Mitigation of Lost Circulation in Oil-Based Drilling Fluids Using Oil Absorbent Polymers

materials
Article
Mitigation of Lost Circulation in Oil-Based Drilling
Fluids Using Oil Absorbent Polymers
Hanyi Zhong 1, * , Guangcheng Shen 1 , Peng Yang 2 , Zhengsong Qiu 1 , Junbin Jin 3
and Xiaodong Xing 4
1 School of Petroleum Engineering, China University of Petroleum (East China), Qingdao 266580, China;
m18754272192@163.com (G.S.); qiuzs@upc.edu.cn (Z.Q.)
2 GWDC Engineering Research Institute, Panjin 124010, China; yangpeng00625@163.com
3 SINOPEC Research Institute of Petroleum Engineering, Beijing 100101, China; jinjb.sripe@sinopec.com
4 China Petroleum Engineering & Construction CORP, North China Company, Renqiu 062552, China;
xingxiaodong@cpeccnc.com
* Correspondence: zhonghanyi@126.com

Received: 26 September 2018; Accepted: 15 October 2018; Published: 18 October 2018
Abstract: In order to mitigate the loss circulation of oil-based drilling fluids (OBDFs), an oil-absorbent
polymer (OAP) composed by methylmethacrylate (MMA), butyl acrylate (BA), and hexadecyl
methacrylate (HMA) was synthesized by suspension polymerization and characterized by Fourier
transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA) and scanning electronic
microscopy (SEM). The oil-absorptive capacity of OAP under different solvents was measured as the
function of temperature and time. The effect of the OAP on the rheological and filtration properties
of OBDFs was initially evaluated, and then the sealing property of OAP particles as lost circulation
materials (LCMs) was examined by a high-temperature and high-pressure (HTHP) filtration test,
a sand bed filtration test, a permeable plugging test, and a fracture sealing testing. The test results
indicated that the addition of OAP had relatively little influence on the rheological properties of
OBDF at content lower than 1.5 w/v % but increased the fluid viscosity remarkably at content higher
than 3 w/v %. It could reduce the HTHP filtration and improve the sealing capacity of OBDF
significantly. In the sealing treatment, after addition into the OBDF, the OAP particles could absorb
oil accompanied with volume enlargement, which led to the increase of the fluid viscosity and
slowing down of the fluid loss speed. The swelled and deformable OAP particles could be squeezed
into the micro-fractures with self-adoption and seal the loss channel. More important, fluid loss
was dramatically reduced when OAP particles were combined with other conventional LCMs by
a synergistic effect.
Keywords: lost circulation; oil-based drilling fluid; oil absorbent polymer; fracture sealing; combination
1. Introduction
In oil and gas drilling engineering, one of the frequently encountered problems is lost circulation,
which is defined as the undesirable partial or complete loss of drilling fluid into formation voids
during drilling, circulation, running casing, or cementing operations [1,2]. Once the total pressure
exerted against the formation exceeds the formation breakdown pressure, lost circulation may be
encountered at any depth. According to the statistics, the occurrence of lost circulation is present in
approximately 20 to 25% of wells drilled around the world during drilling [3], and results in several
troublesome problems such as excessive mud losses, non-productive time, stuck pipe, well kick,
well blow-out and even abandonment of the wells [4–7]. Moreover, it has also been blamed for
minimized production because the loss of fluid into a formation plugs the production zones and leads
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Materials 2018, 11, 2020 2 of 20
to decreased productivity [8,9]. More than 2 billion USD is spent to combat and mitigate this problem
each year [10,11]. Lost circulation poses great challenges for the industry.
Lost circulation is generally observed in four kinds of formation including natural or
induced fractured formations, vugular or cavernous formations, highly permeable formations,
and unconsolidated formations [3]. Although the forms of loss like filtration loss, matrix seepage,
and vugular loss may be of concern, losses through fracture propagation is the primary type and
accounts for over 90% of the operator lost returns expenditures [7].
Over the past years, much effort has been made in an attempt to mitigate or stop lost circulation.
A wide variety of lost circulation materials (LCMs) have been employed to form dense and integrated
fracture sealing barriers [12]. The list of materials commercially available as LCMs is impressive [13,14].
Conventionally, these materials can be classified as fibrous, flaky, granular type, and mixtures of
these [15]. For instance, particulate materials such as calcium carbonate and graphites, fibrous
materials such as wood fiber, mineral fiber, and glass fiber; flake materials such as cellophane,
mica and vermiculite; and granular materials such as perilite, nut shells and ground tires are
widely used [16]. Meanwhile, other types of materials including cement, chemically activated
cross-linked pilles, cross-linked cement, deformable-viscous-cohesive systems, nano-composite gel,
gunk squeezes [17], polyurethane grouting, crosslinked gel, viscoelastic surfactant, nano-particles [18],
reticulated foam [19], and shape memory polymers [20] have also attracted attention. These materials
are generally added either to the drilling fluid or separately in the form of a sweep or a treating pill [21].
Because of the inherent advantages of high temperature stability, excellent lubricity, high wellbore
stability, and tolerance to pollution and so on, invert emulsion drilling fluids (including oil-based
drilling fluid (OBDF) and synthetic-based drilling fluid (SBDF)) are generally preferred when
there are drilling demanding formations and complex conditions such as deep formation drilling,
deep water drilling and gypsum and so on in comparison with water-based drilling fluids [22–24].
However, one potential drawback to the use of these fluids is the high cost associated with lost
circulation [12]. On the one hand, the strong dependency of density on both temperature and
pressure makes the invert-emulsion drilling fluid more compressible than the water-based drilling
fluid, which subsequently results in a narrower drilling fluid density margin and easy occurrence of
lost circulation [25,26]. On the other hand, for the pressure required to initiate hydraulic fracturing of
the formation, there is no difference between water-based drilling fluid and invert emulsion drilling
fluid; however, after the fractures are formed, there is a noticeable difference [9,27,28]. For water-based
drilling fluid, a higher spurt fluid loss causes the almost instantaneous formation of a filter cake, and is
then followed by a higher filtration loss, which results in the formation of thicker filter cakes, shielding
the fracture tip from the maximum wellbore pressure and allowing bridges to develop that prevent
further fracture propagation [26]. Meanwhile, the presence of filter cake can heal the fractures and lead
to higher fracture re-opening pressures. Nevertheless, for invert emulsion drilling fluid, because of
almost no dispersion of drilling cuttings, the filter cake is primarily composed of emulsion droplets and
very thin and impermeable. Meanwhile, after wetting by the invert emulsion drilling fluid, the friction
between LCMs and fracture plane decreases and cause the LCMs relatively difficult to bridging
and forming effective sealing, which facilitate movement along these weak planes [29,30]. Therefore,
once the fracture is initiated, a much smaller pressure is needed to propagate the fracture compared to
water-based drilling fluid. This allows changes in wellbore pressures to be transmitted to the formation
more readily, and further propagates the fracture [9,31]. Furthermore, although a variety of materials
have been used as LCMs, materials specially designed to combat lost circulation in invert-emulsion
drilling fluids are relatively fewer than that for water-based drilling fluids [25]. For solid particles,
oil-wetting chemicals must typically be added to ensure the oil wet property when drilling with
an OBDF [32]. Thereby, when using invert-emulsion drilling fluids, very few lost circulation remedies
have been successful [33,34].
Water-absorbent resin is a kind of polymer with cross-linking structures which render the resin
water-insoluble and capable of absorbing water of several to hundreds of times of its own weight.
Materials 2018, 11, 2020 3 of 20
By deforming and being squeezed into the loss fractures with flexibility, the polymers can absorb
water and fill in the fractures or pores. Due to the adsorption on the rock surface, it is easy for the
polymers to stay in the loss channels and form a strong and pliable plug [35]. Because of the above
advantages, water absorbent resin has been widely used in water-based drilling fluid as an effective
LCM [36,37]. Behaving like water-absorbent resins, oil-absorbent resins having the cross-linked,
three-dimensional, and hydrophobic networks that do not dissolve in oil are mainly used for absorbing
oil in environmental pollution treatment [38]. Therefore, considering the similar properties between
oil-absorbent resin and water-absorbent resin, the object of the current study is to probe the feasibility
of oil absorbent resin in mitigating the loss of OBDFs.
2. Materials and Methods
2.1. Materials
Monomers including methylmethacrylate (MMA) (99%), butyl acrylate (BA) (98%), and hexadecyl
methacrylate (HMA), cross-linking reagent N,N’-Methylenebis (acrylamide) (MBA) (99%) and initiator
benzoyl peroxide (BPO) were purchased from Shanghai Aladdin Biochemical Technology Co. Ltd.
(Shanghai, China) with analytical purity. Polyvinyl alcohol (PVA) using as dispersant agent,
ethyl acetate (EAC) as porogen, and ethanol were bought from Sinopharm Chemical Reagent Co., Ltd.
(Beijing, China) with analytical purity.
The low-toxicity mineral oil of No. 3 white oil used as the base oil was purchased from
Shandong Taichang Petrochemical Technology Co., Ltd. (Qingdao, China). The organic clay with
commercial name VG-Plus was provided by M-I Swaco Company of Schlumberger. Primary emulsifier
BZ-OPE (amidoamine type) and secondary emulsifier BZ-OSE (fatty acid type) were provided by
China National Petroleum Corporation (Tianjin, China). Rheological modifier SD-RM prepared from
a reaction between polyacid and polyethene polyamine was provided by Shandong Shida Chuangxin
Technology Co., Ltd. (Dongying, China). Barite used as weighting material was purchased from
An County Huaxi mineral powder Co., Ltd. (Mianyang, China). Two types of conventional fluid loss
additives including asphaltic additive and modified lignite used in OBDFs were provided by China
National Petroleum Corporation and Shandong Shida Chuangxin Technology Co., Ltd. (Dongying,
China), respectively. Lime (CaO, pH enhancer) and CaCl2 were bought from Sinopharm Chemical
Reagent Co., Ltd. (Beijing, China). Calcium chloride was purchased from Sinopharm Chemical Reagent
Co., Ltd. with analytical purity. The sized calcium carbonate (SCC) particles were provided by Jingmen
Shun Zhan calcium Industry Co., Ltd. (Jingmen, China). The rubber (RUB) particles were obtained
from Dujiangyan Huayi Rubber Co., Ltd. (Dujiangyan, China). The fibers (FIB) using as LCM were
bought from Changzhou Tianyi engineering fiber Co., Ltd. (Changzhou, China). All the reagents were
used as received without further purification.
2.2. Synthesis and Characterization of Oil-Absorbent Polymer (OAP)

The reaction was performed in 500 mL, four-necks, round-bottom flasks equipped with
a mechanical stirrer and heating device. Initially, 240 mL of PVA (2 g) solution was added into the flask
and stirred for 30 min with water bath heated to 60 ◦ C for facilitation of dissolution. The system was
charged with nitrogen gas and then sealed under nitrogen. Then, a mixture containing monomers of
MMA (6 g), BA (16 g) and HMA (18 g), cross-linker MBA (0.3 g), initiator BPO (0.4 g) and porogen EAC
(5 g) was added into the reactor within 10 min. The polymerization reaction was performed at 80 ◦ C
for 6 h under a stirring rate of 600 rpm. After reaction termination, the products were washed with
absolute ethanol several times and then washed with hot deionized water (60–70 ◦ C) several times.
After washing, the sample was dried in vacuum drying oven (Qingdao Haitongda Special Instrument
Co., Ltd., Qingdao, China) at 55 ◦ C for 24 h and finally the product of oil-absorbent polymer (OAP)
was obtained as small beads. The particle size can be controlled by adjusting the stirring rate and the
ratio of reaction monomers.
Materials 2018, 11, 2020 4 of 20
The Fourier transform infrared (FT-IR) spectra were recorded by a Nicolet 6700 FT-IR spectrometer
(Thermo Fisher Nicolet Corporation, Waltham, MA, USA), scanning from 4000 to 400 cm−1 ,
with 4 cm−1 resolution in transmission. A TGA/DSC 1/1600 HT thermal analyzer from Mettler
Toledo (Zurich, Switzerland) was used for thermogravimetric analysis (TGA) with a heating program
from room temperature to 1000 ◦ C at a heating rate of 10 K min−1 in nitrogen flow of 50 mL min−1 .
The morphological features of the OAP were inspected with FEI Quanta FEG 250 field-emission
scanning electron microscope (SEM, Hillsboro, OR, USA). The oil-adsorption capacity was conducted
with the weighting method [39]. A quantity of 1 g of dried OAP samples was put into a filter bag and
immersed in oil at a certain temperature. After a period of oil absorption, the filter bag with the sample
was lifted from the oil and drained for 1 min. Then the sample was immediately taken out, weighed
and recorded. The oil absorbency was calculated as follows:
(W − 1 )
R= (1)
1
where, R is the oil absorbency at a certain testing time, g/g; W is the weight of OAP after oil adsorption
for a certain testing time, g.
2.3. Preparation of Oil-Based Drilling Fluids (OBDFs)

The mineral oil-based drilling fluids were prepared according to the experimental methods
recommended in API RP 13B-2 [40]. The drilling fluid formula with oil to water ratio (OWR) of 90:10
is listed in Table 1. When the OWR of the fluid changed, the concentration of primary emulsifier and
assistant emulsifier would be adjusted correspondingly to ensure the emulsion stability. The fluids
were hot rolled in a rolling oven (Qingdao Haitongda Special Instrument Co., Ltd., Qingdao, China) at
a certain desired temperature for 16 h. After the dynamic aging, the fluids were cooled down to room
temperature and agitated for 10 min at 10,000 rpm before it was analyzed.
Table 1. Base formula of oil-based drilling fluids (OBDF) with oil to water ratio (OWR) of 90:10.
Component Commercial Name Content Unit

White oil No. 3 360 mL
Organic clay VG-Plus 12 g
Primary emulsifier BZ-OPE 12 g
Assistant emulsifier BZ-OSE 12 g
Wetting agent BZ-OWA 8 g
Rheological modifier SD-RM 4 g
CaCl2 solution (25 wt %) 40 mL
CaO 8 g
Barite As required
2.4. Rheological Properties and Electrical Stability Measurement

The rheological properties of the fluids were carried out at 50 ◦ C according to the standard
American Petroleum Institute Recommended Practice (API RP) 13B-2. The rheological parameters
including apparent viscosity (AV), plastic viscosity (PV), yield point (YP), and gel strength of the
OBDFs were measured using a model ZNN-D6 six-speed rotating viscometer (Qingdao Haitongda
Special Instrument Co., Ltd., Qingdao, China). The AV, PV and YP were calculated from 300 and
600 rpm readings by the following equations:
Apparent viscosity (AV) = Φ600/2 (mPa·s) (2)
Plastic viscosity (PV) = Φ600 − Φ300 (mPa·s) (3)
Yield point (YP) = 0.48(Φ300 − PV) (Pa) (4)

Materials 2018, 11, 2020 5 of 20
The Gelin and Gel10min were recorded as the maximum dial reading at a fixed rate of 3 r/min
after undisturbed for 10 s and 10 min, respectively [41]. The electrical stability (ES) of the OBDFs
was measured using the electrical stability tester (Qingdao Shande Petroleum Apparatus Co., Ltd.,
Qingdao, China).
2.5. Filtration Properties

Materials 2018, Measurement
11, x FOR PEER REVIEW 5 of 21
Different filter
2.5. Filtration presses
Properties are used to determine the filtration property of drilling fluids. The API
Measurement
filtrate volume of OBDFs before and after hot rolling was tested by a ZNZ-D3-type medium-pressure
Different filter presses are used to determine the filtration property of drilling fluids. The API
filtration apparatus
filtrate volume of(Qingdao
OBDFs before Haitongda Special
and after hot rollingInstrument
was tested byCo., Ltd., Qingdao,
a ZNZ-D3-type China). The volume
medium-pressure
of filtration
filtrationwas collected
apparatus through
(Qingdao filter paper
Haitongda Specialas filtrationCo.,
Instrument medium under aChina).
Ltd., Qingdao, fixed Thepressure
volumeof 0.7 MPa
for 30ofminfiltration was collected through
as recommended with APIfilterstandard.
paper as filtration medium under a fixed pressure of 0.7 MPa
formost
In 30 minsituations,
as recommended with
drilling API standard.
fluid filtrate into the formation in the drilling is a dynamic process;
In most situations, drilling fluid filtrate into the formation in the drilling is a dynamic process;
therefore, the high-temperature and high-pressure (HTHP) dynamic fluid loss was measured with
therefore, the high-temperature and high-pressure (HTHP) dynamic fluid loss was measured with a
a HTHP HTHP dynamic
dynamic filter
filterpress
press (Figure
(Figure 1)1)(Qingdao
(Qingdao Haitongda
Haitongda Special
Special Instruments
Instruments Co.,
Co., Ltd.) at aLtd.) at a stirring
stirring
speedspeed
of 100 rpm.
of 100 rpm.The
The tests wererun
tests were runforfor 30 min
30 min at a differential
at a differential pressure pressure
of 3.5 MPa ofand3.5
150MPa and 150 ◦ C.
°C. The
The filtrate wascollected
filtrate was collected with
with filter
filter paper
paper as medium.
as filter filter medium.
Figure 1. Scheme
Figure 1. Schemeofofhigh-temperature and
high-temperature and high-pressure
high-pressure (HTHP)
(HTHP) dynamic
dynamic filtrationfiltration
cell. cell.
When When
the the circulation
circulation ofofdrilling
drilling fluid
fluidstops
stopsbecause
becauseof accidents or downhole
of accidents operations,
or downhole a static a static
operations,
filtration occurs. To simulate the static filtration behavior of drilling fluid, the HTHP
filtration occurs. To simulate the static filtration behavior of drilling fluid, the HTHP static fluidstatic fluid loss loss was
was conducted via the HTHP filter apparatus (GGS71-B, Qingdao Haitongda Special Instruments Co.,
conducted via the HTHP filter apparatus (GGS71-B, Qingdao Haitongda Special Instruments Co., Ltd.)
Ltd.) under the condition of a certain temperature and 3.5 MPa pressure difference for a period of 30
undermin.theThecondition
volume of offiltration
a certain temperature
and the thickness and
of the3.5 MPa
filter cakepressure difference for a period of 30 min.
were recorded.
The volume of filtration and the thickness of the filter cake were recorded.
2.6. Properties of Sealing
2.6. Properties of Sealing
To evaluate the sealing performance of OAP, four distinctive tests including HTHP filtration
(including
To evaluate both
thestatic and dynamic
sealing filtration)
performance using API
of OAP, fourfilter paper astests
distinctive the filtration
including medium
HTHP to filtration
simulate the permeable formation [42]; a permeability plugging test using ceramic disk as filtration
(including both static and dynamic filtration) using API filter paper as the filtration medium to simulate
medium to determine the ability of particles in the drilling fluid to bridge pores [43]; a sand bed
the permeable formation [42]; a permeability plugging test using ceramic disk as filtration medium
filtration test using a sand bed as filtration medium to simulate an unconsolidated formation; and a
to determine the
fracture sealing ability of particles
test using wedgedin and theslotted
drilling fluid steel
stainless to bridge pores medium
as filtration [43]; a sand bed filtration
to simulate a test
usingfractured
a sand bed as filtration
formation medium
were carried to simulate an unconsolidated formation; and a fracture sealing
out [44,45].
test usingThe test procedure
wedged of the stainless
and slotted sand bed filtration
steel as test and permeability
filtration medium plugging
to simulatetest refer to Zhongformation
a fractured
et al. [46]. The
were carried out [44,45].sand particles used for sand bed filtration test have the particle size ranging from 380
µm to 830 µm. The sand disk using for permeability plugging test was calibrated to 10 D.
Materials 2018, 11, 2020 6 of 20
The test procedure of the sand bed filtration test and permeability plugging test refer to
Zhong et al. [46]. The sand particles used for sand bed filtration test have the particle size ranging
from 380 µm to 830 µm. The sand disk using for permeability plugging test was calibrated to 10 D.
In order
Materials to
Materials evaluate
2018,
2018, 11,x xFOR
11, the
FORPEER
PEER fracture
REVIEW plugging capacity of LCMs, a fracture sealing testing
REVIEW 6 6ofapparatus
of2121
(Figure 2, Instrument Factory of Petroleum University, Dongying, China) with tapered and slotted
InInorder
order toevaluate
evaluatethe thefracture
fractureplugging
pluggingcapacity
capacityofofLCMs,
LCMs,aafracture
fracturesealing
sealingtesting
testing apparatus
stainless steel discsto(Figure 3) that simulate natural/induced fractures was adopted.apparatus
Firstly, tapered
(Figure 2, Instrument Factory of Petroleum University, Dongying,
(Figure 2, Instrument Factory of Petroleum University, Dongying, China) with tapered and China) with tapered andslotted
slotted
slots were placed
stainlesssteel
stainless
before
steeldiscs the
discs(Figure output
(Figure3)3)that valve.
thatsimulate Then, fluids
simulatenatural/induced containing
natural/inducedfractures
fractureswas LCMs
wasadopted. were forced
adopted.Firstly,
Firstly,tapered to flow at
tapered
a constant
slotsstirring
slots wereplaced
were rate of
placed 100 the
before
before rpm through
theoutput
output the
valve.
valve. discs
Then,
Then, withcontaining
fluids
fluids a gradualLCMs
containing increase
LCMs wereof
were pressure.
forced
forced totoflow
flowTheatataapplied
a
pressureconstant
was initially
constant stirringset
stirring rateto
rate ofofbe100
100 1.0
rpm
rpm MPa andthe
through
through kept stable
thediscs
discs withfor
with 10 min.
aagradual
gradual If theofLCMs
increase
increase effectively
ofpressure.
pressure. Theapplied
The sealed the
applied
pressure
fracturepressure
and thewaswasinitially
pressureinitially settotobe
set
declined be1.0
1.0MPa
withinMPa5%,andkept
and kept
the stablefor
stable
pressure forwas
1010min.
min. IfIfthe
theLCMs
continuously LCMseffectively
effectivelysealed
increased sealed
and the thevolume
the
fractureand
fracture andthe thepressure
pressuredeclined
declinedwithin
within5%,5%,thethepressure
pressurewas wascontinuously
continuouslyincreased
increasedand andthe the
of fluid loss was recorded. Once a continuous leakage of fluid occurred, it was asserted that the LCMs
volumeofoffluid
volume fluidlosslosswas
wasrecorded.
recorded.OnceOnceaacontinuous
continuousleakage
leakageofoffluid
fluidoccurred,
occurred,ititwas
wasasserted
assertedthat that
had reached the
theLCMs
LCMshad
maximum
hadreached
reachedthe
pressure
themaximum
bearing
maximumpressure
capacity
pressurebearing
and
bearingcapacity
the test
capacityand
was
andthe
ceased.
thetest
testwas
Treatments
wasceased.
ceased.Treatments
with
Treatments
lower
the
fluid loss values
withlower
with correspond
lowerfluidfluidloss to
lossvalues effectiveness
valuescorrespond of mitigating
correspondtotoeffectiveness the loss.
effectivenessofofmitigating However,
mitigatingthe theloss. because
loss.However, of
However,because the limitation
becauseofof
that thethe
maximum
thelimitation
limitation applied
thatthe
that thepressure
maximum
maximum is applied
8.0 MPapressure
applied for the isequipment,
pressure is8.0
8.0MPaMPafor the
for maximum
the
the equipment,
equipment, pressure
themaximum
the at which the
maximum
pressure
formed pressure
seal atatwhich
breaks which
andthe theformed
fluid formed sealbreaks
loss seal breakswas
resumes andfluid
and fluidmeasured.
not lossresumes
loss resumeswas wasnot notmeasured.
measured.
Figure 2. Fracture
Figure
Figure pressure
2.2.Fracture
Fracture pressurebearing
pressure capacity
bearingcapacity
bearing test
capacitytest
test apparatus.
apparatus.
apparatus.
Figure 3. Tapered slots with various fracture sizes for fracture sealing testing. Note: (a) Size
Figure 3. Tapered slots with various fracture sizes for fracture sealing testing. Note: (a) Size
Figure 3. Tapered slots with various fracture sizes for fracture sealing testing. Note: (a) Size dimensions;
dimensions;(b)
dimensions; (b)fracture
fractureprofile.
profile.
(b) fracture profile.
Materials 2018, 11, 2020 7 of 20
3. Results
Materials
Materials 2018,
2018, 11,
11, xx FOR
FOR PEER
PEER REVIEW
REVIEW 77 of
of 21
21
3.1. Characterization of OAP
3.
3. Results
Results
3.1.1. Fourier Transform Infrared (FT-IR) Spectra
A possible chemical reaction mechanism for OAP is depicted in Figure 4. The FT-IR spectrum
3.1.1.
3.1.1. Fourier Transform
Fourierprepared
Transformby Infrared
Infrared (FT-IR)
(FT-IR) Spectra
Spectra
of the copolymer suspension polymerization is shown in Figure 5. The characteristic
A
absorption bandspossible chemical
thatchemical
A possible appeared reaction mechanism
at 2920
reaction and 2850for
mechanism cm
for OAP
OAP is
is depicted
−1 were in
in Figure
assigned
depicted 4.
to the
Figure 4. The
The FT-IR
FT-IR spectrum
asymmetric of
and symmetric
spectrum of
the
the copolymer
copolymer prepared
prepared by
by suspension
suspension polymerization
polymerization is
is shown
shown − 1 in
in Figure
Figure 5.
5. The
The characteristic
characteristic
stretching vibrations of C–H, respectively. The bands at 1730 cm were attributed to C=O stretching
absorption
absorption bands
bands that
that appeared
appeared at at 2920
2920−1and
and 2850
2850 cmcm−1 were
−1
were assigned
assigned to to the
the asymmetric
asymmetric and and
vibration. The
symmetric bands at
stretching 1470 and
vibrations 1380
of cm
C–H, corresponded
respectively. The to the C–H −1asymmetric and C=Osymmetric
symmetric stretching vibrations of C–H, respectively. − 1 The bands at 1730 cm were attributed to
bands at 1730 cm −1 were attributed to C=O
bendingstretching
vibration. The bands at 1240atand 1160 cm were the C–O–C asymmetric stretching vibration
stretching vibration.
vibration. The
The bands
bands at 1470
1470 and
and 1380
1380 cm
cm−1 corresponded
corresponded to to the
the C–H
C–H asymmetric
asymmetric and
−1
and
and symmetric − 1
symmetricstretching
symmetric bending vibration,
bending vibration. The respectively.
bands
bands at at 1240Theand band
1160atcm
1160 1030
−1 werecm the
thewasC–O–Cassigned to the C–N
asymmetric
−1
vibration. The 1240 and cm were C–O–C asymmetric
stretching
stretching vibration
vibration.
stretching Theand
vibration bands
and symmetric
at 723stretching
symmetric stretching cm−1 were
and 640vibration,
vibration, respectively.
the outThe
respectively. band
band at
of plane
The 1030
1030 cm
atbending
−1 was
cm−1vibration
was of
assigned
assigned
N–H (amide to the
V)toand C–N
the C–N
C=O stretching
stretching vibration.
(amidevibration. The bands at 723
The bands at 723
VI), respectively. The and
and 640 cm −1 were the out of plane bending
640 cm−1 were theof
disappearance out of plane
C=C bending
bands usually at
vibration of N–H
N–H (amide V)
V) and
and C=O (amide
(amide VI), respectively. The
The disappearance
disappearance of of C=C
C=C bands
1620–1680 cm−1 of
vibration indicated (amide
the thorough C=O reaction VI), respectively.
of the monomers. bands
usually
usually at
at 1620–1680
1620–1680 cm
cm−1 indicated
indicated the
−1
the thorough
thorough reaction
reaction of
of the
the monomers.
monomers.
COO(CH
COO(CH22))33CH
CH33 ++ +
COOCH
COOCH33 + COO(CH
COO(CH22))18CH3
18CH3
H H H
H33C(H
C(H22C)
C)33OOC COO(CH
H
N H
N
OOC COO(CH22))18CH3
18CH3
N N
O
O O
O O COOCH
O COOCH33 O
O
NH
NH HN
HN
NH
NH
O H HN
HN
O H3 COOC
3COOC O
O
H COO(CH
COO(CH22))33CH
H33C(H
C(H22C)
C)18 OOC
18OOC CH33
FigureFigure
Figure 4.
4. Possible
4. Possible
Possible chemical
chemical reaction
reaction
chemical mechanism
mechanism for
reactionmechanism foroil-absorbent
for polymer
oil-absorbent
oil-absorbent (OAP).
polymer
polymer (OAP).
(OAP).
100
100
98
98
1380
841
1240 1380
841
96
96
723
723
1470
640
1470
640
1240
94
T(%)
94
T(%)
2850
1030
2850
1030
92
92
2920
2920
90
90
1160
1160
1730
1730
88
88
4000
4000 3500
3500 3000
3000 2500
2500 2000
2000 1500
1500 1000
1000 500
500
-1
Wavenumber
Wavenumber (cm
(cm-1))
FigureFigure
Figure 5.
5. Fourier
Fourier
5. Fourier transform
transform
transform infrared (FT-IR)
(FT-IR) spectrum
infrared(FT-IR)
infrared spectrum of
spectrum oil-absorbent
ofof
oil-absorbent polymer
polymer
oil-absorbent (OAP).
(OAP).(OAP).
polymer
3.1.2.
3.1.2. Thermogravimetric
Thermogravimetric
3.1.2. Thermogravimetric Analysis
Analysis
Analysis (TGA)
(TGA)
(TGA)
The thermal stability is of vital importance for OAP because it has to experience downhole high
The thermal stability
Thetemperature
thermal stability is ofisvital
of vital importancefor
importance for OAP
OAP because
becauseit has to experience
it has downhole
to experience high high
downhole
temperature conditions.
conditions. Figure
Figure 66 presents
presents the
the resolution
resolution of
of weight
weight percent
percent of of OAP
OAP sample
sample with
with the
the
temperature
changeconditions. Figure 6 presents the resolution of weight percent of OAP sample with
change of
of temperature
temperature and
and the
the first
first derivative
derivative thermogravimetric
thermogravimetric curve.
curve. It
It could
could be
be seen
seen that
that before
before
the change of temperature and the first derivative thermogravimetric curve. It could be seen that
before 100 ◦ C little weight loss was observed. The copolymer began to degrade rapidly when the
temperature reached 300 ◦ C. The sample weight loss is about 50.12% at 386 ◦ C. The maximum pyrolysis
rate occurred at about 392 ◦ C. When the temperature reached 436 ◦ C, the sample came to the total
Materials 2018, 11, x FOR PEER REVIEW 8 of 21
Materials 2018, 11, 2020 8 of 20
100 °C 2018,
Materials little11,weight loss
x FOR PEER was observed. The copolymer began to degrade rapidly when8 ofthe
REVIEW 21
temperature reached 300 °C. The sample weight loss is about 50.12% at 386 °C. The maximum
pyrolysis
100 The
pyrolysis. rate occurred
°C little
results weight at about
loss
indicated was 392 °C. When
observed.
that OAP Thethe
had temperature
a copolymer
good reached
began
thermal 436 °C,
to degrade
stability andthe sample
rapidly
could came
when
be to in high
the
used
the total pyrolysis.
temperature reachedThe300
results
°C. indicated
The samplethatweight
OAP hadlossa is
good thermal
about stability
50.12% at 386and°C.could be used in
The maximum
temperature environments.
high temperature
pyrolysis environments.
rate occurred at about 392 °C. When the temperature reached 436 °C, the sample came to
the total pyrolysis. The results indicated that OAP had a good thermal stability and could be used in
0.2
high temperature environments. 300 C, 4.26% weight loss o
100
0.0
0.2
-0.2
80
100 300 oC, 4.26% weight loss
C) (%/ C)
0.0
-0.4
o
-0.2
60 -0.6
(%)
80
weight
-0.4
o
weight (%/
Weight Weight
-0.8
40 386.2 oC, 50.12% weight loss
60 -0.6
(%)
Derivative
-1.0
-0.8
20
40 386.2 oC, 50.12% weighto loss -1.2
392 C
Derivative
-1.0
436 oC, 98.1% weight loss -1.4
TGA -1.2
0
20
DTG 392 oC -1.6
o
436 C, 98.1% weight loss -1.4
0 TGA 200 400 600 800 1000
0
DTG Temperature (oC)
-1.6
0 200 400 600 800 1000

Figure
Figure 6. 6. Thermogravimetric
Thermogravimetric analysis
analysis (TGA)(TGA)
andand Derivative
Derivative thermogravimetric analysis
thermogravimetric analysis (DTG
(DTG )) curves
curves of OAP. Temperature (oC)
of OAP.
Figure 6. Thermogravimetric analysis (TGA) and Derivative thermogravimetric analysis (DTG )
3.1.3.curves
3.1.3. Scanning Scanning Electron
Electron
of OAP. Microscopy
Microscopy (SEM)
(SEM)
In order to observe the microstructure of OAP, SEM was used to inspect the cross section and
In 3.1.3.
orderScanning
to observe theMicroscopy
Electron microstructure
(SEM) as of OAP, SEM was used to inspect the cross section
surface morphologies of OAP samples, depicted in Figure 7. From Figure 7a, aggregated
and surface morphologies
micrometer-sized
In order to observe
of
spherestheOAP
were samples, as
clearly observed.
microstructure
depicted
It isSEM
of OAP, worth in Figure
mentioning
was
7.thatFrom
used to inspect many Figure 7a, were
small section
the cross pores aggregated
and
micrometer-sized
randomly spheres were
distributed
surface morphologies in
of theclearly
OAP observed.
samples.
samples,There It is support
pores
as depicted worth mentioning
7. From that
the favorable
in Figure many
space
Figure in small
7a,the pores were
polymer
aggregated
randomly distributed
network.
micrometer-sized inspheres
the samples.
The three-dimensional There
network
were clearly pores support
structure
observed. It isand the favorable
micro-pores
worth mentioning with space
thatproper
many insize
theand
small polymer
quantity
pores network.
were
was beneficial
randomly
The three-dimensional fornetwork
the oil
distributed inmolecules
the to enter
samples.
structure intopores
There
and the internal
micro-pores supportspace;
withthe however,
size it
favorable
proper is not
space
and ineasy
thefor
quantity the oil
polymer
was beneficial
molecules
network. to exude
The from the three-dimensional
three-dimensional network crosslinked
structure resin, like with
a sponge [47].
for the oil molecules to enter into the internal space;and micro-pores
however, it is not proper
easy forsizethe
andoil
quantity
molecules to
was beneficial for the oil molecules to enter into the internal space; however, it is not easy for the oil
exude from the three-dimensional crosslinked resin, like a sponge [47].
molecules to exude from the three-dimensional crosslinked resin, like a sponge [47].
Figure 7. Scanning electron microscope (SEM) microphotographs of OAP. Note: (a) Surface; (b) cross
section.
Figure 7. Scanning electron microscope (SEM) microphotographs of OAP. Note: (a) Surface; (b) cross
Figure 7. ScanningCapacity
3.2. Oil-Adsorptive electron microscope (SEM) microphotographs of OAP. Note: (a) Surface;
section.
(b) cross section.
The evolution of oil adsorptive rate which is calculated with Equation (1) with time is depicted
3.2.Figure
in Oil-Adsorptive
8. As canCapacity
be seen from Figure 8, for both No. 3 white oil and diesel oil, a quick adsorption
3.2. Oil-Adsorptive Capacity
The evolution of oil adsorptive rate which is calculated with Equation (1) with time is depicted
Theinevolution
Figure 8. Asofcan
oilbeadsorptive rate which
seen from Figure is calculated
8, for both No. 3 whitewith Equation
oil and diesel oil,(1) withadsorption
a quick time is depicted
in Figure 8. As can be seen from Figure 8, for both No. 3 white oil and diesel oil, a quick adsorption
rate was observed for the initial testing interval of 20 h, followed by a slightly increased adsorptive
rate, and it finally reached saturated adsorption. After testing for 72 h, the white oil absorbency was
8.3, 9.9, 11.4 g/g for testing temperature of room temperature, 90 ◦ C and 120 ◦ C, and the diesel oil
absorbency was 6.7, 7.6, 9.0 g/g accordingly. Based on the field experience, the saturation adsorption
time of water absorbent resin higher than 5 h would be sufficient for the resin to be injected into the
rate was
Materials observed
2018,
Materials 2018, 11, 2020
11, x FORfor theREVIEW
PEER initial testing interval of 20 h, followed by a slightly increased adsorptive 9 of 21
9 of 20
rate, and it finally reached saturated adsorption. After testing for 72 h, the white oil absorbency was
rate
8.3, was observed
9.9, 11.4 g/g for fortesting
the initial testing interval
temperature of room of temperature,
20 h, followed 90by°Ca and
slightly
120 increased
°C, and the adsorptive
diesel oil
rate, and it finally reached saturated adsorption. After testing for 72 h, the
absorbency was 6.7, 7.6, 9.0 g/g accordingly. Based on the field experience, the saturation adsorptionwhite oil absorbency was
downhole 8.3,
and
9.9,
fulfil
11.4
itsforrole
g/g
[48],temperature
testing
therefore for of
OAP,temperature,
room
it would not 90
become
°C and
adsorption
120 °C, and
saturation
the diesel oil
before
time of water absorbent resin higher than 5 h would be sufficient for the resin to be injected into the
reachingabsorbency
the desired
downhole and
thief
wasfulfil zone,
6.7, 7.6, which
9.0 g/g
its role
is advantageous
[48],accordingly.
therefore forBased
OAP,on
for downhole
the field
it would
application.
notexperience, the saturation
become adsorption
OAP particles
adsorption
saturation before
would
still absorb
time oil
reaching when
of water entering
the absorbent
desired the
resin
thief losswhich
higher
zone, fractures and prevent
thanis5 advantageous
h would forfluid
be sufficient forloss.
downhole Meanwhile,
the resin the particles
to be injected
application. OAP oil-adsorptive
into the
downhole
rate increased
would still and
with fulfil
absorb its role
the increasing
oil when [48], therefore
testing
entering for OAP,
thetemperatures,
loss it would
fractures not become
implying
and prevent adsorption
that
fluid saturation
OAPMeanwhile,
loss. would before
adsorb
the oil-a larger
amountreaching
of oil inthe
adsorptive the desired
rate increased
downhole thiefwith
zone, thewhich is advantageous
increasing
environment. forsaturation
testing temperatures,
Moreover, the downhole
implying application.
that OAPOAP
adsorptive wouldparticles
amount adsorb
of white oil
would
a larger still absorb
amount of oil
oil when
in the entering the
downhole loss fractures
environment. and prevent fluid loss.adsorptive
Meanwhile, the oil-
was higher than that of diesel oil, demonstrating thatMoreover,
OAP may thebesaturation
more effective in amount of
white oil-based
adsorptive rate increased with the increasing testing temperatures,
white oil was higher than that of diesel oil, demonstrating that OAP may be more implying that OAP wouldin
effective adsorb
white
drillingafluid.
larger amount offluid.
oil in the downhole environment. Moreover, the saturation adsorptive amount of
oil-based drilling
white oil was higher than that of diesel oil, demonstrating that OAP may be more effective in white
10
oil-based
12 drilling fluid.
10 108
12
(g/g) (g/g)
(g/g) (g/g)
8
oil absorbency
10 86
oil absorbency
6
8
absorbency
absorbency
64
4
6
White
42
Diesel
2 Room temperature
4
Room temperature
White oil
90 oC Diesel oil 20 90 oC
2
0
120 oCtemperature
Room a b
120 oCtemperature
Room
o
-10 0 10 20 30 40 90
50 C 60 70 80 -10 0 10 20 30 40 50 oC 60 70 80
90
0
Time (h) 120 oC a 0
Time (h) 120 oC b
-10 0 10 20 30 40 50 60 70 80 -10 0 10 20 30 40 50 60 70 80
Figure 8.Figure 8. Evolution
Evolution of oilofadsorptive
oil adsorptive
Time (h)
rate
rate withtime
with time under
under various
varioustemperatures.
temperatures.
Time (h)
Note:Note:
(a) white
(a)oil;
white oil;
(b) diesel oil.
(b) diesel oil.
Figure 8. Evolution of oil adsorptive rate with time under various temperatures. Note: (a) white oil;
(b) diesel microscope
Optical oil. photographs of OAP particles before and after white oil adsorption are
Optical microscope photographs of OAP particles before and after white oil adsorption are
displayed in Figure 9. An explicit distinction was observed between original OAP and swollen OAP.
displayed in Figure
Optical
As shown 9. An
in microscope
Figure explicit
photographs
9a, before distinction
of OAP
oil adsorption, wasamount
observed
particles
a large before between
and original
afterparticles
of spherical white oil OAP and
adsorption
with areswollen
some cavities
OAP. As were accumulated together and formed an irregular surface, whereas, after reaching saturated some
shown
displayed in
in Figure
Figure 9. 9a,
An before
explicit oil adsorption,
distinction was a large
observed amount
between of spherical
original OAP and particles
swollen with
OAP.
As shown
cavities adsorption,
were inthe
Figure
accumulated
small9a,particles
before oil
together adsorption,
and
expanded formed a large amount
an irregular
significantly of spherical
surface,
and filled particles
whereas,
in the gap with some
after
space between cavities
reaching saturated
the adjacent
were accumulated
particles, forming together
a smooth and formed an irregular surface, whereas, after reaching saturated
surface. significantly and filled in the gap space between the adjacent
adsorption, the small particles expanded
adsorption, the small particles expanded significantly and filled in the gap space between the adjacent
particles, forming a smooth surface.
particles, forming a smooth surface.
Figure 9. Microphotogram of OAP particles before (a) and after (b) No. 3 white oil adsorption.
Figure Figure 9. Microphotogram of OAP particles before (a) and after (b) No. 3 white oil adsorption.
9. Microphotogram of OAP particles before (a) and after (b) No. 3 white oil adsorption.
3.3. Influence of OAP on the Properties of OBDFs

The effect of OAP particles (particle size of 80–100 mesh) on the properties of OBDFs was
investigated firstly. OAP with various contents was added into the OBDFs. The fluid was hot-rolled
at 120 ◦ C for 16 h. The properties of the fluids before and after hot rolling are given in Table 2.
Before hot rolling, the addition of OAP had little influence on the rheological properties of the OBDFs,
scuh that AV (calculated with Equation (2)), PV (calculated with Equation (3)), YP (calculated with
Equation (4)) and Gel changed slightly with the increase of OAP content; however, after hot rolling,
the rheological parameters including AV, PV, YP and Gel strength all increased gradually initially
when the OAP content was lower than 1.5 w/v %, and showed a significant increase at content of
Materials 2018, 11, 2020 10 of 20
3 w/v %. In terms of filtration control, as shown in Table 2, the API fluid loss decreased gradually with
the increasing content of OAP for both before and after hot rolling. Also as depicted in Figures 10
and 11, for the HTHP static filtration test conducted under 120 ◦ C and 3.5 MPa after hot rolling, both of
the HTHP static fluid loss volume and filter cake thickness decreased with the increased content of
OAP, which was reduced by 74% and 24%, respectively, when 3 w/v % OAP was added, indicating that
OAP could effectively reduce the filtration loss and improve the filter cake quality. In regard to the
electrical stability (ES) of the drilling fluid, which is one of the vital properties of an oil-based drilling
fluid, this shows the voltage of the current flowing in the fluid and represents the emulsion stability of
the fluid. The emulsion-breaking voltage decreased generally with the increasing content of OAP.
Table 2. Effect of OAP on the properties of oil-based drilling fluid (OBDF) base formula.
Testing AV PV YP Gel FLAPI ES

Content (w/v %)
Condition (mPa·s) (mPa·s) (Pa) (Pa/Pa) (mL) (Volt)
BHR 11 9 1.9 1.5/2 7
0 2047
AHR 12 9 2.9 2.0/3 7.4
BHR 12.5 9 3.4 1.0/1.0 5.6
0.5 2047
AHR 18 14 3.8 1.0/1.5 5.3
BHR 15 12 2.9 1.0/1.5 4.8
1 1980
AHR 28 18 9.6 1.5/2 3.1
BHR 11.5 10 1.4 1.5/2 5.6
1.5 1562
AHR 31 18 12.5 3.5/4.5 2.4
BHR 17 10 6.7 1.5/1.75 2.2
3 1345
AHR 98.5 65 32.2 8.0/9 1.2
20
20
Fluid loss volume 2.1
Fluid loss volume 2.1
18 Filter cake thickness
(mL)
18 Filter cake thickness

volume(mL)
16 2.0
(mm)
16 2.0
thickness(mm)
filtrationvolume
14
14
cakethickness
1.9
1.9
staticfiltration
12
12
10 1.8
10 1.8
Filtercake
HTHPstatic
8
8 1.7
Filter
HTHP
1.7
6
6
1.6
4 1.6
4
0.0 0.5 1.0 1.5 2.0 2.5 3.0
0.0 0.5 1.0 1.5 2.0 2.5 3.0
OAP Content (w/v%)
OAP Content (w/v%)
Figure
Figure Figure
10. 10. Variation
Variation of HTHPstatic
of ofHTHP static filtration
filtrationvolume and and
volume filter cake
filterthickness as a function
cake thickness asofof OAP
a OAP
function of
10. Variation HTHP static filtration volume and filter cake thickness as a function
content.
OAP content.
content.
Figure 11. Photograph of HTHP filtration cakes with varying OAP contents. Note: (a) control sample;
Figure Figure
11.
(b) 0.5
11. Photograph of HTHP filtration cakes with varying OAP contents. Note: (a) control sample;
Photograph
w/v % OAP;of(c)HTHP
1.0 w/vfiltration
% OAP; (d)cakes with
1.5 w/v varying
% OAP; (e) 3.0OAP contents.
w/v % OAP. Note: (a) control sample;
(b) 0.5 w/v % OAP; (c) 1.0 w/v % OAP; (d) 1.5 w/v % OAP; (e) 3.0 w/v % OAP.
(b) 0.5 w/v % OAP; (c) 1.0 w/v % OAP; (d) 1.5 w/v % OAP; (e) 3.0 w/v % OAP.
3.4.Sealing
3.4. SealingProperties
PropertiesofofOAP
OAP
The impact of OAP particles on the properties of OBDF could be explained by the fact that,
3.4.1.High-Temperature
when OAP
3.4.1. High-Temperature
particles were addedandHigh-Pressure
and High-Pressure
into the fluid Filtration Test it began to adsorb oil, but the adsorptive
initially,
Filtration Test
content wasTworelatively
Two low. available
commercially
commercially After hot
available rolling
fluid
fluid at highincluding
lossadditives
loss additives temperatures
including for
asphaltic
asphaltic a certain
additive
additive time, a large
andmodified
and modified ligniteamount
lignite
wereused
were usedasasreference
referencetotocompare
comparethetheversatility
versatilityof
ofOAP.
OAP.TheThefluid
fluidloss
lossadditives
additiveswith
with11w/vw/v%%contents
contents
were added into the base formula of the OBDF and hot rolled at 120 °C for 16 h, and
were added into the base formula of the OBDF and hot rolled at 120 °C for 16 h, and then the HTHP then the HTHP
filtration tests were performed. As shown in Figure 12, for the HTHP static filtration test, the
filtration tests were performed. As shown in Figure 12, for the HTHP static filtration test, the fluid loss fluid loss
volume was 32.4, 13.2, 20.4 and 23.6 mL for the base fluid, fluid containing OAP, modified
volume was 32.4, 13.2, 20.4 and 23.6 mL for the base fluid, fluid containing OAP, modified lignite and lignite and
asphalticadditives,
asphaltic additives,respectively,
respectively,showing
showingthethecapacity
capacityofofdecreasing
decreasingHTHPHTHPstatic
staticfiltration
filtrationwith
withthe the
sequence of OAP > modified lignite > asphaltic additives. For the HTHP dynamic
sequence of OAP > modified lignite > asphaltic additives. For the HTHP dynamic filtration test, thefiltration test, the
Materials 2018, 11, 2020 11 of 20
of oil was adsorbed by OAP, resulting in the decreased amount of free oil in the system. Meanwhile
the swelled volume of OAP particles increased the friction of the fluid. The decreased content of free
base oil and increased friction in the fluid contributed to the viscosity buildup, lower fluid loss and
reduction of emulsion stability. Furthermore, the expansive OAP particles participated in forming the
filter cake, which was also favorable for reducing filtration.
3.4. Sealing Properties of OAP
3.4.1. High-Temperature and High-Pressure Filtration Test

Two commercially available fluid loss additives including asphaltic additive and modified lignite
were used as reference to compare the versatility of OAP. The fluid loss additives with 1 w/v % contents
were added into the base formula of the OBDF and hot rolled at 120 ◦ C for 16 h, and then the HTHP
filtration tests were performed. As shown in Figure 12, for the HTHP static filtration test, the fluid
loss volume was 32.4, 13.2, 20.4 and 23.6 mL for the base fluid, fluid containing OAP, modified lignite
and asphaltic additives, respectively, showing the capacity of decreasing HTHP static filtration with
the sequence of OAP > modified lignite > asphaltic additives. For the HTHP dynamic filtration test,
the fluid loss volume increased to 115.2, 52.0, 97.6 and 62.4 mL for the four fluids, showing the ability
of decreasing HTHP dynamic filtration following the order of OAP > asphaltic additive > modified
lignite. The significant increase of fluid loss compared with that of static filtration lies in the fact
that filter cake was more difficult to form under a dynamic shear condition [49]. Overall, the three
candidate additives all exhibited effective performance in HTHP filtration control.
18 Base fluid
Base fluid 60
Base fluid + 1 w/v% OAP Base fluid +1 w/v% OAP
16
Base fluid + 1 w/v% Modified lignite Base fluid + 1 w/v% Modified Lignite
HTHP dynamic fluid loss (mL)
Base fluid + 1 w/v% Asphaltic additive 50 Base fluid + 1 w/v% Asphaltic additive
HTHP static fluid loss (mL)
14
12 40
10 30
8
20
6
10
4
2
a 0
b
1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 0 1 2 3 4 5 6
Square root of time (min0.5) Square root of time (min0.5)
FigureFigure 12. HTHP

12. HTHP static
static fluidfluid loss
loss (a)(a)and
anddynamic
dynamic fluid
fluidloss (b)(b)
loss versus square
versus root ofroot
square time.
of time.
The cumulative
The cumulative fluidvolume
fluid loss loss volume of HTHP
of both both HTHP
staticstatic filtration
filtration testtest
andand HTHP
HTHP dynamic
dynamic filtration
filtration test as a function of square root of time was analyzed with different mathematic models.
test as a function of square root of time was analyzed with different mathematic models. For HTHP
For HTHP static filtration, a typical model recommended by API standard was given as follows [50],
static filtration, a typical model recommended by API standard was given as follows [50],
V = V + m √t (5)
√
where Vsp and m are the intercept and slopeV= of V
the + mrepresenting
spline, t the spurt loss and filtration rate, (5)
respectively.
where Vsp and mfor
While areHTHP
the intercept and slope
dynamic filtration test, of the line,
another model representing
describing thethe spurtinloss
filtration and filtration
a dynamic
test consisting
rate, respectively. of three separate steps: (1) spurt loss, (2) filter-cake deposition (square-root-of-time
dependence), and (3) limitation of cake buildup by erosion (linear time dependence), was proposed
While for HTHP dynamic filtration test, another model describing the filtration in a dynamic
by Roodhart [51] as follows,
test consisting of three separate steps: (1) spurt loss, (2) filter-cake deposition (square-root-of-time
dependence), and (3) limitation of cake buildup V = Vby+erosion
m√t + Bt(linear time dependence), was proposed(6) by
Roodhart [51]Vas
where follows,the spurt loss, the constants m and
sp indicates
√ B represent the static and dynamic filtration
components. V = Vsp + m t + Bt (6)
According to the proposed models (Equations (5) and (6)), the HTHP filtration test data were fitted
where Vand
sp indicates the 3.
given in Table spurt loss,bethe
It could seenconstants m models
that the two and B represent
appeared tothe static
fit well as and dynamic
the value filtration
of R2 all
approached to 1. With regard to the HTHP static filtration test, the addition of fluid loss reducers caused
components.
the increase of spurt loss, but lowered the filtration rates. The fluid in the presence of OAP generated
the lowest filtration rate. For the HTHP dynamic filtration test, all the filtration components including
spurt loss, static filtrate rate, and dynamic filtration rate decreased obviously after addition of the fluid
loss reducers. The difference of filtrate rate between static and dynamic filtration was not clear, whereas,
it was obvious that OAP was capable of reducing HTHP fluid loss more effectively than modified lignite
and asphaltic additive under both static and dynamic conditions.
Materials 2018, 11, 2020 12 of 20
According to the proposed models (Equations (5) and (6)), the HTHP filtration test data were
fitted and given in Table 3. It could be seen that the two models appeared to fit well as the value of R2
all approached to 1. With regard to the HTHP static filtration test, the addition of fluid loss reducers
caused the increase of spurt loss, but lowered the filtration rates. The fluid in the presence of OAP
generated the lowest filtration rate. For the HTHP dynamic filtration test, all the filtration components
including spurt loss, static filtrate rate, and dynamic filtration rate decreased obviously after addition
of the fluid loss reducers. The difference of filtrate rate between static and dynamic filtration was not
clear, whereas, it was obvious that OAP was capable of reducing HTHP fluid loss more effectively
than modified lignite and asphaltic additive under both static and dynamic conditions.
Table 3. HTHP static filtration and dynamic filtration test results for OBDFs containing various fluid
loss additives.
HTHP Static Filtration HTHP Dynamic Filtration

Drilling Fluid Formula
Vsp m R2 Vsp m B R2
Base fluid 0.1075 2.8814 0.9982 14.771 3.2301 0.8218 0.9989
Base fluid + 1 w/v % OAP 0.4689 1.1507 0.9960 2.3177 2.5393 0.3072 0.9971
Base fluid + 1 w/v %
0.3295 1.8622 0.9942 4.9221 1.6198 1.1411 0.9984
Modified lignite
Base fluid + 1 w/v %
0.7577 1.9535 0.9955 3.3494 2.9944 0.3557 0.9977
Asphaltic additive
3.4.2. Permeability Plugging Test

The results of the permeability plugging tests of OBDFs with and without fluid loss reducers are
3.4.2. Permeability Plugging Test
shown in Figure 13 and Table 4. The total loss of control sample was as high as 47.6 mL, indicating
that base fluidThe results
was notof the permeability
able to plug plugging tests of OBDFs
the micro-pores with and
of disks. without fluid
However, anloss reducers
obvious are
decrease of
shown in Figure 13 and Table 4. The total loss of control sample was as high as 47.6 mL, indicating
total loss was observed after the addition of 1 w/v % fluid loss reducers. Furthermore, the static
that base fluid was not able to plug the micro-pores of disks. However, an obvious decrease of total
filtration rate decreased from 6.57 mL/min1/2 to 0.95, 2.26, 3.43 mL/min1/2 after incorporation
loss was observed after the addition of 1 w/v % fluid loss reducers. Furthermore, the static filtration
of OAP,rate modified
decreasedlignite, and
from 6.57 asphalt
mL/min 1/2 toadditive,
0.95, 2.26, respectively. Because
3.43 mL/min1/2 after of the elastic
incorporation of OAP,and deformable
modified
properties, OAP
lignite, particles
and asphalt could berespectively.
additive, easily squeezed Because intoofthe
themicro-pores. After entering
elastic and deformable the micro-pores,
properties, OAP
particles
the particles could beto
continued easily squeezed
absorb oil and into the micro-pores.
swell to saturation After entering
state. the micro-pores,
The enlarged volume thecould
particles
effectively
continued
fill in the to absorb
micro-pores andoillead
and to
swell
thetodecrease
saturationof state. The
fluid enlarged volume could effectively fill in the
loss.
micro-pores and lead to the decrease of fluid loss.
Base fluid
25 Base fluid + 1 w/v% OAP
Base fluid + 1 w/v% Modified lignite
Base fluid + 1 w/v% Asphalt additive
Acumulative fluid loss (mL)
20
15
10
0
1 2 3 4 5 6
Square root of time (min0.5)
Figure Figure 13. Fluid

13. Fluid losses
losses versus
versus thethe squareroot
square root of
of minutes
minutesforfor
thethe
permeability plugging
permeability test. test.
plugging
Table 4. Effect of various sealing agents on the fluid loss of OBDFs obtained via permeability plugging test.
Static Filtration Rate

Testing Sample Total Fluid Loss (mL) Spurt Loss (mL)
(mL/min1/2)
Base fluid 47.6 11.6 6.57
Base fluid + 1 w/v % OAP 10.2 5 0.95
Base fluid + 1 w/v % Modified lignite 19.4 7 2.26
Base fluid + 1 w/v % Asphalt additive 23.6 4.8 3.43
3.4.3. Sand Bed Filtration Test

The sand bed filtration test was designed to more realistically evaluate the tendency of a fluid to
invade a permeable and unconsolidated formation [42]. As shown in Figure 14 and Table 5, when
there was no sealing agent in the control sample, the base fluid invaded the sand bed readily and
Materials 2018, 11, 2020 13 of 20
Table 4. Effect of various sealing agents on the fluid loss of OBDFs obtained via permeability
plugging test.
Total Fluid Spurt Loss Static Filtration Rate

Testing Sample
Loss (mL) (mL) (mL/min1/2 )
Base fluid 47.6 11.6 6.57
Base fluid + 1 w/v % OAP 10.2 5 0.95
Base fluid + 1 w/v % Modified lignite 19.4 7 2.26
Base fluid + 1 w/v % Asphalt additive 23.6 4.8 3.43
3.4.3. Sand Bed Filtration Test

The sand bed filtration test was designed to more realistically evaluate the tendency of a fluid to
invade a permeable and unconsolidated formation [42]. As shown in Figure 14 and Table 5, when there
was no sealing agent in the control sample, the base fluid invaded the sand bed readily and rapidly,
and the total invasion depth reached about 7.2 cm after the test. After addition of sealing agents,
the invasion depth decreased to a different extent. Compared with modified lignite and asphalt
additive, OAP exhibited a better sealing performance. In the testing process, there was a small amount
of initial invasion, followed by the rapid formation of a dense and extremely low permeability seal in
just a few seconds. The fluid invasion ceased with an invasion depth of only 1.5 cm, which was the
shortest invasion depth observed in contrast with other two products. This rapid shutoff of invasion
was crucial in achieving the excellent results seen in the field.
Figure 14. Comparison of the sand bed invasion depths for various fluid loss additives. Note: (a)
Figure 14. Comparison of the sand bed invasion depths for various fluid loss additives. Note: (a) control
control sample; (b) OAP; (c) asphaltic additive; (d) modified lignite.
sample; (b) OAP; (c) asphaltic additive; (d) modified lignite.
Table 5.Table 5. Comparison of invasion depths of various OBDF formulas for a sand bed filtration test.
Comparison of invasion depths of various OBDF formulas for a sand bed filtration test.
Testing Sample Average Invasion Depth (cm)
Testing
BaseSample
fluid Average Invasion
7.2 Depth (cm)
Base fluid
Base+fluid
1 w/v % OAP 1.57.2
BaseBase fluid
fluid + 1 w/v
+ 1 w/v % OAPlignite
% Modified 2.21.5
Base fluid++11w/v
Basefluid w/v % Asphaltic
Modified additive
lignite 2 2.2
Base fluid + 1 w/v % Asphaltic additive 2
3.4.4. Fracture Sealing Test
3.4.4. Fracture Sealing Test

(1) The sealing capacity of OAP in OBDF with a 0.2 mm width slot.
(1) TheFirstly,
sealing thecapacity of OAP
fracture sealing in OBDF
ability of OAPwith a 0.2 mmbywidth
was evaluated slot.
a 0.2 mm width slot to simulate light
losses. OBDF with OWR of 80:20 containing 1 w/v % OAP with size of 80–100 mesh was poured into
Firstly, the fracture sealing ability of OAP was evaluated by a 0.2 mm width slot to simulate light
the cell. When the pressure increased to 1.0 MPa, almost all of fluid was lost, indicating sealing failure.
losses. OBDF
After thewith OWR ofthe
experiment, 80:20 containing
fracture 1 w/v
was taken % shown
out. As OAP with size15,
in Figure of the
80–100 mesh
swollen OAPwas poured into
particles
the cell.had
Whenbeenthe pressure
forced into theincreased towere
fracture and 1.0 MPa, almost
distributed all the
along of fluid was
fracture lost,Unlike
plane. indicating sealing failure.
rigid materials
After thewith high strength,
experiment, theOAP particles
fracture wasexhibited low As
taken out. compressive
shown instrength
Figureafter oil adsorption,
15, the swollen OAP which particles
could not form effective sealing alone. However, taking other materials such as SCC
had been forced into the fracture and were distributed along the fracture plane. Unlike rigid materials particles and
sized RUB particles in combination, this relatively narrow fracture was easy to seal.
with high strength, OAP particles exhibited low compressive strength after oil adsorption, which could
(1) The sealing capacity of OAP in OBDF with a 0.2 mm width slot.
Firstly, the fracture sealing ability of OAP was evaluated by a 0.2 mm width slot to simulate light
losses. OBDF with OWR of 80:20 containing 1 w/v % OAP with size of 80–100 mesh was poured into
the cell. When the pressure increased to 1.0 MPa, almost all of fluid was lost, indicating sealing failure. 14 of 20
Materials 2018, 11, 2020
After the experiment, the fracture was taken out. As shown in Figure 15, the swollen OAP particles
had been forced into the fracture and were distributed along the fracture plane. Unlike rigid materials
not formwith high strength, OAP particles exhibited low compressive strength after oil adsorption, which
effective sealing alone. However, taking other materials such as SCC particles and sized RUB
could not form effective sealing alone. However, taking other materials such as SCC particles and
particlessized
in combination, this relatively narrow fracture was easy to seal.
RUB particles in combination, this relatively narrow fracture was easy to seal.
FigureFigure 15. Performance of OAP to control the lost circulation in OBDFs (0.2 mm slot).
15. Performance of OAP to control the lost circulation in OBDFs (0.2 mm slot).
(2) The sealing capacity of LCMs in a 1 × 0.5 mm width slot.

This fracture was selected to model light to medium losses. Because OAP individually could not
effectively seal small fractures, to deal with this kind of loss it is widely accepted that combinations
of LCMs are much more effective compared to just one type of LCM when curing lost circulation.
The LCM’s type, concentration, particle size distribution and fracture width are the vital factors for
effective sealing [52]. Based on general experience, rigid particles like calcium carbonate, deformable
particles like rubber, and fibers were used in combination to improve the sealing capacity in this
study. The particle size classification of LCMs is presented in Table 6. According to effective bridging
theory [53] and numerous laboratory experiments, an acceptable LCM formula No. 1 aimed for the
1 × 0.5 mm tapered slot was established as a control sample and shown in Table 7.
Table 6. Classification of lost circulation materials’ (LCM) particle sizes.
Number 0 I II III IV
Mesh 6~10 10~20 20~40 40~80 >80
Particle size/mm 3.2~2.0 2.0~0.9 0.9~0.45 0.45~0.2 <0.2
Table 7. LCM formula for lost circulation control of oil-based drilling fluids in a 1 × 0.5 mm slot.
Testing Sample SCC-II RUB-II SCC-III RUB-III SCC-IV FIB OAP

No. 1 2.0% 0.5% 3.0% 0.5% 1.0% 0.1% -
No. 2 2.0% 0.5% 3.0% 0.5% 1.0% 0.1% 1.0%
The testing results shown in Figure 16 indicates that, for the control sample of formula No. 1,
the fluid loss volume kept stable when the pressure less than 4.0 MPa, indicating the blended materials
formed effective sealing in the fracture. After that, the fluid loss volume increased to 17 mL regardless
of the increase of pressure. While for formula No. 2, the fluid loss volume was 5 mL at pressure of
1.0 MPa, then it increased to 7 mL and kept constant with the change of pressure, demonstrating that
addition of OAP promoted formation of a tighter sealing in the fracture. As shown in Figure 17a,
SCC particles and rubber particles were trapped with fibers to form a sealing integrity in the fracture.
After OAP incorporation, as depicted in Figure 17b, SCC particles, rubber particles and OAP particles
lodged against each other with the help of fibers binding. After rigid particles bridging, the resilient
and deformable particles could fill in the formed voids, which was favorable for forming a tighter seal
and lower fluid loss.
pressure of 1.0 MPa, then it increased to 7 mL and kept constant with the change of pressure,
demonstrating that addition of OAP promoted formation of a tighter sealing in the fracture. As
shown in Figure 17a, SCC particles and rubber particles were trapped with fibers to form a sealing
integrity in the fracture. After OAP incorporation, as depicted in Figure 17b, SCC particles, rubber
particles and OAP particles lodged against each other with the help of fibers binding. After rigid
Materials 2018, 11, 2020
particles bridging, the resilient and deformable particles could fill in the formed voids, which was 15 of 20
favorable for forming a tighter seal and lower fluid loss.
20
15
Fluid loss volume (mL)

10
OBDF + LCM blends

OBDF + LCM blends + 1 w/v% OAP
0
0 1 2 3 4 5 6 7 8 9
Pressure (MPa)
Figure 16.Figure 16. Performance

Performance of LCM
of LCM blendsand
blends and LCM
LCM blends
blendscombined
combinedwithwith
OAPOAP
to control the lostthe lost
to control
circulation
circulation in in oil-based
oil-based drilling
drilling fluids
fluids (1 (1
× ×0.5
0.5mm
mm slot).
slot).
Figure 17. LCMs distribution in the slots after the fracture sealing test. Note: (a) formula No. 1;
Figure
(b) formula No.17.2.LCMs distribution in the slots after the fracture sealing test. Note: (a) formula No. 1; (b)
formula No. 2.
(3) The sealing capacity of LCMs in a 2 × 1 mm width slot.
(3) The sealing capacity of LCMs in a 2 × 1 mm width slot.
This typeThis of
typeslot waswas
of slot used
usedtotosimulate moderate
simulate moderate to severe
to severe losses.losses.
To formTo form sealing,
effective effective thesealing,
the SCCSCCparticles, rubber
particles, rubberparticles
particlesand fiberswith
and fibers withappropriate
appropriate sizesize distribution
distribution and concentration
and concentration were were
optimized after extensive
optimized after extensive experiments,
experiments, then
thenthe
the optimized formula
optimized formula No.No.3 was 3 was established
established as control
as control
sample and shown in Table 8. The fracture sealing test results for OBDFs
sample and shown in Table 8. The fracture sealing test results for OBDFs containing formulas No. containing formulas No. 3 3 and
and No. 4 are given in Figure 18. It was clear that, for both formulas No.
No. 4 are given in Figure 18. It was clear that, for both formulas No. 3 and No. 4, a jump of fluid loss3 and No. 4, a jump of fluid
loss was observed at pressure of 2.0 MPa. For formula No. 3, the fluid loss increased to 40 mL at 2.0
was observed at pressure of 2.0 MPa. For formula No. 3, the fluid loss increased to 40 mL at 2.0 MPa
MPa and kept almost constant with the further increase of pressure. When the pressure reached 8.0
and kept almost
MPa, constant
the fluid loss was with the further
45 mL. A similarincrease
phenomenon of pressure.
was observedWhen for the pressure
formula No. 4,reached
where the 8.0 MPa,
the fluidfluid
lossloss
wasincreased
45 mL. A to similar phenomenon
15 mL and kept unchangedwas observed
regardless for formula
of the increase No.of4,pressure,
where the againfluid loss
increased to 15 mL
indicating thatand kept unchanged
incorporation regardless
of OAP contributed to of the increase
a denser sealing and of pressure,
lower fluidagain indicating
loss. As shown that
in Figure 19a, it was seemed that the blended LCMs without OAP were
incorporation of OAP contributed to a denser sealing and lower fluid loss. As shown in Figure 19a, mainly distributed on the tail
of the fracture, which was relatively easy to be extruded out of the fracture and led to failure of
it was seemed that the blended LCMs without OAP were mainly distributed on the tail of the fracture,
sealing. While in the presence of OAP, as observed in Figure 19b, the blended LCMs filled along the
which was relatively easy to be extruded out of the fracture and led to failure of sealing. While in
entire fracture, beneficial to forming a steady sealing. The results also verified that the addition of
the presence of OAP,the
OAP improved as retention
observed in Figure
of LCMs in the19b, the blended
fractures, LCMs
which in turn filled
caused alongfluid
lowered theloss.
entire fracture,
beneficial to forming a steady sealing. The results also verified that the addition of OAP improved the
retention of LCMs Table in8. LCM formula for lost
the fractures, which circulation
in turncontrol
causedof oil-based
lowereddrilling fluids
fluid in a 2 × 1 mm slot.
loss.
Testing Sample SCC-I SCC- RUB- SCC- RUB- SCC- FIB OAP
No. 3 4.0% 2.0% 0.5% 3.0% 0.5% 1.0% 0.2% -
No. 4 4.0% 2.0% 0.5% 3.0% 0.5% 1.0% 0.2% 1.0%
Materials 2018, 11, 2020 16 of 20
Table 8. LCM formula for lost circulation control of oil-based drilling fluids in a 2 × 1 mm slot.
Testing Sample SCC-I SCC-II RUB-II SCC-III RUB-III SCC-IV FIB OAP
No. 3 4.0% 2.0% 0.5% 3.0% 0.5% 1.0% 0.2% -
No. 4 4.0% 2.0% 0.5% 3.0% 0.5% 1.0% 0.2% 1.0%
50
50 OBDF + LCM blends
OBDF + LCM blends
OBDF + LCM blends + 1w/v% OAP
OBDF + LCM blends + 1w/v% OAP
40
40
(mL)
volume(mL)
30
30
lossvolume
20
Fluidloss
20
Fluid
10
10
0
0
0 1 2 3 4 5 6 7 8 9
0 1 2 3 4 5 6 7 8 9
Pressure (MPa)
Pressure (MPa)
Figure 18. Performance
Performance of LCM
of LCM blends and LCM
blends LCM blends combined with OAPOAP
to control the lost
Figure 18.
Figure 18. Performance of LCM blendsand blendscombined
and LCM blends combined
withwith to control
OAP to control the lostthe lost
circulation
circulation in in oil-based
oil-based drilling
drilling fluids
fluids (2 (2
× ×11mm
mm slot).
slot).
circulation in oil-based drilling fluids (2 × 1 mm slot).
Figure 19. LCM distribution in the slots after the fracture sealing test. Note: (a) Formula No. 3, (b)
Figure 19. LCM
LCM distribution
ininthe
theslots
slots after
afterthe
thefracture sealing test. Note:
test. (a) Formula
(a) No. 3, (b) No. 3,
Figure 19.
Formula No.distribution
4. fracture sealing Note: Formula
Formula No. 4.
(b) Formula No. 4.
3.5. Probable Mechanism of Mitigation of Lost Circulation
OAP particles were synthesized by MMA, BA and LHA with typical crosslinked structure. The
OAP particles were synthesized by MMA, BA and LHA with typical crosslinked structure. The
OAP particleschemicals
crosslinking
crosslinking were synthesized
chemicals
tied the chainsby MMA,
tied the chains together
together BA and
to form
to form LHA with typical
a three-dimensional
a three-dimensional
network,
network,crosslinked
which enabled
which enabled structure.
the polymers
The crosslinking to absorbtied
chemicals oil into
the the spaces
chains in the molecular
together to form anetwork and thus formed
three-dimensional a gel that
network, locksenabled
which
the polymers to absorb oil into the spaces in the molecular network and thus formed a gel that locks
up the liquid. The oil-absorption process was an expansion process of this three-dimensional
the polymers
up the to absorb
liquid. Theoiloil-absorption
into the spaces in the
process wasmolecular
an expansion network
processand of thus formed a gel that locks
this three-dimensional
network, which had a clear transition from the high initial rate to the slow rate and toward the end
network,
up the liquid. which
The had a clear
oil-absorption transition
process from
was the
an high initial
expansion rate to
process the slow
of thisrate and toward the end
three-dimensional network,
of swelling equilibrium by the van der Waals attractive forces between molecules [54].
of swelling equilibrium by the van der Waals attractive forces between molecules [54].
which had aBecause
clear transition from the high initial rate to the slow rate and toward
the oil absorption depended mainly on van der Waals attractive force, the oil absorption the end of swelling
Because the oil absorption depended mainly on van der Waals attractive force, the oil absorption
equilibrium
speedby wasthe van derslow
relatively Waals attractive
compared to thatforces
of waterbetween molecules
absorption [54]. pumped to downhole
resins; when
speed was relatively slow compared to that of water absorption resins; when pumped to downhole
before the
Because absorption
oil saturation,
absorption it would have
depended mainly a lower
on viscosity
van der and small
Waals volume. force,
attractive Upon entering the
the oil absorption
before absorption saturation, it would have a lower viscosity and small volume. Upon entering the
speed waslost-circulation
relatively zone,
slow the absorptiontoofthat
compared oil continued,
of water forming a viscous
absorption plug,when
resins; and created
pumped a barrier
to to
downhole
lost-circulation zone, the absorption of oil continued, forming a viscous plug, and created a barrier to
the subsequent flow of drilling fluid into the fracture channels. Meanwhile, after thorough adsorption
the subsequent flow of drilling fluid into the fracture channels. Meanwhile,
before absorption saturation, it would have a lower viscosity and small volume. Upon entering the after thorough adsorption
under downhole conditions, the OAP particles swelled appreciably in volume and became resilient,
under downhole
lost-circulation zone, them conditions,
the absorption the OAP particles
of oil continued,swelled appreciably in volume andand
became resilient,
which enabled to be more effective in packing forming a viscous
fractures even plug,
with smaller created
widths. a barrier to
However,
which enabled them to be more effective in packing fractures even with smaller widths. However,
the subsequent flowlow
due to their of compressive
drilling fluid into the
strength, thefracture channels.
OAP particles wereMeanwhile,
not efficient in after thorough
closing off the adsorption
lost
due to their low compressive strength, the OAP particles were not efficient in closing off the lost
under downhole
circulation zone alone. When taking the rigid particles, elastic particles, fibers and OAP particles inresilient,
conditions,
circulation zone alone. Whenthe OAP
takingparticles swelled
the rigid particles, appreciably
elastic particles,infibers
volume and
and OAP became
particles in
combination
which enabled them bytoconsidering
be more the particle
effective in shape, surface
packing fractures texture,
even concentration,
with smaller particle
widths. size
However,
combination by considering the particle shape, surface texture, concentration, particle size
Materials 2018, 11, 2020 17 of 20
due to their low compressive strength, the OAP particles were not efficient in closing off the lost
circulation zone alone. When taking the rigid particles, elastic particles, fibers and OAP particles in
combination by considering the particle shape, surface texture, concentration, particle size distribution
and fracture width, a synergistic effect was obtained. The rigid SCC particles firstly formed bridging
in the fracture, which was the framework of the sealing zone. The fibers that wrapped the mixture of
other particles together improved the compactness of the sealing zone. After bridging in the fractures
by rigid particles, deformable particles like OAP particles were able to occupy the voids among the
previously bridged particles and reduce the permeability of the formed seal. Finally, a tight sealing
zone was formed and resulted in a significant drop of fluid loss.
4. Conclusions
In this study, the oil-absorbent polymer (OAP) including MMA, SA, and BA was prepared by
suspension polymerization. The OAPs had spherical and porous structure, and were capable of
absorbing white oil and diesel oil several times of its own weight at temperatures ranging from room
temperature to 120 ◦ C.
The addition of OAP had relatively little influence on the rheological properties of OBDF at
content lower than 1.5 w/v % but increased the fluid viscosity remarkably at content higher than
3 w/v %. OAP particles could reduce the HTHP filtration and improve the sealing capacity of OBDFs
effectively under downhole conditions. OAP particles used individually showed poor fracture-sealing
capacity, but could effectively decrease fluid loss when treated conjunct with calcium carbonate
particles, rubbers and fibers by a synergistic effect.
After addition of OAP into the OBDF, the volume of OAP would increase with time, which resulted
in the increase of viscosity of the fluid and slowed down the fluid loss speed. Meanwhile, the swelled
and deformable OAP could be compressed to enter an opening that is substantially smaller and
different in shape. OAP particles would conform to the openings with various shapes and sizes.
More importantly, OAP particles could occupy the voids of the bridging layer, and resulted in a tight
sealing zone when used in combination with other conventional LCMs.
Author Contributions: Conceptualization, H.Z. and Z.Q.; Methodology, G.S., Investigation, X.X., Resources, P.Y.;
Data Curation, H.Z. and G.S.; Writing—Original Draft Preparation, H.Z.; Funding Acquisition, J.J.
Funding: This work was financially supported by National Natural Science Foundation of China (No. 51704322,
No. U1562101), Natural Science Foundation of Shandong Province (No. ZR2017QEE011), the 13th Five-year Plan
National Key project (2017ZX05005005-006) and Program for Changjiang Scholars and Innovative Research Team
in University (IRT_14R58) and the Fundamental Research Funds for the Central Universities (No. 18CX02099A).
Acknowledgments: The authors are grateful to Jiaxu Chen and Jia Li for their assistance in the preparing of
fracture-sealing experiments.
Conflicts of Interest: There are no conflicts to declare.
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© 2018 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access
article distributed under the terms and conditions of the Creative Commons Attribution
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Mitigation of Lost Circulation in Oil-Based Drilling Fluids Using Oil Absorbent Polymers

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materials

Materials 2018, 11, 2020; doi:10.3390/ma11102020 www.mdpi.com/journal/materials

2. Materials and Methods

2.2. Synthesis and Characterization of Oil-Absorbent Polymer (OAP)

2.3. Preparation of Oil-Based Drilling Fluids (OBDFs)

Component Commercial Name Content Unit

2.4. Rheological Properties and Electrical Stability Measurement

Apparent viscosity (AV) = Φ600/2 (mPa·s) (2)

Plastic viscosity (PV) = Φ600 − Φ300 (mPa·s) (3)

Yield point (YP) = 0.48(Φ300 − PV) (Pa) (4)

2.5. Filtration Properties

0 200 400 600 800 1000

3.3. Influence of OAP on the Properties of OBDFs

Testing AV PV YP Gel FLAPI ES

18 Filter cake thickness

3.4. Sealing Properties of OAP

3.4.1. High-Temperature and High-Pressure Filtration Test

Square root of time (min0.5) Square root of time (min0.5)

FigureFigure 12. HTHP

HTHP Static Filtration HTHP Dynamic Filtration

3.4.2. Permeability Plugging Test

Square root of time (min0.5)

Figure Figure 13. Fluid

Static Filtration Rate

3.4.3. Sand Bed Filtration Test

Total Fluid Spurt Loss Static Filtration Rate

3.4.3. Sand Bed Filtration Test

3.4.4. Fracture Sealing Test

(2) The sealing capacity of LCMs in a 1 × 0.5 mm width slot.

Table 6. Classification of lost circulation materials’ (LCM) particle sizes.

Testing Sample SCC-II RUB-II SCC-III RUB-III SCC-IV FIB OAP

Fluid loss volume (mL)

OBDF + LCM blends

Figure 16.Figure 16. Performance

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