SPE-192309-MS

Nanoparticle-based chemical treatment for preventing loss circulation

Vikrant Wagle, Rajendra Kalgaonkar and Abdullah S. Al-Yami, Saudi Aramco

Copyright 2018, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE Kingdom of Saudi Arabia Annual Technical Symposium and Exhibition held in Dammam, Saudi Arabia, 23–26
April 2018.

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
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Abstract
This paper provides development of a novel nanoparticle-based chemical treatment composition for its
potential use a loss circulation material. The novel loss circulation material is based on a delayed activation
chemistry to gel up an environmentally friendly nanomaterial based dispersion. The chemical treatment
composition comprises of two major components viz. nanoparticle based dispersion and a chemical
activator. A major advantage of the activator used to gel up nanoparticle-based dispersion is its ability to
place the treatment composition in to the target zone before the nanoparticle based dispersion gels up thus
avoiding premature setting of the treatment fluid. The newly developed system can be used effectively up
to 300oF. The gelation times were evaluated at different temperatures up to 300oF. The effects of pH and
different concentration of activators on gelation times of the new treatment fluid has also been studied.
The effectiveness of the newly developed composition as a loss circulation treatment was also evaluated
by performing permeability plugging tests to test the plugging capacity of this novel system.
The novelty of the newly developed treatment composition is to have a controllable gelation time under a
variety of downhole conditions to allow accurate placement of the treatment fluid inside the wellbore
without premature setting of the fluid. It was shown that the gelation time of the treatment composition
could be controlled by adjusting the concentration of the activator. The system gives a predictable and
controllable pumping time, ranging from a few minutes to several hours at over a wide range of
temperatures. This is an important advantage of as it allows the treatment composition to remain pumpable
for sufficient time for placement and develops the network structure that leads to gelation, over a
predictable period of time. The set gel, which appears as a crystalline solid, could remain homogenous
and stay in place thereby preventing loss circulation.

Introduction
Various challenges are encountered during drilling and production operations of oil and gas wells. For
example, fluids used in drilling, completion, or servicing of a wellbore can be lost to the subterranean
formation while circulating the fluids in the wellbore. In particular, the fluids may enter the subterranean
formation via depleted zones, zones of relatively low pressure, lost circulation zones having naturally
occurring fractures, weak zones having fracture gradients exceeded by the hydrostatic pressure of the
drilling fluid, and so forth. The extent of fluid losses to the formation may range from minor losses (for
example less than 10 barrels/hour ((bbl/hr), also referred to as seepage loss, to severe (for example, greater
than 100 bbl/hr), or higher, also referred to referred to as complete fluid loss (Nayberg 1986). As a result,
the service provided by such fluid is more difficult or costly to achieve.
SPE-KSA-110-MS 2

Such lost circulation can be encountered during any stage of operations and occurs when drilling fluid
pumped into a well returns partially or does not return to the surface. While minimum fluid loss is
expected, excessive fluid loss is not desirable from a safety, an economical, or an environmental point of
view. Lost circulation is associated with problems with well control, borehole instability, pipe sticking,
unsuccessful production tests, poor hydrocarbon production after well completion, and formation damage
due to plugging of pores and pore throats by mud particles. Lost circulation problems may also contribute
to non-productive time (NPT) for a drilling operation. In extreme cases, lost circulation problems may
force abandonment of a well.
A number of treatments have been described in literature which try to address this problem of loss
circulation. Treatments involving the use of cross linked nanocomposite gels to control severe losses
(Lecolier 2005); use of crosslinked cements (Mata 2005), acid-soluble cement (Yami 2014), gunk
squeezes (Collins 2010), high strength pill comprising of inert blend of mineral, synthetic and cellulosic
fibers (Sanders 2010). However most of these treatments have both advantages as well as disadvantages.
This paper thus decribes a novel loss circulation composition that can be used to plug seepage to
moderate losses. The novel loss circulation composition treatment fluid comprises of two different
components viz. nanoparticle based dispersion and an activator. The activator used in this study has a
property of having an initial alkaline pH that changes to acidic pH with time and temperature. This change
in pH of the composition converts the nanoparticle based dispersion from a liquid state into a gelled solid
state. The advantage of this loss circulation composition is that it has a very low initial viscosity of less
than 5cp. The initial low viscosity of the loss circulation composition would allow for low pump pressures.
The gelation process of the loss circulation composition is also dependant on the formation temperature.
This change in pH along with temperature effect results in in-situ gelation of the nanoparticle based
dispersion and thereby would plug the loss circulation zones in the wellbores. The loss circulation system
can be effectively used to counter seepage to moderate losses from 70°C to 300°C. The gelling time for
the loss circulation composition is dependant on the activator concentration and can be easily controlled
by adjusting the amount of activator in the loss circulation composition. It gives a predictable and
controllable pumping time, ranging from a few minutes to several hours at a given temperature. The gelled
loss circulation material appears as a crystalline solid as shown in Fig 5 in this paper.

Procedures for evaluating the nanoparticle-based chemical treatment

(A) Evaluation of Gelling Time of the novel loss circulation composition
The LCM composition comprising of the nanoparticle dispersion and the activtor after pumping has to
reach the loss circulation zone where it gels and then forms a solid. The gelling time of the LCM
composition should be such that the mud engineer should be able to pump the LCM composition without
giving it a chance to gel before it reaches the loss circulation zone. The gelling time thus defines the
amount of time available to the mud engineer before the pumping pressure of the gel system significantly
increases when applied in the field. In this study, two different methods have been used to evaluate the
gelling time of the novel LCM compostion
(i) Inverted sealed-tube method
(ii) Dynamic viscosity method using a Model 50 type rheometer
(i) Inverted Sealed-Tube Method
In this method, the loss circulation composition comprising of the nanoparticle based dispersion and the
activator was taken in a test tube. 25ml of the composition was taken in a test tube. The test tube was then
subsequently sealed off using a cap. The test tubes were then subsequently kept in a preheated oven. This
oven was then set at the desired test temperature and the tubes were periodically taken out of the oven for
SPE-192309-MS 3

observation. The experiments for gelling time determination of the loss circulation composition were
performed at 80°C. The gelling time of the loss circulation composition is defined as the time required for
the composition to reach a specified gel strength and this determination relies on the visual evaluation of
the researcher.
(ii) Dynamic Viscosity Method
A Model 50 type HPHT rheometer was used to determine the gelling time of the loss circulation
composition under dynamic conditions. A No. 05X bob was used with a speed of 3 rev/min. In this test,
44 mL of the loss circulation composition taken in the HPHT viscometer cup. The sample was subjected
to the desired pressure and was heated using a thermostatically controlled electric heating bath. The change
in viscosity of the loss circulation composition was monitored at fixed intervals of time. Gelling time as
obtained by this method is the time when the loss circulation composition begins to build viscosity.

(B) Particle plugging tests (PPT)

A PPT test is performed in a specialized filtration-type apparatus (particle-plugging apparatus) to
determine the effectiveness of additives to prevent fluid loss into a permeable medium. The novel
nanoparticle based composition was thus tested as a treatment to prevent loss circulation using the PPT.
The particle plugging apparatus for the test is shown in Fig 1. The following procedure was used during
the test.
 Set the temperature controller to the desired temperature.
 Pour the sample into the cell and place the cell into the heating jacket in the same orientation
 Apply appropriate amount of pressure through the back pressure regulator to the top of the cell.
 After opening the top valve, collect the fluid from the back pressure collector in a measuring cylinder
and record the amount. Ensure that all the fluid has been expelled. This will be reported as the Spurt
volume (ml).
 Keep collecting periodically over the next 30 minutes and record the total fluid collected over the 30
minute period as Total fluid (ml).
 The PPA fluid loss (PPA Total) is calculated as follows
Total fluid volume – spurt volume = Fluid loss………………Equation 1
PPA Total = Spurt volume + (2 x Fluid loss)…………………Equation 2

Fig 1: Test assembly for Particle plugging test

Results and Discussion

(A) Evaluation of Gelling Time of the novel loss circulation composition
(i) Inverted Sealed-Tube Method
SPE-192309-MS 4

To evaluate the gelling time, the novel loss cisculation composition was initially subjected to inverted
tube tests. The effect of concentration of the activator and the effect of pH on the loss circulation
composition was studied using the inverted sealed-tube tests
(a) Dependence of gelling time on activator concentration
Inverted tube tests were performed on the loss circulation composition by changing the concentration of
the activator. This was done to determine the effect of the concentration of the activator on the gelling
time of the loss circulation composition. Tests were performed using 5 different acitivator concentrations
viz. 1%, 2.25%, 5%, 7.5% and 10%. The nanoparticle dispersion was initially taken into a test tube and
the activator was added into by constant stirring. After proper mixing, the test tubes were then kept in a
static oven at 80°C in an air circulatory oven. The test compositions in the tubes were kept under
observation for a period of 24 hours at 80°C. Fig. 2 shows a representative inverted sealed tube comprising
the loss circulation composition and the activator.

LCM composition

Inverted sealed tube

Fig. 2− Inverted sealed-tube test with the novel loss circulation composition

The results of the inverted sealed-tube tests involving the LCM composition are shown Fig. 3. An activator
concentration of 1%, 2.5%, 5%, 7.5% and 10% results in a gelling time of 13hrs, 12hrs, 8hrs, 4hrs and 1
hr respectively. The results thus show that the gelling time of the LCM composition is inversely
proportional to the concentration of the activator. Thus lower concentrations of activators used in these
tests resulted in longer gelling times. Thus for a loss circulation zone at certain depth and temperature, the
activator concentration can be optimized to get the desired gelling time for the loss circulation
composition. It was also noted in the tests that the activator concentration also governs the strength of the
gel. Activator concentrations below 1% resulted in less stronger gels which would be ineffective in
plugging the loss circulation zones. Also, for a particular activator concentration, an increase in
temperature would result in a shorter gelling time thus rendering the gelling 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. Tests were also performed with activator concentrations greater
than 10%. However, the loss circulation compositions gelled immediately at such high activator
concentrations at ambient temperature conditions. This instantaneous gelling of the loss circulation
composition at higher activator concentrations thus show that there is a need to optimize the activator
SPE-192309-MS 5

concentration before the loss circulation composition is pumped into the loss circulation zone at a certain
temperature to avoid instant gelling.

16

14 13
12
12
Gelling time in hrs

10
8
8

6
4
4

2 1

0
1 2.5 5 7.5 10

Concentration of activator (%)

Fig. 3− Relationship between activator concentration and gelling time of the loss circulation
composition

(b) Effect of pH on the gelling time of the nanoparticle based loss circulation composition
The loss circulation zones are located at different depths and temperatures. This necessitates the
optimization of the loss circulation composition is terms of its ability to start gelling at a particular
temperature. The pH of the loss circulation composition can thus be adjusted so as to have the desired
gelling time for a particular well and at a certain temperature. This will eliminate premature gelling of the
nanoparticle based dispersion before it reaches the loss circulation zone.
To study the effect of pH on the gelling time, 10 different solutions of nanoparticle based dispersion
were prepared in beakers. 200ml of nanoparticle dispersion and 10ml of activator were taken in each
beaker. The starting pH of this loss circulation composition was around 10. The pH of the loss circulation
composition kept in 9 beakers were adjusted in between 1 to 9 using a weak acid. No pH adjustment by
acid addition was made for the sample with pH 10. 25ml from each solution was then kept in 10 different
test tubes. Gelling time was determined after adding the weak acid to the loss circulation composition. All
ten compositions were maintained at 80°C under static conditions in an air circulatory oven and were
subsequently monitored to determine the gelling time. Fig. 4 shows the gelling time under different pH
conditions at 80°C for ten different loss circulation compositions.The nanomaterial based loss circulation
composition is a stable aqueous dispersion of discrete nonporous particles. The nanoparticle dispersion is
stable at a moderate pH of 9.5 to 10.5. As the pH of the system decreases to a more acidic pH, interparticle
collision of the nanoparticles mainly causes the aggregation into long chain-like networks and forms the
gel. This particle collision is possible by increasing temperature and reducing the pH of stable alkaline
solution. Gelation is the time when particle aggregates complete and form uniform 3D networks of long,
bead-like strings of nanoparticles. In the pH range of 5 to 7, because not many ions are present that can
prevent interparticle aggregation, this ultimately results in low gelation time, of approximately one hour
SPE-192309-MS 6

or even less, as can be seen in Fig. 4. Minimum gel time is exhibited in the pH range of 1 to 7. The increase
in pH above 7 leads to surface ionization that promotes charge repulsion and ultimately result in increased
gelation time. Fig. 5 shows complete gelation at pH of 2 in presence of activator at 80oC. Gelation times
of approximately 2 to 8hr have been observed in the pH range of 8 to 10.

9
8
7
6
Gelling time (hours)

5
4
3
2
1
0
0 2 4 6 8 10 12
pH

Fig. 4− Effect of pH on the gelling time of loss circulation composition

Fig. 5−Gelled nanoparticle dispersion

SPE-192309-MS 7

(ii) Dynamic Viscosity Method

(a) Effect of concentration of activator on the dynamic gelation of nanoparticle based loss
circulation composition at 300oF
When the nanoparticle dispersion and the activator are mixed at ambient conditions and subsequently
subjected to a high temperature, there are chances of the loss circulation composition experiencing a
thermal shock. Thus to determine this effect of thermal shock, tests were performed at two different
conditions viz. a) the nanoparticle dispersion and the activator were both conditioned at the test
temperature and were then subsequently mixed and b) both the nanoparticle based dispersion and activator
were placed in a pre-heated sample cup. The loss circulation composition was carefully monitored for any
sudden change in either appearance or viscosity. However, in both the situations neither was there any
change in aapearance nor any onset of instant gelling or viscosity increase in the loss circulation
composition. These results show that the mud engineer would be able to design and pump the loss
circulation pill without any fear of instantaneous gelling of the loss circulation pill before it reaches the
loss circulation zone.
Since the loss circulation composition did not show any instantaneous gelling, the loss circulation
composition was further tested by placing and mixing both the 200ml nanoparticle based dispersion and
activator in the test cup at ambient conditions and subsequently gradually heating up to the desired test
temperature. In this study, three different activator concentrations were used, viz. 0.5ml, 2.5ml and 5ml.
Tests were performed at 300oF and the effect of activator concentration on the gelling time under dynamic
conditions was studied. The results of this study is shown in Fig. 6. For all the activator concentrations,
the loss circulation composition as expected showed low viscosity initially. However, over a period of
time the viscosity of the composition begins to build up. This is expected as the nanoparticle dispersion
which is in liquid state transitions into a solid with time. The time at which the viscosity starts to increase
was noted as the gelling time for the loss circulation composition. It can be thus observed from Fig. 6 that
an increase in activator concentration results in a decrease in the gelling time values for loss circulation
composition.

Fig. 6−Effect of activator concentration on the dynamic gelation of nanoparticles at 300°F

SPE-192309-MS 8

(b) Effect of pH on viscosity of the nanoparticle based loss circulation composition as a function of
time
The loss circulation composition is so designed that the pH of the composition changes from alkaline to
acidic over a period of time under wellbore conditions. Thus, there was a need to determine the change in
viscosity of the loss circulation composition even as the pH of the composition changes from alkaline to
acidic. This study of the change in pH is important as it would help the mud engineer to to design the loss
circulation conmposition so that it does not gel up before being placed in the loss circulation zone at a
certain temperature. This change in viscosity of the loss circulation composition as the pH changes from
alkaline to acidic is given in Fig 7. At ambient temperature and at 0 hours, the starting pH of the loss
circulation composition is 10. At this initial point, the viscosity of the composition is 4cp. The composition
was then heated up and subjected to a temperature of 300°F. The pH and the viscosity of the system was
then measured at a fixed time interval of 1hour. As can be seen from Fig.6 that with time, as the pH of the
loss circulation composition decreases the viscosity of the composition increases.

Fig. 7−Effect of pH as a function of time on viscosity of nanoparticles at 300°F

(B) Particle plugging tests (PPT)

The nanoparticle based loss circulation composition was also tested for its efficiency to seal or plug loss
circulation zones using the particle plugging tests. Particle plugging tests is used in the industry to
SPE-192309-MS 9

determine the effectiveness of different materials to prevent fluid loss into a permeable medium. The
method to perform the particle plugging tests has been given in the lab procedures. 2mm slotted disks
were used as a filter medium in this test in order to simulate fractures of 1-2mm width in the loss
circulation zone. The nanoparticle based loss circulation composition was thus tested for its ability to seal
off these 2mm slots. The test was performed at 250oF at a differential pressure of 1500psi. The loss
circulation composition was kept static for 3 hours before the top valve was opened. The results of the
particle plugging tests in shown in Table 1. The test results show that the loss circulation composition
gave no fluid loss and zero loss of filtrate for the entire test period at 250oF. This test shows that the
nanoparticle based composition would be able to plug loss circulation zones and control moderate losses.

Table 1: Results of particle plugging test at 250oF.

Test temp. 250oF
Spurt loss, ml 0
Fluid loss, ml 0
PPA Total, ml 0

Summary
 A novel nanoparticle-based chemical treatment composition was evaluated for its potential use as a loss
circulation material.
 The loss circulation composition which maintained low viscosity at ambient temperature conditions
gelled up at higher temepratures over periods of time
 The loss circulation composition was evaluated by performing both static and dynamic gelation studies.
Static tests showed longer gelling time as compared to dynamic tests. Gelling times as obtained from
the dynamic viscosity studies should be used when designing a loss circulation treatment pill.
 Gelling times of the loss circulation composition were inversely proportional on the activator
concentration. Decrease in the concentration of the activator resulted in longer gelling times.
 The gelling time of the loss circulation composition can be controlled by optimizing the activator
concentration for a loss circulation zone at a certain depth and temperature in a well.
 A decrease in pH of the loss circulation composition results in a decreasein gelling time
 Viscosity of the nanoparticle based loss circulation composition is inversely proportional to a decrease
in pH. A decrease in pH of the composition resulted in an increase in viscosity of the loss circulation
composition
 Sealing efficiency as demonstrated by the particle plugging tests show that the novel nanoparticle based
composition has the potential to seepage to moderate losses encountered during drilling.

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