 627

efficiency and excessive water production, which significantly investigate the effect of component concentrations on bulk
increases the operation cost. Conformance control that gen- gelation properties; (2) study the effect of gel strength
erally refers to using chemical or mechanical methods to modifier concentration on gelation properties and gel
reduce undesired water production has been proved as an morphology to reveal the mechanism of controllable gel
effective water control technology, which can improve sweep strength; and (3) evaluate the gel propagation properties
efficiency and thus result in an increase in ultimate oil recov- in porous media to demonstrate whether the gel can
ery.[3–8] Polymer gels have been successfully applied to con- propagate in porous media.
trol water production from hydrocarbon wells in many
mature oilfields. Due to the covalent bonds between polymer
and the organic crosslinker, organically cross-linked gels 2. EXPERIMENTAL SECTION
have good long term thermal stability such as 2.1. Materials
phenol-formaldehyde polymer gel, which has been widely
The polymer used in this study was partially hydrolyzed
used to control water production in high temperature reser-
polyacrylamide with high molecular weight of 2  107
voirs.[9–13] However, the key issues associated with phenol
Dalton and a hydrolysis degree of 24.25%. The crosslinkers
and formaldehyde are that they are not environment
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used in this study were resorcinol and hexamethylenetetra-


friendly. To overcome the toxicity, phenol and formaldehyde
mine in AR grade. The gel strength modifier used in this study
could be substituted for less toxic derivatives like resorcinol
was tert-butyl hydroperoxide (TBHP) in AR grade. The
and hexamethylenetetramine (HMTA), respectively.[14–19]
synthetic formation brine with TDS of 2902.22 mg  L1
Polymer gel has been widely used to control excessive water
contained 950.89 mg  L1 Naþ, 11.78 mg  L1 Ca2þ,
production in mature oilfields. However, in view of oilfield
18.83 mg  L1 Mg2þ, 845.52 mg  L1 Cl, 43.62 mg  L1
reservoir characterized by serious heterogeneous thick oil
SO4 2 , 107.14 mg  L1 CO3 2 , and 924.25 mg  L1 HCO 3.
layers, to achieve good treatment efficiency, the conventional
gel should have some characteristic properties such as high
gel strength and good in-depth propagation ability. 2.2. Preparation of the Gelant Solution
However, there exists a contradiction between gel strength The gelant solution was prepared by adding predeter-
and in-depth propagation ability. Previous literatures have mined amounts of polymer, crosslinker, acetic acid and gel
shown that weak gel composed of low concentration strength modifier. Then 15.0 mL gelant solution was injected
polyacrylamide and organic metallic Cr3þ can propagate in into the ampule tube sealed by a torch, after which, the
porous media. While for strong gel, the gel could only pen- ampule tube was placed into a thermostat water bath and
etrate from the fractures in the matrix.[20–22] To improve periodically removed from the water bath for observation.
gel treatment efficiency, different conventional polymer gels
with different gel strength have been combined to achieve 2.3. Gelation Time and Gel Strength Measurement
in-depth conformance control. Compared with in-depth con- Gelation time and gel strength are important parameters
formance control treatment, the conventional near wellbore determining gel placement and plugging efficiency. The gel-
conformance control has some limitations as follows: ation time should be long enough to make sure the gelant
solution can be pumped into the target zone safely. The gel-
1. The remaining oil saturation is low in the immediate
ation time is semi-quantitatively measured by Sydansk
vicinity of wellbore, especially after multiple conform-
gel-strength code method. In this study, the gelation time
ance control treatments, which makes in-depth
is defined as the time when the gel strength of gelant
conformance control needed to make better results.
solutions reaches grade G (Grade G: the gel is described
2. For serious heterogeneous thick oil layers, the conventional
as moderately deformable non-flowing gel and flows
near wellbore conformance control can no longer meet the
approximately half way down the bottle upon inversion).
demand of improving conformance efficiency, resulting in
The gel strength is measured by using the breakthrough
short term fluid diversion of near wellbore. Once injected
vacuum method.[25,26] Figure 1 shows the schematic dia-
fluid bypass near wellbore into deep formation, the valid
gram of gel strength measurement apparatus. The gel
period of conformance control treatment will shorten.
strength is reflected by the pressure difference between
Therefore, in-depth conformance control has become an
the atmospheric pressure and the pressure of suction bottle.
important technology to improve water flooding and
The procedures are as follows: About 15.0 mL gelant sol-
polymer flooding efficiency in recent years.[23,24]
ution was injected into the ampule tube sealed by a torch
Based on the concept of in-depth conformance control, for gelation at a constant temperature of 57 C.Then the
in this article, a novel gel with controllable strength that U tube was quickly put into the gel, and the biggest value
composed of polymer, resorcinol, HMTA, acetic acid and on the pressure gage was defined as the breakthrough vac-
gel strength modifier was developed for in-depth conform- uum value. The bigger the breakthrough vacuum value is,
ance control. The objectives of this research are to: (1) the higher the gel strength is. Before measuring the gel
628 H. HE ET AL.

to the pressure changes, it can be inferred whether the


novel gel can propagate or not in porous media.

3. RESULTS AND DISCUSSION

3.1. Idea and Mechanism of Novel Gel with


Controllable Gel Strength
3.1.1. Idea of Novel Gel with Controllable Strength
FIG. 1. Schematic diagram of gel strength measurement apparatus. Based on the concept of in-depth conformance control, the
idea of novel gel with controllable gel strength is referred to as
strength, water can be used to calibrate the measurement the variable gel strength that can be controlled by adding gel
apparatus. The breakthrough value of water is 0.007 MPa. strength modifier. There exist some differences between the
Each sample was measured three times, and the average conventional gel and novel gel. For the novel gel, the gel
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value was used as the gel strength of the sample. strength can be controlled by adding gel strength modifier
and change with time under reservoir condition. The novel
gel with controllable strength has some characteristic proper-
2.4. Sandpack Flow Experiments ties as follows: (1) easy to be injected and can propagate into
Figure 2 shows the schematic diagram of sandpack flow in-depth formation; (2) changeable gel strength with gel
experimental apparatus used to determine whether the strength modifier concentration and aging time; (3) possible
novel gel can propagate in porous media with aging time. synergic effects of conventional gel with variable strength,
The sandpack (U2.5 cm  100 cm) with multi-point press- which can achieve in-depth fluid diversion in different loca-
ure taps was used to simulate porous media. The experi- tions in reservoir. For the conventional gel, although the gel
mental procedure was as follows: strength can change with time, only the weak gel can propa-
gate into in-depth formation. Figure 3 shows the transport
1. The sandpacks were filled with clean quartz sand of dif-
schematics of combined conventional polymer gel with differ-
ferent mesh size and saturated with synthetic formation
ent strength and novel gel during propagation into formation.
brine.
2. The sandpacks were flooded with synthetic formation
3.1.2. Gelation Mechanism
brine at a flow rate of 1 mL  min1 until the pressure
The gelation mechanism is as follows:
drop across the sandpacks was stable. The permeability
of sandpack was measured by use of Darcy’s law. 1. The hexamethylenetetramine can decompose formalde-
3. Then 0.3PV (pore volume) of gelant solution was hyde slowly under high temperature and acidic condition:
injected into the sandpacks at a flow rate of
1 mL  min1. Then the sandpacks were shut in for a

period of time at the reservoir condition. ðCH2 Þ6 N4 þ 6H2 O ! 6CH2 O þ 4NH3 : ½1
4. Then several pore volumes of synthetic formation brine
were injected into the sandpacks to measure the 2. Then the formaldehyde can react with resorcinol to
multi-point pressure at different aging time. According form hydroxymethyl resorcinol:

FIG. 2. Schematic diagram of sandpack flow experimental apparatus.


NOVEL GEL FOR IN-DEPTH CONFORMANCE CONTROL 629

3.1.3. Controllable Mechanism of Gel Strength


The controllable mechanism of gel strength is as follows:
1. The gel strength modifier TBHP can decompose sponta-
neously to release free radicals under reservoir temperature

ðCH3 Þ3 COOH ! ðCH3 Þ3 CO  þHO: ½4

2. Then the free radicals can destroy the polymer chain,


weakening three-dimensional network structures and
decreasing the gel strength.

3.2. Bulk Gelation Performance


3.2.1. Effect of Polymer and Crosslinker Concentration
The effect of polymer and crosslinker concentration on
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gelation was studied by preparing polymer and crosslinker


solutions with different mass concentrations. The crosslin-
ker was composed of resorcinol and HMTA, of which the
concentration ratio was 1:4. Figures 4 and 5 show the gel-
ation time and gel strength as a function of polymer and
crosslinker concentration. As polymer and crosslinker con-
centration increased, the gelation time decreased and gel
strength increased. The reaction chances between the amide
groups (-CONH2) and hydroxymethyl (-CH2OH) groups
increased, which resulted in a decrease in gelation time
FIG. 3. Schematics of combined conventional polymer gel with different and an increase in gel strength.
strength and novel gel during propagation into formation: (a) conventional
gel with different strength and (b) novel gel with controllable strength.
3.2.2. Effect of Gel Strength Modifier Concentration
The novel gel with controllable strength can be con-
trolled by adding TBHP as gel strength modifier. The gel
strength modifier was added to control the gel strength,
which can alter the gel strength with aging time. Figure 6
shows the gelation time and gel strength as a function of
TBHP concentration. Figure 7 shows the gel strength of
3. The formaldehyde and hydroxymethyl resorcinol react novel gel with different TBHP concentrations as a function
with the amide groups of polyacrylamide to form
three-dimensional network structure. The reaction
equation are listed as follows:

FIG. 4. Effect of polymer concentration on gelation time and gel


strength (57 C).
630 H. HE ET AL.

of aging time. As we can see from Figure 6, the gelation


time and gel strength changed slightly with increasing
TBHP concentration, which indicated that the TBHP
could not affect the gelation. However, the gel strength
changed with increasing TBHP concentration at different
aging time. The higher the TBHP concentration was, the
lower the gel strength was.
Therefore, on the basis of bulk gelation performance
studies, according to proper gel strength and gelation time,
the gel formulation was optimized as follows: (1500–2000)
mg  L1 polymer þ (1000–1500) mg  L1 resorcinol=
HMTA crosslinker þ (1000–1500) mg  L1 acetic acid þ
(100–300) mg  L1 gel strength modifier.
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FIG. 5. Effect of crosslinker concentration on gelation time and gel


strength (57 C).
3.3. Gel Morphology Study
To determine the mechanism of decreased gel strength,
we investigate the effect of aging time on the morphology
of conventional gel and novel gel. The gel morphology that
corresponds to different aging time was studied by scan-
ning electron microscopy (SEM). Figure 8 shows the gel
microstructures of conventional gel and novel gel after
aging for different time. The conventional gel formulation
was composed of 2000 mg  L1 polymer, 1250 mg  L1
resorcinol=HMTA crosslinker, and 1250 mg  L1 acetic
acid. The novel gel was composed of 2000 mg  L1 poly-
mer, 1250 mg  L1 resorcinol=HMTA crosslinker,
1250 mg  L1 acetic acid, and 300 mg  L1 gel strength
modifier. The gel microstructure of conventional gel aged
for 3 days was similar to the novel gel. The gel microstruc-
tures were both tight network structure. However, after
aging for 30 days, the network structure of novel gel was
destroyed more seriously than conventional gel. SEM
FIG. 6. Effect of TBHP concentration on gelation time and gel
strength (57 C). results showed that due to the free radical released from
TBHP, it can destroy the polymer chain, resulting in
decreasing the gel strength.

3.4. Propagation Properties in Porous Media


To evaluate the in-depth propagation of the novel gel in
porous media, sandpack flow experiments were carried out
on long sandpack with diameter of 2.5 cm and length of
100 cm, which can help us determine whether the novel
gel can propagate into formation. The sandpack was div-
ided into three sections and the pressure distribution along
the sandpack was monitored during water flooding at dif-
ferent aging time. Figure 1 shows the schematic of the test
sandpack. The initial permeability and pore volume of the
sandpack were 2.07 mm2 and 190.0 mL respectively.
Figures 9 and 10 show the propagation properties of novel
gel in porous media at different aging time. After aging for
3 days, with increasing injected pore volumes, the inlet
FIG. 7. The gel strength of novel gel with different TBHP concentra- pressure first increased, while the pressure of sections 1
tions versus aging time (57 C). and 2 remained stable. However, after aging for 30 days,
NOVEL GEL FOR IN-DEPTH CONFORMANCE CONTROL 631
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FIG. 8. SEM images of conventional gel and novel gel aged for 30 days: (a) initial SEM image of conventional gel; (b) initial SEM image of novel
gel; (c) SEM image of conventional gel aged for 30 days; (d) SEM image of novel gel aged for 30 days.

FIG. 9. The propagation of novel gel in porous media (sandpack) FIG. 10. The propagation of novel gel in porous media (sandpack)
after aging for 3 days. after aging for 30 days.

the pressure of section 1 increased slightly with injected 5. CONCLUSIONS


pore volumes and the pressure of section 2 remained stable. Based on the concept of in-depth conformance control,
The results indicated that the gel could propagate in porous this article involves bulk gelation performance, gel morpho-
media according to the pressure change in different logy, and propagation properties of a novel gel with control-
sections of sandpack. lable strength. The gel strength of novel gel with controllable
632 H. HE ET AL.

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Thanks to all individuals associated with the project. control. Paper SPE 35444 presented at SPE=DOE
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