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org/EF Article

Simultaneous Control of Formation and Growth of Asphaltene

Solids and Wax Crystals Using Single-Walled Carbon Nanotubes: an
Experimental Study under Real Oilfield Conditions
Saber Mohammadi* and Fatemeh Mahmoudi Alemi
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ABSTRACT: Asphaltene and wax depositions in oil production

systems have been recognized as the most serious flow assurance
concern of petroleum engineering. Despite the several chemicals
offered for treatment of issues induced by these organic deposits,
proposing a single efficient chemical to control simultaneously both
asphaltene and wax precipitation has not been attended yet. Here,
single-walled carbon nanotubes (SWCNTs) were synthesized to
assess their effects on controlling the formation and size growth of
asphaltene particles and wax crystals in live oil under realistic
production conditions. SDS experiments showed that during
depressurization at 125 °C, the asphaltene onset pressure decreased
from 5946 psi in untreated live oil to 4375 in treated live oil with
100 ppm SWCNTs. High-pressure microscopy revealed that
SWCNTs efficiently controlled the growth of asphaltene aggregates and reduced the size of asphaltenes in live oil during
depressurization at 125 °C. This is ascribed to the strong π−π interactions between the aromatic rings of SWCNTs and electron
clouds of asphaltenes. Results of cross-polarized microscopy showed that SWCNTs at an optimum concentration of 75 ppm
postponed the wax formation temperature and gelation point from 32.6 and 21.5 °C to 23.2 and 14.7 °C, respectively. In addition,
the morphology of the wax crystals with an average size of 756 nm in untreated oil changed from dense spherical-like into thin
needle-like with an average size of 86 nm in treated oil with SWCNTs at 75 ppm. The changes in the wax crystal size and structure
via X-ray powder diffraction analysis after crude oil treatment with SWCNTs confirm interactions between the carbon nanotubes
and active sites of the wax crystals. The findings of this research prove that synthesized carbon nanotubes can be used as efficient
inhibitor and dispersant agents for stabilizing the waxes and asphaltenes in live oil with controlling the rate of aggregation under
high-pressure−high-temperature conditions.

1. INTRODUCTION AND MOTIVATION Coincident precipitation of these components results in the

Solid organic depositsmostly asphaltenes and waxes
during production, transport, and storage of crude oils are
the most challenging issues in petroleum industry. These
deposits accumulate around the wellbore in porous media and
the oil well column, which restricts the flow of hydrocarbon
reservoir fluids and decreases the oil well productivity. Organic
deposits are mainly composed of asphaltene and wax
components of the crude oil. Asphaltene is defined as a
complex mixture that is soluble in aromatic solvents (e.g.,
toluene and benzene) and insoluble in light paraffins (e.g., n-C5
and n-C7).1 Wax components contain a high-molecular weight
n-paraffin and consist mainly of straight-chain alkanes with
small amounts of branched chain paraffin and cyclo-paraffin
(naphthene) with 20−50 carbon atoms.2 Based on the
operation under oilfield conditions, asphaltenes and waxes
precipitate independently, or in some situations, the
intermolecular interactions of the precipitating asphaltenes
with the wax molecules induce their coprecipitation.
formation of a deposit, which differs considerably in physical−
chemical properties from the corresponding waxes and
asphaltenes in the crude oil. The presence of asphaltene
molecules in bulk medium of the crude oil has potential
influence on wax dispersants/inhibitors and pour point
depressants. They interfere with modification mechanisms of
wax inhibitors (or vice versa), and they may change the
morphologies of the wax crystal in crude oils.3,4 However, the
role of asphaltene molecules during the wax crystallization and
deposition has not been satisfactorily described.
Received: July 5, 2021
Revised: August 14, 2021
Published: August 26, 2021

© 2021 American Chemical Society https://doi.org/10.1021/acs.energyfuels.1c02244

14709 Energy Fuels 2021, 35, 14709−14724
Energy & Fuels pubs.acs.org/EF
The mechanisms of asphaltene and wax precipitation and
deposition are fundamentally different. The asphaltene
particles precipitate from the crude oil as thermodynamic
equilibrium conditions, such as pressure and temperature, or
composition changes.5 By disruption of the thermodynamic
equilibrium, pressure of the system drops below the asphaltene
onset pressure (AOP). Precipitated asphaltene particles grow
in size due to the molecular diffusion and the particle−particle
aggregation and eventually may deposit in different sections of
the production integrated system.6 The wax deposition process
involves three main phases: nucleation, growth of wax crystals,
and wax deposition.7 However, nucleation and crystal growth
occur simultaneously in the oil streams. Wax precipitation or
formation occurs as a solid-phase separation as the crude oil
temperature falls below the wax appearance temperature
(WAT).8,9 WAT, also known as the cloud point, is defined
as the temperature at which the first wax crystals precipitate
out of the crude oil in a cooling process. Heat loss or reduction
of temperature is known as the predominant and most critical
factor in wax precipitation and deposition due to the direct
dependence of paraffin solubility on temperature. However,
other factors, such as pressure, oil composition, gas−oil ratio,
and flow rate, also contribute to the wax crystal growth and
deposition.10 Different mechanisms, such as molecular
diffusion, shear dispersion, Brownian diffusion, particle
agglomeration, and gravity settling, are associated with the
wax deposition process.11,12 However, molecular diffusion and
shear dispersion mechanisms are established to be the main
responsible driving forces for wax deposition.13
Proposing practical prevention and treatment methods of
asphaltene and wax precipitation and deposition poses a
serious challenge to the efficient production operation.14
Different strategies have been offered to deal with asphaltene
deposition problems, such as the periodic removal of deposited
asphaltenes by mechanical or chemical washing and inhibition
of asphaltene precipitation by injection of polymeric
surfactant-based chemicals and ionic liquids.15,16 Similarly,
there are different methods that have been developed to handle
the wax deposition problems including removal and inhibition/
prevention approaches. The wax-deposit removal methods
include heat treatment and pipe insulation, mechanical
removing of wax deposits by pigging or scraping, and solvent
injection.8,17 In inhibition or prevention plans, wax inhibitors,
dispersants, or crystal modifiers are utilized to control the size
growth of wax crystals, suspend the dispersed wax particles in
crude oil, and so reduce the wax deposition rate.3,18,19 The wax
inhibitor or dispersant is also effective in depressing of the wax
pour point, which can be called as pour point depressants or
flow improvers.3,4,20 Mechanical-based methods for the
removal of both asphaltenes and wax deposits are time-
consuming and costly, which is aggravated by oil well
shutdowns and production reduction.21 In addition, it is not
practical to apply the mechanical methods within the
formation, especially near the wellbore region, where the
maximum formation damage induced by the organic solid
deposit occurs. Therefore, chemical injection scenarios, such as
asphaltene and wax inhibitors or dispersants, are becoming
more attractive and prevalent. Specifically, because of the long
distances covered by hydrocarbon flow lines, the mechanical
methods are not applicable, and the chemical-based scenarios
are the best solution.22 Asphaltene and wax inhibitors may
function by different mechanisms to control the precipitation
and growth of asphaltene particles and wax crystals in oil
14710
Article
streams. Mechanisms of different types of asphaltene and wax
inhibitors/dispersants have been discussed in detail in the
open literature.7,23−27
Due to the recent developments in nanoscience, nano-
technology has exhibited potential applications in different
sections of the petroleum industry, such as exploration and
production, drilling operations, enhanced oil recovery (EOR),
and petrochemical refinery processes.28−30 The potential of
nanostructured materials is attributed to their unique proper-
ties, such as a large specific surface area, high mechanical and
thermal stability, biocompatibility, or electroactivity. These
tempting properties make some of them attractive as green
chemicals for many situations.31−34 Nanoparticles and nano-
fluids have gained great attention as an efficient alternative
solution to traditional techniques for the mitigation of issues
induced by asphaltene and wax precipitation and deposi-
tion.3,35−41
A comprehensive survey demonstrates that the simultaneous
use of a single chemical as both an asphaltene and wax
inhibitor/dispersant has not been evaluated and developed to
date. Generally, in oilfield applications, asphaltene and wax
inhibitors/dispersants are utilized separately, which results in
an expensive production operation. In addition, separate
injection of chemicals during the oil production may result
in material incompatibility and its detrimental side effects, such
as corrosion of production equipment and pipelines. The effect
of different classes of nanostructured materials such as the
metallic-type (Fe2O3, ZnO, MgO, TiO2, etc.) and silica-based
nanoparticles on solid deposits, especially asphaltene, has been
widely investigated in the literature. However, the use of
carbon-structured nanomaterials has been rarely reported.
Carbon nanotubes present certain unique properties such as a
high aspect ratio, tremendous strength, ultra-light weight, high
thermal conductivity, and remarkable electronic properties
ranging from metallic to semiconducting.42 To address the
mentioned challenges in the petroleum industry, in this
research, a unique class of single-walled carbon nanotubes
(SWCNTs) is developed and utilized to control the formation
and growth of both asphaltene particles and wax crystals in the
production system (i.e., reservoir porous medium, oil well
column, flow lines, and transportation facilities). The
synthesized SWCNTs are characterized by X-ray powder
diffraction (XRD), field-emission scanning electron micros-
copy (FESEM), Brunauer−Emmett−Teller (BET) and
Barrett−Joyner−Halenda (BJH) analyses, transmission elec-
tron microscopy (TEM), and Raman spectroscopy techniques.
A solid detection system (SDS) and high-pressure microscopy
(HPM) are used to evaluate the effect of synthesized SWCNTs
on the precipitation and growth of asphaltenes under high-
pressure−high-temperature (HPHT) conditions. At the end of
the asphaltene HPHT experiments, to assess the asphaltene−
SWCNT interaction mechanisms, the asphaltenes in the
untreated crude oil (free of nanoparticles) and in the treated
crude oil with SWCNTs are extracted and analyzed using
FESEM and XRD techniques. Then, the WAT, crystal
structure/morphology of the wax, and rheological or gelation
behavior of the crude oil with and without SWCNTs are
studied using cross-polarized microscopy (CPM), differential
scanning calorimetry (DSC), and a controlled stress
rheometer. In addition, the industrial applications of the
obtained results are presented and discussed in details. Finally,
the performance of the synthesized SWCNTs is compared with
that of the most common asphaltene and wax inhibitors
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(dodecyl benzene sulfonic acid “DBSA” and polyethylene vinyl Table 1. Properties and Specifications of the Oil Sample
acetate “EVA”) used in industry. To the best of our knowledge,
component unit value uncertainty
this is the first study in which carbon nanotubes are fabricated
and utilized for concurrently controlling the formation and H2S mol % 0.00 ±5 × 10−3
growth of both asphaltene and wax deposits under real N2 0.13 ±5 × 10−3
conditions of oilfields. CO2 1.75 ±5 × 10−3
C1 40.93 ±5 × 10−3
C2 9.42 ±5 × 10−3
2. MATERIALS AND METHODOLOGY
C3 4.84 ±5 × 10−3
2.1. Synthesis and Characterization of Nanoparticles. Here, iC4 0.61 ±5 × 10−3
the SWCNTs were synthesized via the chemical vapor deposition
nC4 3.30 ±5 × 10−3
(CVD) method. The detailed procedure for the synthesis of
SWCNTs can be found in Mahmoudi Alemi et al.43 The crystal iC5 2.66 ±5 × 10−3
structures of the SWCNTs in the absence and presence of the nC5 3.93 ±5 × 10−3
asphaltenes and wax have been specified with XRD, using a C6 4.27 ±5 × 10−3
PANalytical X’Pert PRO diffractometer, with a Cu Kα-ray generator, C7 3.98 ±5 × 10−3
operating at 60 kV, 40 mA, andλ = 1.54060 Å. The surface area and C8 3.32 ±5 × 10−3
pore size distribution of the SWCNTs were calculated using standard C9 2.78 ±5 × 10−3
BET and BJH algorithms. The morphology and particle size of the C10 2.06 ±5 × 10−3
SWCNTs with and without the solid deposits (i.e., asphaltene and C11 1.76 ±5 × 10−3
wax) were also studied by FESEM (FEI Nova NanoSEM 450) images. C12+ 14.25 ±5 × 10−3
Raman spectra were recorded with a Teksan Raman analyzer (model:
molecular weight of residual oil g/mol 231 ±6 × 10−1
TakRam N1-541) excited at wavelength of 532 nm. The Raman
spectroscopy technique was employed as the measurement tool, since molecular weight of the C12+ 473 ±6 × 10−1
fraction
it has been verified to be a nondissipative and nondestructive
molecular weight of reservoir oil 107 ±6 × 10−1
characterization method for low-dimensional materials such as
nanostructured materials. solution−gas oil ratio SCF/STB 926.3 ±6 × 10−2
2.2. Properties of the Oil Sample. In this work, for asphaltene- reservoir temperature (TR) °C 126.1 ±5 × 10−1
related studies, the live oil sample comes from a light oil reservoir reservoir pressure (PR) psia 7850 ±10
(API = 29.1) located in south Iran. Precise experiments for asphaltene bubble point pressure (Pb) by PVT 3105 ±7
studies require single-phase oil samples, sampled at or over the gravity of dead oil API 29.1 ±2 × 10−1
reservoir pressure.44 The conventional sampling tools do not keep the saturates mass % 61.3 ±5 × 10−4
fluid pressure above the AOP. AOP is defined as the pressure at which aromatics 28.0 ±5 × 10−4
the first asphaltene particles come out of the solution as a solid. A resins 8.5 ±5 × 10−4
nonrepresentative reservoir oil sample may contain the incorrect
asphaltenes 2.2 ±5 × 10−4
amount of asphaltene due to the irreversible nature of the asphaltene
precipitation.45,46 The most consistent and reliable sampler tool for wax content 7.6 ±6 × 10−4
asphaltene studies is the single-phase reservoir sampler (SRS) or one- CII 1.74
phase sampler (OPS).47 Thus, to obtain precise experimental results,
in this work, the sampling was performed with OPS technology to microscope is used to investigate the effect of synthesized SWCNTs
collect a representative oil sample. The C12+ composition, general on asphaltene formation (i.e., AOP) and the growth of asphaltene
properties, and results of saturate−aromatic−resin−asphaltene particles or aggregates by isothermal pressure decline. The goal was to
(SARA) analysis of the oil sample are given in Table 1. assess the performance of the SWCNTs as an asphaltene inhibitor and
Due to the prohibitive cost of high-pressure and -temperature dispersant. The SDS measures the light transmission or laser power
experiments, the reservoir fluid is usually screened first by some through the live oil sample to determine the AOP when pressure
criteria such as the colloidal instability index (CII). The screening changes at constant temperature. The trace of the light transmission
approach is employed to judge the potential of the reservoir oil for during pressure decline detects the approximate value of the bubble
asphaltene precipitation- and deposition-related problems and the pressure, which can be used as a checking procedure for the classical
necessity of HPHT studies. In this work, the CII is used to evaluate P−V curve. Bubble point pressure is defined as the highest pressure at
the reservoir fluid for possible asphaltene precipitation. The CII is which the first bubbles of gas are liberated from the oil. At the bubble
defined as the ratio of the sum of the asphaltenes and saturates point pressure, the light transmission through the fluid in the PVT cell
fractions to the sum of the aromatics and resins of crude oil.48 The is essentially zero due to the evolution of gas bubbles. Any abrupt
obtained CII for the studied oil sample, reported in Table 1, is about change in the NIR graph versus pressure is representative of the
1.74, which exhibits high risk of asphaltene precipitation during oil appearance of asphaltene solids in the live oil sample, which is defined
production from the considered reservoir oil. Thus, HPHT asphaltene as the AOP. To start the experiment, about 80 mL of live oil sample is
studies are necessary for this oil sample. The pure asphaltene solids transferred from the sampling cylinder into the SDS cell at an initial
and those treated with nanoparticles are extracted using the IP-143 pressure of 8500 psia (58.6 MPa) and temperature of 125 °C (i.e.,
method,49 and the nature and characteristics of the solid asphaltenes reservoir temperature). Due to the possible error in the temperature
are analyzed using the FESEM technique. set point of the electrical heater covered around the sampling cylinder,
To study the wax, the oil was sampled from the surface flowing line. the sample in the cell is agitated for 24 h to assure the equilibrium
The pressure and temperature of the sampling points were 1150 psi conditions before isothermal pressure decline of the live oil. After
and 87 °C, respectively. As the temperature of the sampling point was equilibration of the fluid sample, the pressure declined at a rate of 15
well above the temperature of the wax formation (nearly 32−33 °C), psi/min from the initial pressure down to the bubble point pressure.
the crude oil sample contained all wax content. Finally, wax crystals in Using HPM, the growth process of asphaltene particles and their
untreated and treated oil samples with SWCNTs are extracted by the morphology during pressure decline with and without the chemicals
BP-237 method50 to explore the wax−SWCNT interactions by XRD such as inhibitors and dispersants can be monitored. The high-
and FESEM. pressure microscope consists of a HPHT cell with two sapphire
2.3. Experimental Procedure and Subsequent Analyses. windows and a light source. The thickness of the cell is 0.3 mm, and
2.3.1. Inhibition and Dispersion of Asphaltene by SWCNTs. A SDS the sapphire diameter is 9.2 mm. The cell thickness can be adjusted
equipped with a near-infrared (NIR) laser and high pressure based on the specific tasks or studies. The temperature of the cell is

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Figure 1. Schematic diagram of the SDS equipped with a high-pressure microscope. Reproduced from ref 52. Copyright 2015, American Chemical
Society.
controlled using a circulation silicone oil bath, made by HUBER-
GmbH, Germany. In addition, a positive displacement pump is used
to sustain the pressure inside the HPHT cell. In this work, the HPHT
microscope (model Leica Z16 APO, Germany) is used to explore the
effect of SWCNTs on the growth pattern of asphaltenes and
asphaltene adsorption onto the surface of the nanoparticles. The
contents of the HPM cell are observed, and micrographs are taken
using a video camera during the course of the experiment. High-
resolution images of the fluid sample inside the cell are recorded at
specific pressure steps to monitor the asphaltene aggregation in blank
live oil (free of SWCNTs) and in live oil treated with synthesized
SWCNTs. The Java-based ImageJ package (version 1.6) developed at
the National Institutes of Health is used to process the obtained
micrographs.51 The SDS and high-pressure microscope assemblies are
operated at a maximum working pressure of 15,000 psi (103.4 MPa)
and temperature of 175 °C. Details of the SDS and HPM procedure
can be found in articles published by Mohammadi et al.52 The
schematic diagram of the SDS equipped with the high-pressure
microscope is represented in Figure 1.
2.3.2. Controlling Wax Formation and Rheological Properties
with SWCNTs. In this section, CPM (ZEISS AXIO, Germany) and
DSC (Mettler Toledo TGA 4000 system) are used to investigate the
effect of synthesized SWCNTs on WAT. In CPM, the oil sample is
initially heated to 80 °C for 15 min to ensure that all wax crystals have
been dissolved. Then, it is cooled to 0 °C at a cooling rate of 0.5 °C/
min. The microscopy images are recorded at each temperature point,
and the images are analyzed to visually determine the WAT in
untreated and treated oil samples with SWCNTs. WAT is defined as
the first temperature point in which waxy materials come out of the
solution, which is detected visually on the CPM images. In addition,
the shape, structure, and size of the wax crystals and their growth are
monitored by CPM.
In DSC, the sample material and the reference material are placed
separately in containers called the sample pan and reference pan,
which are equipped with thermocouples and electric heaters for the
heating/cooling process. The differential scanning calorimeter was
calibrated using indium and normal paraffins, as they have known
melting temperatures and enthalpies of fusion (ΔH). During the
cooling process, the oil sample is cooled at a rate of 1.0 °C/min.
Because of the difference in heat capacity of the sample material and
pubs.acs.org/EF Article
the reference material, the energy used to maintain the temperature of
the sample material and the reference material will be different, and
the difference in this amount of energy will be plotted in terms of
temperature. The crystallization onset temperature or WAT appears
as a sharp peak in the heat flow signal corresponding to the liquid−
solid transition. The accuracy of the DSC measurement has been
calculated to be about 0.2 °C.
A controlled stress rheometer (Physica MCR-301, Anton Paar Co.,
Germany) is used to determine the rheology and gelation point of the
crude oil sample with and without nanoparticles. The gelation point
or gelation temperature is the point at which the deposition process
begins. In other words, at the gelation point, the solid-like behavior of
a waxy crude oil takes predominance over its liquid-like behavior. For
assessing the gelation point of waxy materials, the oil sample was
initially maintained at 80 °C for 15 min and cooled quiescently to 45
°C at a rate of 10 °C/min. Afterward, the oil is cooled at a rate of 0.5
°C/min and sheared under the imposed shear stress of 0.1 Pa. The
variation in the shear rate with the temperature is monitored, and the
gelation point is recognized as the point at which the storage modulus
(identified as G′, in Pa) becomes equal to the loss modulus (identified
as G″, in Pa). In viscoelastic materials, the storage modulus (G′)
measures the stored energy, representing the elastic portion, while the
loss modulus (G″) determines the energy dissipated as heat,
representing the viscous portion.53
2.3.3. Live Oil Sample Preparation with Nanoparticles. For SDS
and HPM studies, the experiments are repeated in the presence of the
synthesized SWCNTs, and the results are compared with those in the
case of untreated live oil (i.e., free of nanoparticles). For preparation
of the fluid sample containing SWCNTs, a definite amount of the
SWCNTs is added to an empty high-pressure cylinder at laboratory
temperature. Calculations are then made such that the concentration
of the SWCNTs under the desired HPHT conditions is known. Thus,
a well-defined amount of live oil is added to the cylinder at fixed
pressure. The cylinder is shaken for 5 h to homogenize the content of
the cell at initial pressure. Finally, for each SDS or HPM experiment,
the required volume of the treated live oil sample is utilized. As
HPHT tests are expensive and time-consuming, an optimum dosage
of the nanoparticles needs to be selected for the HPHT studies. Here,
asphaltene dispersant tests (ADTs) are conducted at ambient pressure
and temperature and at SWCNTs concentrations of 50, 100, 150, 300,
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600, and 1500 ppm to obtain an optimum dosage for SDS and HPM distributions of the SWCNTs using the BJH algorithm
experiments. ADT enables to determine the dispersion performance discloses that the majority of the pore sizes are in the range
of the asphaltene−SWCNTs. Experimental results showed that the of 5−40 nm, which confirms the mesoporous scale of the
dosage of 100 ppm leads to maximum SWCNT efficiency. carbon nanostructures.
For wax-related experiments, crude oil from the reservoir under
consideration is sampled. To start the designed experiments, a suitable
Figure 3 shows the TEM photomicrograph and magnified
amount of crude oil is centrifuged for 15 min at a speed of 4000 rpm image of the red-marked area of SWCNTs. TEM photomicro-
to remove any extra solids and water. Then, different dosages of 50,
75, 150, 300, and 600 ppm SWCNTs are mixed with crude oil, and
they are well shaken for 1 h. The obtained solutions are heated to
about 85−90 °C (sufficiently higher than the wax formation
temperature) to dissolve any possible waxy materials. Finally,
designed experiments are conducted, and the results for untreated
and treated oil samples are compared.

3. RESULTS AND DISCUSSION

3.1. Characterization of Synthesized SWCNTs. Figure 2
exhibits the characteristics of synthesized SWCNTs via XRD, Figure 3. (a) TEM photomicrographs of synthesized SWCNTs and
(b) close-up view of the red-marked section.

graphs confirm that the shape of the SWCNTs seems long,

sinuous, tubular filament- or fiber-like structures. As measured
from the TEM micrographs, SWCNTs feature an average outer
diameter in the range of 3−10 nm. Results obtained by TEM
are in good accordance with the BET measurements, given in
Table 2. Figure 4 displays the FESEM images of the

Figure 2. XRD pattern of synthesized SWCNTs.

Figure 4. FESEM images of synthesized SWCNTs at different
which verifies the structure and morphological features of the magnifications. Scale bars represent (a) 3 μm and (b) 500 nm.
single-walled carbon tubes. The characteristic Bragg peaks are
located around 2θ = 26 and 42°, which are allocated to (002)
synthesized SWCNTs at different magnifications. It can be
and (100) reflection of the graphite, respectively.54 In fact, they
confirmed again that the morphology of the SWCNTs is
represent the orientation of the crystal faces. In addition, the
tubular in shape. FESEM determines the average outer
sharpest peak at 26° is a reflection of graphite in SWCNTs.
diameter of SWCNTs (analyzed using ImageJ), which is in
Typically, for carbon nanotubes, the characteristic peak at
the range of 4−12 nm. The structural and surface morphology
about 42° is related to the crystalline or amorphous nature of
characterizations of the SWCNTs by FESEM are in agreement
the nanomaterial; accordingly, the width of the pattern
with TEM observations. However, due to the higher resolution
increases with reduction in intensity or length, which indicates
of TEM than that of FESEM, it allows for more detailed
the existence of the amorphous form for the synthesized
characterization of the nanotube type and size in synthesized
nanostructure.55 The surface properties and textural character-
nanostructured materials. It should be mentioned that based
istics of the SWCNTs via N2 adsorption experiments are
on the Raman spectrum of the produced carbon nanotubes,
summarized in Table 2. The specific surface area and average
the synthesized SWCNTs are majorly of the single-walled type.
pore diameter by the BET model have been calculated to be
The details of the Raman spectroscopy results and related
149.3 m2/g and 10.9 nm, respectively. The pore size
discussion are presented in the Supporting Information.
3.2. Effect of SWCNTs on Precipitation and Growth of
Table 2. Textural and Surface Properties of Synthesized Asphaltenes. 3.2.1. Results of SDS Experiments. Figure 5
Nanoparticles displays the traces of the isothermal (125 °C) depressurization
process in untreated (free of SWCNTs) live oil and live oil
specification unit value
treated with SWCNTs at a concentration of 100 ppm. SDS
BET specific surface area m2/g 149.3 experiments were performed at an initial pressure of 8000 psi
inside diameter Nm 6.6 down to the bubble point pressure. Due to the severe
average pore diameter, dBET Nm 10.9 scattering of the laser beam through the fluid by gas bubble
total pore volume of pores cm3/g 0.3765 evolution, the light transmittance power (LTP) at bubble point
BJH cumulative pore volume cm3/g 0.3678 pressure is essentially zero. The exact bubble point pressure at
mean length μm 5−13 125 °C by SDS was visually determined to be 3099 psi, which
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Figure 5. Depressurization process of the untreated live oil and treated live oil with SWCNTs (100 ppm) during SDS experiments at 125 °C.

Figure 6. HPM micrographs during isothermal depressurization at 125 °C for (a) untreated live oil and (b) treated live oil with SWCNTs (100
ppm). For pressure steps below the AOPs, HPM displays the asphaltene aggregation process.

is in accordance with he obtained bubble point pressure by
classical PVT tests (3105 psi). As presented in Figure 5 (blue
color data points), the AOP for untreated live oil at 125 °C is
about 5946 psi, which has been detected by decrease in LTP
versus pressure. During the depressurization process at
pressures higher than the AOP, the LTP increases linearly
because of a decrease in live oil density by pressure decrement
until the formation of asphaltene solids. Formation of
detectable asphaltene solids results in the LTP decrement
due to the growth of asphaltene particles (asphaltene
aggregation phenomenon). Based on the NIR light, the
minimum detectable asphaltene size by the SDS is about 1−
14714
1.5 μm. The overall trend of SDS traces at 125 °C in presence
of the SWCNTs (red color curve) at a concentration of 100
ppm is similar to that of the trace of the untreated live oil.
However, in the presence of the SWCNTs, the AOP has been
significantly decreased to 4375 psi, that is, 1571 psi decrement
of the AOP in comparison to the untreated live oil. Thus, using
synthesized SWCNTs, the production life of the reservoir can
be extended, and the production phase shifts to safer regions.
Accordingly, SWCNTs can be used as an efficient asphaltene
inhibitor for retarding the initial pressure for asphaltene
formation under operational conditions of oilfields.
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3.2.2. Results of HPM Experiments. Using HPM experi- electron clouds of asphaltenes. The presence of π−π
ments, the AOP and asphaltene aggregation process at specific interactions between the SWCNTs and asphaltenes is verified
pressure steps have been visualized. Figure 6 shows the through the simulation by density functional theory (DFT).
micrographs of HPM for untreated live oil and live oil treated An output of the performed DFT simulation for this study is
with SWCNTs (100 ppm) at different pressures and a schematically presented in Figure 8. This figure shows the
temperature of 125 °C. The minimum size of asphaltene
detected by HPM is about 0.50−0.60 μm, which is smaller
than that of the detected asphaltenes using the SDS. Thus, the
measured AOP by HPM is to some extent higher than the
corresponding value using the SDS. The size distribution of the
asphaltene aggregates versus pressure is given in Table 3 and

Table 3. Average Size of Asphaltene Aggregates (Dave) at

Different Pressure Steps and a Temperature of 125 °C in
HPM Experiments; Analyses Were Performed Using the
ImageJ Package
Dave.untreateda in Dave.treateda in treated live oil Dave.untreated
pressure untreated live oil with 100 ppm SWCNTs
(psi) (μm) (μm) Dave.treated
5000 1.37
4500 2.65
4250 3.21 0.69 4.7
4000 3.95 0.78 5.0
3750 4.96 0.85 5.8
3500 6.59 0.96 6.8
a
The uncertainty in the calculation of the average size is ±2.5 × 10 −3
μm.
Figure 8. Most stable complex of asphaltene with SWCNTs by DFT
simulation; dark gray color: carbon atoms (C), light gray: hydrogen
Figure 7. As represented in Figure 7, in the presence of 100 atoms (H), and blue color: nitrogen atom (N).
ppm SWCNTs, the average size of the asphaltenes and the
intensity of the asphaltene aggregation phenomenon are most stable complex of the asphaltenes and SWCNTs. As can
significantly lessened in comparison to those of the untreated be seen, the results approve that the asphaltene molecule
live oil. Similarly, the carbon nanotubes have prevented adsorbs onto the surface of the carbon nanotubes with large
asphaltene aggregation by reducing the size of the asphaltenes adsorption energy, demonstrating the chemisorption of
in the live oil. The effective performance of the synthesized asphaltene over the SWCNTs. Adsorption of asphaltene
SWCNTs can be explained by strong π−π interactions molecules onto the surface sites of the carbon nanotubes
between the aromatic rings of the carbon nanotubes and the results in a stable dispersion of the asphaltene solids in oil

Figure 7. Average size of the asphaltene aggregates versus pressure at 125 °C for the untreated live oil and treated live oil with 100 ppm SWCNTs
in HPM experiments. Image analysis was performed using the ImageJ package. Pressure steps of 4000 psi and 3500 psi are equivalent to HPM
images in Figure. 6; due to the different AOPs in Figure. 6, other pressure steps have not been represented.

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Figure 9. FESEM images of (a) pure SWCNTs at the 1 μm scale, (b) pure asphaltene at the 1 μm scale, and (c, d) adsorbed asphaltenes onto the
surface of the SWCNTs at 1 and 5 μm scales, respectively; asphaltenes were extracted from the live oil after HPM experiments.
medium, which can prevent asphaltene deposition on reservoir
rock or production equipment surfaces. In other words, the
high potential of SWCNTs for controlling the asphaltene
aggregation in live oil under HPHT conditions is attributed to
the numerous and strong intermolecular interactions of the
carbon nanotube active sites with the acidic and basic
functional groups of the asphaltenes. In consequence,
SWCNTs have efficiently controlled the size and growth of
the asphaltene aggregates at HPHT. Based on the obtained
results (i.e., reduction of the AOP and average size of
asphaltene aggregates), synthesized carbon nanotubes can be
employed as both an asphaltene inhibitor and dispersant for
oilfield applications.
3.2.3. Analysis of Asphaltene−SWCNT Intermolecular
Interactions by FESEM. At the end of the HPM experiments,
pure asphaltenes in untreated live oil and asphaltenes in treated
live oil with SWCNTs were extracted by the IP-143
procedure.49 The extracted asphaltenes were analyzed by
high-resolution FESEM to assess the adsorption behavior of
the asphaltene molecules onto the surface of the carbon
nanotubes and their corresponding intermolecular interactions.
FESEM observation in Figure 9a shows that pure SWCNTs are
spaghetti- or rope-like with a tubular style, as explained in
Section 3.1. The structure and surface characteristics of the
pure asphaltene extracted under HPHT conditions are
visualized in Figure 9b. Pure asphaltenes comprise smooth
and rough surfaces with some cracks or fractures distributed
through the surface of the aggregates. These created cracks are
ascribed to the removal of resin and/or maltene components of
oil during asphaltene extraction, which reside in the cracks of
the asphaltene structure. The surfaces of the SWCNTs and
asphaltene aggregates in treated live oil are shown in Figure
pubs.acs.org/EF Article
9c,d. The tubular morphology of the carbon nanotubes has
been changed to an irregular agglomerated pattern (Figure 9c).
In addition, the average size of the SWCNTs has been
increased compared to that of the pure carbon nanotubes. The
produced irregular shape and increment in the size of the
SWCNTs are associated with adsorption or loading of
asphaltenes onto the surface of carbon nanotubes. The loading
of asphaltenes onto the surface of the SWCNTs causes weaker
interactions of the carbon nanotubes with adjacent undeco-
rated nanoparticles. Furthermore, reduction in the precipitated
asphaltenes in the presence of the SWCNTs reveals that the
adsorbed asphaltenes onto the surface of SWCNTs are
stabilized in oil; thus, affinity of adsorbed asphaltenes to
interact with the dispersed asphaltenes in the bulk of oil
medium or those asphaltenes adsorbed onto the neighboring
nanotubes is decreased, and consequently, asphaltenes are
stabilized in oil medium. As displayed in Figure 9d, the surface
of the SWCNTs has changed, and the created large cracks on
the surface of asphaltenes have been occupied with carbon
nanotubes. To sum up, FESEM images demonstrates good
adsorption of asphaltenes onto the surface of the carbon
nanotubes. Synthesized SWCNTs act similar to the natural
resin fraction of the oil and control the asphaltene particle
growth in the nanometer scale, which prevents asphaltenes to
be deposited on the surface of the rock or different facilities
(e.g., flow lines, tubing, separator, chokes). The average radius
size of the pores and throats of the usual reservoir rocks is
within the micrometer scale (0.1−100 μm).56,57 In addition,
size analysis of the aggregated asphaltenes adsorbed onto the
surface of the carbon nanotubes shows that the average sizes of
these aggregates are almost smaller than the average radius size
of the typical pores and throats in the reservoir porous media.
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Table 4. WAT by CPM and DSC Methods for Untreated Oil and Treated Oil with Different Concentrations of SWCNTsa
SWCNTs concentration 0 ppm 50 ppm 75 ppm 150 ppm 300 ppm 600 ppm
WATb by CPM (°C) 32.6 24.1 23.2 25.9 27.2 29.4
WATc by DSC (°C) 33.8 23.9 21.8 25.6 28 30.1
a
CPM: cross-polarized microscopy; DSC: differential scanning calorimetry; and WAT: wax appearance temperature bThe uncertainty in WAT
measurement by CPM is ±0.1 °C. cThe uncertainty in WAT measurement by DSC is ±0.2 °C.

Figure 10. Oil cooling process by CPM: (a) untreated oil, (b) treated oil with SWCNTs at 75 ppm, and (c) treated oil with SWCNTs at 600 ppm.

Figure 11. DSC thermograms for determination of WAT; blue color: untreated oil, green color: treated oil with 75 ppm SWCNTs, and red color:
treated oil with 600 ppm SWCNTs; cooling rate = 1.0 °C/min.

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Thus, the pores-throats plugging concern during injection of
the carbon nanotubes in porous media can be alleviated.
However, the electron micrographs show that the carbon
nanotubes usually create a mesh-like aggregate, which raises
the pore-plugging issues within the reservoir porous media.
Consequently, before usage of the carbon nanotubes, the
accurate analysis of the pore and throat size distribution of the
reservoir rock is crucial. Regarding the transfer of the carbon
nanotubes to the surface, it should be noted that as the carbon
nanotubes suspend in the oil medium as an emulsion, they will
be transferred to the surface by oil production.
3.3. Effect of SWCNTs on Formation and Growth of
Wax Crystals. 3.3.1. Effect of SWCNTs on WAT and Crystal
Size. The measured WAT values using CPM and DSC
techniques for different untreated and treated samples are
given in Table 4. For crude oil free of SWCNTs, the wax
crystals have appeared at a temperature of 32.6 °C via CPM.
Dispersing SWCNTs in crude oil has decreased the WAT, with
the highest SWCNT efficiency observed at a concentration of
75 ppm. SWCNTs at a concentration of 75 ppm have reduced
the WAT to 23.2 °C (i.e., about 9 °C reduction of the wax
formation temperature). Beyond this concentration, the
efficiency of SWCNTs for reduction of the WAT has been
decreased. However, at all concentrations of SWCNTs, the
measured WAT is lower than in the case of the untreated crude
oil, which demonstrates that synthesized carbon nanotubes
have postponed the wax formation temperature. As it can be
seen in Table 4, the values and the trend of the WATs by DSC
are in agreement with those of CPM analysis. As an example,
the CPM micrographs and DSC thermogram of the cooling
procedure in untreated crude oil and treated crude oils with 75
and 600 ppm SWCNTs are shown in Figures 10 and 11,
respectively. The crystal shapes in the untreated oil sample are
dense and rod-like or spherical-like with an average size of
about 0.7−0.8 μm (Table 5). The large relative surface area
Table 5. Average Wax Crystal Size at 22 °C for the
Untreated Oil and Treated Oil with Different
Concentrations of SWCNTs; Analyses Were Performed on
CPM Micrographs Using the ImageJ Package
SWCNT concentration
(ppm) 0 50 75 150 300
average crystal sizea (nm) 756 189 86 223 482
a
The uncertainty in the calculation of the average size is ±2.5 × 10−4
μm.
and disc-like morphology of the wax crystals indicate that they
easily form strong lattice structures. After addition of the
SWCNTs, the sizes of the wax crystals have decreased in
comparison to those of the untreated crude oil (Figure 10a);
meanwhile, the number of the wax crystals has increased, and
wax crystal morphology changed into needle- or thin platelet-
like, especially at 600 ppm SWCNTs. Specifically, via visual
observation at the optimum concentration of the SWCNTs
(75 ppm), the wax crystal growth has been well controlled, and
Table 6. Gelation Temperature for the Untreated Oil and Treated Oil with Different Concentrations of SWCNTs; Applied
Shear Stress = 0.1 Paa
SWCNTs concentration 0 ppm 50 ppm
gelation point (°C) 21.5 16.2
a
The uncertainty in measurement of the gelation point is ±0.1 °C.
pubs.acs.org/EF Article
smaller crystals have been produced. As analyzed by CPM and
DSC, at 75 ppm SWCNTs, the crystal size reduction is
optimized. The average crystal sizes at a temperature of 22 °C
for untreated oil and treated oil with different concentrations
of SWCNTs are summarized in Table 5. The reduction of the
WAT and wax crystal size in the presence of the carbon
nanotubes can be described by three different possible
mechanisms/scenarios:
• If the size of SWCNTs is larger than that of the created
wax nuclei: Due to the high specific surface area and
porosity of the carbon nanotubes, the small wax nuclei
adsorb physically onto the surface of the nanoparticles;
these nuclei are inactivated and trapped between the
cavities and surface pores of the nanoparticles, and their
size growth is controlled. Consequently, fewer nuclei will
be accessible for the growth process of wax crystals.
• If the size of SWCNTs is smaller than that of the created
wax nuclei: Carbon nanotubes surround the crystal
nuclei without absorbing them and prevent them from
absorbing each other. Thus, the formation of larger
nuclei and the crystalline growth process (i.e.,
aggregation theory) are prohibited. In this case, the
nanoparticles act as stabilizing agents.
• If the sizes of SWCNTs and the paraffin nuclei are nearly
in the same order: in this circumstance, the nano-
particles act as nucleation centers and form more nuclei
but in smaller sizes at the same concentration of paraffin,
to inhibit the formation of larger crystals. As a result,
SWCNTs prevent the growth of crystals under the
theory of homogeneous growth. Microscopic observa-
tions also help to better understand the abovementioned
findings.
3.3.2. Effect of SWCNTs on Wax Gelation Behavior and Its
Rheological Properties. The gelation temperature was
determined under the quiescent (static) circumstances. The
gelation points for both untreated oil and treated oil with
different concentrations of SWCNTs are given in Table 6. As
given in Table 6, similar to the obtained results for WAT, the
most efficient performance of the SWCNTs for reduction of
the gelation temperature has been achieved at a dosage of 75
ppm. Example results of the rheometer for determination of G′
600 and G″ in untreated oil and treated oil with the optimum
625 concentration of SWCNTs (i.e., 75 ppm) are displayed in
Figure 12. The gelation temperatures for untreated and treated
(75 ppm SWCNTs) samples are 21.5 and 14.7 °C,
respectively. Consequently, addition of the SWCNTs to the
crude oil has significantly delayed the onset point of gelation. It
should be emphasized that each experiment was performed
twice to assure the repeatability and accuracy of the results.
The results of viscosity tests are described in Figure 13. As
the temperature of the crude oil falls below the formation
temperature of the first wax crystal (i.e., WAT), the crystals
begin to interact with each other to form a three-dimensional
network. It ultimately results in the bonding of the lighter
components of the crude oil. This phenomenon in turn leads
75 ppm 150 ppm 300 ppm 600 ppm
14.7 18.3 19.6 20.0
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Figure 12. Storage modulus (G′) and loss modulus (G″) of the oil sample versus temperature for determination of the gelation point: (a) untreated
oil and (b) treated oil with SWCNTs at 75 ppm; cooling rate = 0.50 °C/min.

to oil trapping and thus raises the crude oil viscosity, while
reducing the oil flow assurance and pressure drop in the flow
lines. It is evident that cooling temperature has a negative
effect on the flow rate of crude oil, changing its rheological
behavior to a non-Newtonian behavior.
The synthesized carbon nanotubes at all tested dosages have
reduced the viscosity of the crude oil sample, which leads to a
smooth flow and transportation of the crude oil through
pipelines. The dynamic viscosities of the crude oil at any
temperature below the WAT in the presence of the SWCNTs
have been drastically decreased with an increase in nano-
particle concentration up to a dosage of 75 ppm. For higher
14719
concentrations, the effectiveness of the carbon nanotubes for
reduction of the crude oil viscosity has declined.
3.3.3. Analysis of Wax−SWCNT Intermolecular Interac-
tions by FESEM and XRD. After the CPM experiments, the
wax components of the crude oil in both untreated and treated
samples have been extracted using the BP-237 standard,50 to
study the wax morphology and structure, its adsorption onto
the surface of the carbon nanotubes, and related interactions.
Figure 14a−c shows the FESEM images of the wax crystals in
untreated oil and treated oil with 75 ppm SWCNTs. FESEM in
Figure 14a shows a soft-layered smooth surface for the
extracted wax structure in untreated crude oil (without
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Energy & Fuels pubs.acs.org/EF Article

Figure 13. Flow curve for the oil sample: dynamic viscosity versus temperature; cooling rate = 0.5 °C/min.

Figure 14. FESEM images of (a) wax crystals in the untreated oil with a resolution of 100 μm and (b,c) wax crystals in the treated oil with 75 ppm
SWCNTs with a resolution of 100 and 200 μm, respectively.

SWCNTs). The morphology of the wax surface is clearly
observable with an average dimension of around 15−20 μm.
According to Figures 14b,c, by dispersing the SWCNTs in the
crude oil sample, the smooth and layered surface of the wax
changes into a rugged surface with some breakages, which
confirms the physical interactions between the wax molecules
and SWCNTs. Consequently, FESEM images in the treated
crude oil with carbon nanostructures can demonstrate
14720
incorporation of the carbon nanotubes in the matrix of the
paraffin wax, which has also been discussed elsewhere.58,59
XRD can describe the transformation of the wax crystal
structure and the related interplanar spacing of the crystals
before and after treatment of the crude oil with nanoparticles.
The XRD patterns of the extracted waxes in untreated oil and
SWCNT-treated oil are presented in Figure 15. Each detected
peak represents a crystal plate. The angle of each peak specifies
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Energy & Fuels
Figure 15. XRD patterns of the wax crystals in the untreated oil and treated oil with 75 ppm SWCNTs.
the distance between the plates, and the intensity of each peak
is associated with the type, number, and arrangement of atoms
in the same plane. In the presented XRD of wax deposits in the
untreated oil (blue curve), three characteristics peaks
appearing at the 2θ of 24, 41.1, and 76° are attributed to
(012), (113), and (211), respectively, which are the customary
Bragg peaks of the paraffins. The sharp peak at the 2θ of 41.1°
for wax in the untreated oil has been also observed for the wax
structure in the treated oil with carbon nanotubes but with
much less intensity (curve in red). The decrease in peak
intensity at the 2θ of 24° or lack of peaks at the 41.1 and 76° in
the treated crude oil with SWCNTs is an indication of changes
in size of the crystals (i.e., smaller wax crystals). Moreover, the
decreasing peak intensity implied the loosely packed crystal
structure in the treated crude oil with carbon nanotubes. The
XRD results established that the crystal shape and size were
modified by SWCNTs. This change in the crystal size and
structure certifies strong interactions between the carbon
nanotubes and active sites of the wax crystals, which produces
a different pattern.
Reported documents in the literature show that the
acceptable performance of the metallic and silica-based
nanoparticles for controlling asphaltene and wax formation
has been typically attained at high dosages.60−62 However, as
discussed, the effective performance of the synthesized
SWCNTs at low dosages for controlling the formation and
size growth of wax (75 ppm) and asphaltene (100 ppm) solids
resolves the challenge of using other types of nanostructured
materials (e.g., metallic-type, silica-based) at high concen-
trations (500−15,000 ppm). In addition, usage of SWCNTs at
low concentrations and instead of the simultaneous use of both
asphaltene and wax inhibitors is cost-effective and compatible.
Regarding the environmental aspects of nanostructure
materials, risks to human health and the environment should
be recognized for successful implementation of the carbon
nanotubes in industry. Recent studies on the environmental
effects of different types of nanoparticles disclose that the
harmfulness of nanoparticles depends on specific physiochem-
ical and environmental factors, which can be handled during
pubs.acs.org/EF Article
the synthesis.63,64 Applications of carbon-based nanoparticles
at high volume may raise environmental and public health
concerns.65−68 However, many research studies verify that
applications of carbon nanotubes at low concentrations do not
cause any major adverse effects.69−73 Furthermore, it has been
found that functionalization of the carbon nanotubes makes
them generally biocompatible without any risk to health.73−76
4. CONCLUSIONS
In this research, SWCNTs were synthesized, and their effects
on formation and growth of asphaltene and wax deposits in live
oil were investigated under realistic production conditions.
SDS and HPM experiments showed that the SWCNTs
successfully postponed the onset pressure of asphaltene
formation and lessened the rate of the asphaltene aggregation
process in live oil. Analysis of the intermolecular interactions
by FESEM verifies the results of asphaltene-HPHT experi-
ments. FESEM images of asphaltene deposits established good
adsorption of the asphaltenes onto the surface of the carbon
nanotubes. The high surface area of the carbon nanotubes and
strong π−π interactions formed between the electron cloud of
aromatic rings of the SWCNTs and asphaltene molecules are
in charge of asphaltene adsorption onto the surfaces of the
nanoparticles. Wax formation temperature and the size of wax
crystals were decreased in all tested concentrations of
SWCNTs via CPM and DSC experiments. The optimum
efficiency of SWCNTs was achieved at a concentration of 75
ppm. At other concentrations, the efficiency of SWCNTs for
the reduction of the WAT decreased. The more pertinent
mechanism of the SWCNTs is their influence upon the crystal
morphology. The wax crystal morphology changed from dense
spherical-like in the untreated crude oil into thin needle-like in
the treated crude oil with SWCNTs. In the presence of the
SWCNTs, the average size of the crystals decreased from 756
to 86 nm. Addition of the SWCNTs at 75 ppm to the crude oil
considerably delayed the gelation temperature from 21.5 to
14.7 °C. XRD analysis showed changes in the crystal size and
structure, which exhibit the strong interactions between the
carbon nanotubes and active sites of the wax crystals.
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Energy & Fuels
Considering the average radius of the pores and throats in
reservoir rocks, the synthesized SWCNTs can be injected in
the porous media without the plugging problems to control the
asphaltene−wax aggregation phenomenon. The high concen-
tration and environmental issues for utilization of different
types of nanoparticles can be alleviated by effective use of
synthesized SWCNTs at low dosages (75−100 ppm).
Comparison of the efficiency of the SWCNTs with DBSA
and EVA, as the most widely used asphaltene and wax
inhibitors, exhibits that the produced carbon nanotubes act
better than DBSA and EVA in delaying the asphaltene/wax
formation and controlling their growth in oil medium (results
of this comparison are provided in the Supporting
Information).
■
ASSOCIATED CONTENT
*
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.energyfuels.1c02244.
Raman spectroscopy of synthesized SWCNTs and
performance of synthesized SWCNTs versus common
asphaltene and wax inhibitors (PDF)
■
AUTHOR INFORMATION
Corresponding Author
Saber Mohammadi − Petroleum Engineering Department,
Research Institute of Petroleum Industry (RIPI), Tehran
1485733111, Iran; orcid.org/0000-0002-2919-6719;
Email: mohammadi.sab@gmail.com
Author
Fatemeh Mahmoudi Alemi − Petroleum Engineering
Department, Research Institute of Petroleum Industry
(RIPI), Tehran 1485733111, Iran; orcid.org/0000-
0002-1555-6891
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.energyfuels.1c02244
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The authors wish to thank the Research Institute of Petroleum
Industry (RIPI) for providing live oil samples and techno-
logical support.
■
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