Kalgaonkar & Chang (2017) Self-Assembling Nanoparticles A Unique Method For Downhole Sand

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SPE-187237-MS

Self-Assembling Nanoparticles: A Unique Method for Downhole Sand

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Consolidation

Rajendra Kalgaonkar and Frank Chang, Saudi Aramco

Copyright 2017, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE Annual Technical Conference and Exhibition held in San Antonio, Texas, USA, 9-11 October 2017.

This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents
of the paper have not been reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material does not necessarily reflect
any position of the Society of Petroleum Engineers, its officers, or members. Electronic reproduction, distribution, or storage of any part of this paper without the written
consent of the Society of Petroleum Engineers is prohibited. Permission to reproduce in print is restricted to an abstract of not more than 300 words; illustrations may
not be copied. The abstract must contain conspicuous acknowledgment of SPE copyright.

Abstract
When the formation is unconsolidated, sand particles can be produced into the wellbore. Such production
of sand particles is undesirable as it lowers the permeability of the producing zone, erodes surface and
downhole equipment. Costly intervention may be required to mitigate the damage to the well integrity
and the reservoir deliverability. The most common methods of controlling this unwanted sand production
involve: 1. Filter produced fluids through a gravel pack retained by a screen or 2. Use of consolidating
fluids such as resin, a curing agent, along with other chemicals to create a conducive environment for
the resin curing reaction to occur. The gravel packing completion requires special tools and equipment
therefore higher cost. In the case of sand control by chemical consolidation, the resinous material tends
to have relatively uncontrollable setting times, strength, placement, and regained permeability leading to
unsuccessful treatment. With both cost and treatment effectiveness in mind, it is desirable to develop an
improved material and method to mitigate sand production by consolidating the formation sand without
impairing well productivity or injectivity.
The present paper describes the development of a unique chemistry for sand control in unconsolidated
formations. This chemistry involves using positive charge modified nanoparticles that can self-assemble
over the unconsolidated formation sand particles to form a layer of consolidating material thus preventing
any unwanted sand production. The new consolidation treatment material consists of colloidal nanoparticles
modified using a cationic modifier and ionic strength modifier that can be placed downhole as a single
pill. The pill has high affinity to the solid surface therefore less prone to build up in the pore space. Once
cured at reservoir temperature it forms a thin layer of hard gel around the surface of the sand particles,
thus cementing the sand grains together at the same time maintaining open porosity to ensure easy flow of
produced hydrocarbons or injected water.
The newly developed sand consolidation formulation was studied for their ability to consolidate
loose sand and at the same time maintain good permeability. The effect of various ionic modifiers on
consolidation properties was studied. The ability of the cationic modified nanoparticles to self-assemble
around unconsolidated sand and eventually cure to form a consolidated sand pack was investigated. Regain
permeability studies showed good regain permeability of the consolidated sand pack. Furthermore, this
paper describes the concentration effect of the cationic modifier on the regain permeability. Finally, it
2 SPE-187237-MS

shows that the new product provides a controllable curing time, thus avoiding any premature setting of the
nanoparticles in the wellbore.

Introduction
Some subterranean formations are not sufficiently competent to prevent erosion of the formation by the

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flow of the hydrocarbons through the formation. Such formations, often referred to as unconsolidated
or incompetent formations, contain uncemented or loosely consolidated grains of sand, clay or rock (for
example, sandstone, limestone, quartz, zeolites, siltstone, shale or gravel). When the hydrocarbons or water
flows through the formation, the loose materials, in particular, grains of sand, move along with the fluid
causing erosion and disintegration of the formation. The loose sand can accumulate in the formation near
wellbore or in the wellbore. Such an accumulation can cause clogging and reduced flow of the recoverable
fluid thus leading to productivity and injectivity decline (Rahim et al.). These entrained particles of sand
can also cause erosion of the underground equipment (for example, strainers, liners, valves and pumps),
reduce pressure and restrict flow of the fluid (Boudi; Wong et al.; Graham et al.). Loose sand can be carried
by fluid flow to the surface causing erosion to the surface equipment. If a sufficient amount of the sand is
carried away from the producing formation, the formation may collapse causing significant damage to the
well. Further when sand piles up in the bottom holes, they need to be cleaned out to resume the normal
production and injection operations adding well maintenance cost.
Many technologies have been used to prevent sanding in the wells. They are generally categorized into
mechanical, cement packing, gravel packing and chemical methods (Mcleod, 1977; Karian et. al., 1999). The
mechanical sand control methods are broadly used and they include screens, gravel pack, and frac and pack
(Woiceshyn et al. 2010; Hainey et al. 1992). When these mechanical means are used for sanding prevention,
they need to be designed and implemented during the well completion phase. The chemical methods require
pumping a chemical that keeps the sand grains bond together so that they do not produce with the fluids
(Nguyen et al. 2007; Penberthy et al. 1978). The chemicals commonly used include various resins (Nguyen
et al. 2009) such as furan resins or epoxy resins (Friedman and Surles; 1989, 1991). Various researchers
have also proposed the use of polymers like polyacrylamides for sand consolidation (Syndansk, 1993;
Falk, 1984; Moradi-Araghi et al., 1993; Swanson, 1981). Resin consolidation can be used for mitigation
or prevention of sanding in the wells, therefore it provides a cost effective process than mechanical sand
control techniques. Parlar et al. (1998) summarized many benefits of resin consolidation compared to other
sand control methods. These chemical treatments can be performed on the fly, and no additional rigging is
necessary. This technique of treating the unconsolidated formation with a resin that can cure to consolidate
the loose sand can be applied as a remediation technique in mature production wells or to treat openhole
wells or standalone screen wells (Madasu et al. 2016). The drawbacks of chemical sand consolidation
methods are (1) the resulted consolidated sand pack could lack in compressive strength, therefore the sanding
issue could reoccur soon after the treatment; (2) the resin could severely impair the formation permeability;
and (3) some chemistries could be sensitive to formation sand and fluid type, making the effectiveness of
sand consolidation success a hit and miss, and (4) proper placement of the resin into the right zone could
be difficult. Kalgaonkar et al. (2017) proposed the use of a permeability enhancement additive with resin
treatment in order to improve the regain permeability without loss of compressive strength. Various studies
have also been carried out using non polymeric materials like sodium silicate to consolidate sand in oil and
gas producing wells (Cobianco et al., 1999).
Sand control by chemical consolidation involves injecting chemicals into the unconsolidated formation to
provide grain-to-grain cementation. These conventional methods of sand consolidation by chemical reagents
tend to have relatively uncontrollable setting times. A setting time that is too long can result in the fluids
flowing into areas with lower permeability rock, which leads to formation damage. A setting time that is
too short can lead to premature curing of the resin, which leads to an unsuccessful treatment.
SPE-187237-MS 3

The present paper describes a method of sand control in unconsolidated formations using positively
charged modified nanoparticles that can assemble over the sand particles of the unconsolidated formation.
The positive charge modified nanoparticles form a thin layer of consolidating material across the
unconsolidated formation to provide sand control with desired permeability characteristics. The main
advantage of this treatment method is that the entire treatment can be placed downhole in a single step
operation. The pill is initially a low viscosity fluid. In presence of an ionic strength modifier the cationic

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nanoparticles eventually hardens to cement the sand grains together and at the same time ensures that
permeability is retained through the treatment material to facilitate production of hydrocarbons. When
mixed with field sand, the cationic nanoparticles form a strong bond among the grains. Moreover, the
consolidated cationic nanoparticles exhibit good permeability. The concentration of cationic nanoparticles
has been optimized to produce desirable balance between the permeability and the consolidation strength.

Cationic Nanoparticles for Sand Control


The surface of the unconsolidated sand grains has a net negative charge. The positively charged
nanoparticles modified with the cationic species can self-assemble over the unconsolidated formation sand
particles due to electrostatic attraction, to form a layer of consolidating material. Initially the cationic
nanoparticles exist as a low viscosity solution. In presence of an activator these cationic nanoparticles gel up
to form a hard composition. Upon hardening of the composition, a thin layer of a hard gel is formed around
the unconsolidated sand grains. This hard gel can cement the sand grains together while also maintaining
a desired porosity through the treated consolidated material to facilitate production of hydrocarbons. The
positive charge of the cationic nanoparticles leads to repulsion between these nanoparticles that helps to
maintain the low viscosity of the composition and prevent the premature hardening of the composition, while
being delivered downhole to the target zone. The charge repulsion between positively charged nanoparticles
prevents any unwanted agglomeration of the nanoparticles. Furthermore, the similar charge repulsive forces
ensure a monolayer coating of surface of the sand grains in the unconsolidated formation. The positively
charged nanoparticles, having an affinity for the negatively charged sand grains in the formation, produce
a thin layer coating on the surface of the negatively charged grains of the unconsolidated formation. Fig. 1
and 2 shows the SEM analysis of the untreated pristine sand sample and a treated sand sample with cationic
nanoparticles. It clearly shows that there is a thin layer of coating of the cationic nanoparticles around the
sand particles. Moreover, the treated sand particles are cemented together due the gelling up of cationic
nanoparticles coating. It can also be seen the gelled up nanoparticles are able to maintain interstitial void
space for hydrocarbon production. The cationic nanoparticles create anionic bonding between the negatively
charged unconsolidated formation sand grains and cationically modified nanoparticles. This eventually
leads to modifying the relative permeability of the formation.
4 SPE-187237-MS

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Figure 1—ESEM micrograph for untreated pristine sand particles

Figure 2—ESEM micrograph for sand treated with cationic nanoparticles based sand control pill

Laboratory Procedures
Evaluation of Gelation Time
Gelation time defines the amount of time available to the operator before the pumping pressure of the gel
system significantly increases when applied in the field. A reasonable gelation time must be known to allow
safe pumping of the consolidation fluid through the tubular and into the near-wellbore zone. Two methods
were used in this study to measure gelation time: the dynamic viscosity method using a Model 50 type
rheometer and the sealed-tube method.

Dynamic Viscosity Method


Gelation time of the gel system was determined using a Model 50 type HPHT rheometer. A No. 05X bob was
used with a speed of 3 rev/min. Approximately 44 mL of the fluid system were measured and placed in the
HPHT viscometer cup. The cup was mounted with pressure and heated using a thermostatically controlled
electric heating bath. The viscosity changes were monitored as a function of time. This method defines
gelation time as the time required to begin building viscosity. The time when the viscosity begins to build
can be defined as "gel time."

Inverted Sealed-Tube Method


The fluid system comprising of the cationically modified nanoparticles and the activator was filled in a
testing tube with a cap to approximately 1/3 of its volume. The testing tubes were placed in a preheated
SPE-187237-MS 5

oven set at the test temperature and taken out for observation periodically. This method defines the gelation
time as the time required for a system to reach specified gel strength and relies on the visual evaluation
of the researcher. Gel-time measurements were performed with this method for testing temperatures from
200 to 300°F.

Batch screening Tests

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Batch tests were conducted to visualize and estimate the effectiveness of the cationically modified
nanoparticles in consolidating the loose sand while maintaining the high permeability. Many different ratios
of the cationically modified nanoparticles to the activator were tested to select the optimum concentrations.
The procedure to conduct such screening test is as follows:
1. Mix formation sand with brine in a beaker. The amount of brine is sufficient to saturate the sand pack
to make a slurry but not overly abundant such that a free water layer exists above the sand pack.
2. Load the sand slurry into syringe.
3. Squeeze a pre-flush fluid through the sand pack in the syringe. The preferred pre-flush fluid is a brine
such as NaCl.
4. Inject the mixture containing cationically modified nanoparticles and activator until the mixture breaks
through from the outlet of the sand pack.
5. Inject post-flush fluid. Preferred post flush fluid is also NaCl brine.
6. Set in temperature (90°C) for 48 hours
Retrieve the consolidated sand to check strength and permeability

Core flooding
Core flooding experiment is conducted with the similar procedure to that of batch screening tests but at
reservoir pressure condition.
1. Loose sand grains are packed in a rubber sleeve fitted inside a core holder. The initial brine
permeability of the sand pack is first measured with 6% NaCl.
2. Pre-flush with NaCl for one pore volume.
3. Inject one pore volume of the fluid system comprising cationically modified nanoparticles and an
activator.
4. Post flush with NaCl at various pore volumes for the purpose to investigate the effect of post flush
on the regained permeability.
5. Shut in the core under reservoir temperature (90°C) for 48 hours.
6. Measure the regain permeability to brine using 6% NaCl.

Results and Discussion


Effect of Activators on Gelation Time
Inorganic activators or ionic strength modifiers (ISM) were investigated to study the effect on the gelation
properties of cationic nanoparticles. To study this effect, the cationic nanoparticles solution was mixed
with different ionic strength modifiers of varying specific gravities (SG). Clear solutions were obtained
by varying the specific gravities of ionic strength modifiers. A variety of ionic strength modifiers were
used for the study. Table 1 summarizes the experimental observations for the compatibility study of these
activators. It was observed that most of the activators studied herein formed clear solutions when mixed
with the cationically modified nanoparticles, except for ISM 1. ISM 2 through ISM 4 were investigated
further as gelation activators for cationic nanoparticles.
6 SPE-187237-MS

Table 1—Compatibility of the cationic nanoparticles with the ionic strength modifiers (ISMs).

Specific Result of mixing


Sample No. ISM Concentration (gpt)
Gravity of ISM Positive surface charge

1 ISM1 100 1.520 Precipitation

2 ISM1 200 1.265 Precipitation

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3 ISM1 200 1.245 Precipitation

4 ISM1 100 1.200 Precipitation

5 ISM1 50 1.200 Precipitation

6 ISM1 150 1.038 Slightly Opaque

7 ISM1 100 1.038 Slightly Opaque

8 ISM2 100 1.041 Clear solution

9 ISM2 300 1.044 Clear Solution

10 ISM3 100 1.041 Clear solution

11 ISM4 100 1.044 Clear solution

12 ISM4 125 1.044 Clear solution

13 ISM4 150 1.044 Clear solution

14 ISM4 175 1.044 Clear solution

15 ISM4 200 1.044 Clear solution

16 ISM4 100 1.08 Clear solution

17 ISM4 200 1.08 Clear solution

18 ISM4 100 1.188 Clear Solution

19 ISM4 200 1.188 Clear Solution

In order to select an optimum activator for the cationically modified nanoparticles, the samples that gave
clear solutions were kept in an air circulating oven to monitor the static gelation under reasonable time
frames. Table 2 summarizes the performance of selected ISMs to gel up the nanoparticles at 90°C. In order
to be applicable downhole as a sand control pill, the system needs to show the preferred gelation time of 12
to 72 hours. Based on this argument, it was observed that ISM 4 gave the best gel times that would avoid
any premature gelling of the sand control pill while it's being pumped downhole. Whereas, ISM 2 and 3
did not gel up even after 72 hours, thus cannot be used applied in field conditions for lack of timely gel
up. When ISM 4 was used in lower concentration it also did not show any gel up after 72 hours at 90°C.
ISM 4 with SG values of 1.08 and 1.188 (designated as sample number 16, 17, 18 and 19 in Tables 1 and
2) showed most controlled gelation. ISM 4 with SG 1.188 (sample number 18 from Tables 1 and 2) was
selected for further investigation.

Table 2—ISM performance as activator to gel up the cationic nanoparticles at 90 °C.

Sample No. ISM Gelation time

8 ISM2 No gelation after 4 days (test aborted)

9 ISM2 No gelation after 4 days (test aborted)

10 ISM3 No gelation after 4 days (test aborted)

11 ISM4 No gelation after 4 days (test aborted

15 ISM4 No gelation after 4 days (test aborted)

16 ISM4 72 hours
SPE-187237-MS 7

Sample No. ISM Gelation time

17 ISM4 <15 hours

18 ISM4 7.5 hours

19 ISM4 4 hours

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Effect of Composition and Temperature on Gelation Time
Dynamic Viscosity Method. To verify the effect of sudden thermal shock on the cationically modified
nanoparticle solution and the activator two approaches were investigated. (1) The samples were conditioned
at the test temperature, before mixing with each other. (2) The nanoparticle solution and activator were added
to pre-heated sample cup. Any change in the appearance of the sand control pill or instantaneous change in
viscosity was carefully monitored. It was observed that in both the situations there was no marked change in
the appearance of the pill, neither it showed any immediate viscosification. This test proves the robustness
of the pill under high temperature conditions and provides the operator with confidence that the pill will not
prematurely gel up while pumping or before being placed in the target zone. As there was no sudden gel
up of the pill, further tests were conducted by loading the sample in the test cup at room temperature and
gradually heating up to test temperature. The effect of activator composition and temperature on the dynamic
gelation time is shown in Fig. 3 and 4 at 250 and 300 °F, respectively. The pill exhibited low viscosity
initially and over period of time the viscosity starts to build up. This is a typical representation of liquid to
solid transition. The point where the viscosity starts to increase was taken as the gel time for the sample.

Figure 3—Dynamic gelation of cationic nanoparticles with composition ratio of 1:0.15 nanoparticle: activator at 250 °F
8 SPE-187237-MS

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Figure 4—Dynamic gelation of cationic nanoparticles with composition ratio of 1:0.15 nanoparticle: activator at 300 °F

Inverted Sealed-Tube Tests. To understand the effect of composition of activator as a function of


temperature on gelation time of the cationically modified nanoparticles, inversion tests were performed.
The samples were subjected to a range of temperatures from 80°C to 150°C in static condition using
an air circulatory oven. A representative inverted sealed-tube test is depicted in Fig. 5. All the test
samples were observed for 24 hours for this set of tests. Any samples that did not gel up 24 hours were
not monitored further. Fig. 6 summarizes the results of inverted sealed-tube tests. The gelation of these
cationic nanoparticles required longer times at lower temperature and low concentrations of activators. Thus
temperature and concentration of activator showed a linear relationship to decreasing gelation times. By
optimizing concentration of activators at higher temperature one can easily achieve longer gelation time.
The strength of the gel is a function of the activator concentration. At some point, the activator concentration
would be too low to provide a usable gel. Moving to higher temperatures also makes the gelation time
harder to control. A difference of a few degrees between estimated and actual temperature will produce
a much larger deviation in gelation times at high temperatures. Furthermore, it should also be noted that,
with higher concentrations of the activator such as more than nanoparticle to activator composition ratio of
1:0.35 of nanoparticles, the solution gelled instantly before the activator could uniformly disperse through
the solution. Such instantaneous gelation could be avoided with a controlled drop by drop addition of
the activator to the nanoparticles solution under continuous agitation. However, the sample still gelled in
less than a minute even under ambient temperature conditions. This implies the necessity to optimize the
concentration of the activator in order to avoid any premature gelling of the sand control pill before it is
placed in the target zone.
SPE-187237-MS 9

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Figure 5—Representation of the inverted sealed-tube test demonstrating gelation under static conditions

Figure 6—Static gel time as a function of temperature and activator concentration

It should be noted from the static and dynamic gelation time tests that the cationic nanoparticles gel up in
shorter time frames under dynamic conditions as compared to that under static condition. This is expected
because solution to gel transition time established as the onset of viscosity increase in dynamic experiments
represents the onset of gelation, which always takes place before the gelant becomes a rigid gel. Although
it could be argued that the gelation time obtained from the static inverted testing tube method is a more
accurate measure of the available pumping time through the tubing till the sand control pill hardens into
10 SPE-187237-MS

a crystalline solid. It is recommended to design the pumping sequence based on gelation time determined
using the dynamic viscosity method. It is a more conservative approach and it will give a safety control
point to avoid any premature gelling up of the pill before it is place in the target zone.

Regained Permeability
A qualitative permeability measure was conducted to demonstrate the permeable nature of the consolidated

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sand pack using cationic nanoparticles treatment fluid. The permeability of the consolidated sand pack
increases with decreasing treatment fluid concentration without sacrificing much compressive strength.
However as the treatment fluid concentration is reduced the time taken to consolidate the sand pack
increases. In some cases this consolidation time can extend from a few days to weeks. This is impractical
when applying the treatment fluid as a sand control pill. A quicker turnaround in putting the well on
production is what is desirable. Considering this only those concentrations of the cationic nanoparticle
treatment fluid that consolidate sand in around 24 hours were chosen for further testing. Fig. 7 shows the
representative sand pack consolidated by the cationic nanoparticle treatment fluid. A simple qualitative
indication of the high permeability can be observed by dropping water on the top of the cured cylindrical
sand pack, it is observed that the water seeps through the porous medium immediately and penetrates all the
way to the other end of the cylindrical core. Continuously dropping water on top face of the consolidated
core sample results in a continuous drip from the bottom face with merely hydrostatic head. Such low flow
resistance Indicates high regained permeability of the consolidated pack.

Figure 7—Representative sand pack consolidated by the treatment fluid

Core flooding experiments were conducted using a sand pack to study the performance of the new sand
control pill to retain the formation permeability after consolidating the sand. The sand pack was prepared
using a 1:1 mixture of 100 mesh and 20:40 mesh sand. A ratio of 1:0.15 of cationic nanoparticles to the
activator was used for the regain permeability studies. A temperature of 140°C was maintained throughout
the core flooding test. System pressure was kept at 3500 psi to simulate reservoir conditions. The overburden
stress was maintained at 500 psi above the injection pressure to prevent any flow around the sand pack.
Initial permeability using 6% NaCl was measured with multiple flow rates to confirm that the pressure
transducer readings are correct as the permeability remained constant at different injection rates. The NaCl
SPE-187237-MS 11

treatment also served as the preflush for conditioning the sand pack for the nanoparticle treatment, due
to the compatibility of the new nanoparticle treatment fluid with aqueous fluids. The sand pack was then
exposed to the treatment fluid. The treatment was followed by a 48 hours shut in period at 140°C. After, the
shut in, regain permeability was measured with the NaCl brine. Results of regain permeability experiments
using this system formulation are summarized in Table 3. The average permeability was maintained between
around 50% under multiple rates of brine injection. The consolidated sand pack post the regain permeability

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tests was found to remain intact.

Table 3—Regain permeability test result.

Sample Type Initial Perm Regain Perm

Sand Pack 1:1 mix of 100 mesh 800 mD 50%


and 20/40 mesh sand

Finally the test core sample consolidated with the cationic nanoparticles was exposed to 15% HCl to
check the effect of acid on post treatment core. The regain permeability remained the same after exposing the
consolidated core to the acid. It appeared that the consolidated core did not disintegrate on exposure to acid.

Conclusions
The new downhole sand consolidation system comprising of cationically modified nanoparticles and an
activator that initiates the consolidation has shown properties and performance in addressing the drawbacks
of the currently available chemical based sand consolidation systems. Static and dynamic gelation time
experiments were performed. A controllable gelation time can be achieved by varying the concentration
ration of the cationic nanoparticles to the activator. The gelation times were found to be shorter in the
dynamic tests as compared to the static tests. This difference was attributed to the onset of gelation under
dynamic conditions as against complete gelation in static conditions. The dynamic gelation data should be
taken into consideration when designing a field job. The regain permeability testing showed the new sand
control chemical can consolidate loose sand pack without significantly damaging the formation. The newly
developed sand control system comprising of cationic nanoparticles provided 60% regain permeability.

Acknowledgements
The authors thank Abdullah Abadi for the coreflood experiments.

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