SPE-191656-MS

Case Study on Fluorocarbons Interior Coating for Anticorrosion

and Wax-Deposition Inhibition in ASP Flooding Production

Yang Liu, Xianglong Zhuge, Zhihua Wang, and Bin Huang, Northeast Petroleum University;
Xinpeng Le, Daqing Oilfield Company Limited

Copyright 2018, Society of Petroleum Engineers

This paper was prepared for presentation at the 2018 SPE Annual Technical Conference and Exhibition held in Dallas, Texas, 24-26 September 2018.

This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents
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Abstract
Under the hovering background of low oil price, alkali/surfactant/polymer (ASP) flooding technique is
proven to be vitally important for enhance oil recovery (EOR) in oil industry. The production practice in
Daqing Oilfield (China) shows that the EOR of ASP flooding is more than 10% original oil in place (OOIP)
over conventional polymer flooding. However, the problems of corrosion and scaling that surface facilities
and pipelines encounter with still remain very challenging in ASP flooding production, especially in the
strong alkali (NaOH) ASP flooding fields. In the industrialized-application of ASP flooding process, these
problems are drawing more and more attention.
The corrosion behaviors of surface facilities and pipelines that utilized in strong alkali (NaOH) and weak
alkali (Na2CO3) ASP flooding fields were characterized with the integration of production practice, the
general anticorrosion measures and the failure of internal coating in fields were presented and demonstrated.
A coating solution for fluorocarbons surface treatment was proposed and tested in this case study. The
performance of interior surface coatings including corrosion-scaling resistance, wax-deposition inhibition
and drag reduction was evaluated with the existence of ASP chemicals in produced emulsions, and
the mechanism was discussed from both film-forming and reducing surface energy aspect. The distinct
competitive advantage of fluorocarbons interior coating for anticorrosion and wax-deposition inhibition in
ASP flooding production was presented.
Considerable corrosion and scaling were created and covering the surface facilities such as the storage
tanks of ASP chemicals, the pipelines for injection and production, and the heating furnaces in ASP flooding
production. Both of the applied physical and chemical protection measures are facing to the challenges of
service life, potential environmental threats and unpredictable cost-effectiveness. High bond energy and
strong chemistry inertia of fluorinated resins can prevent the coating structure from being destroyed and
develop flexibility and weatherability of the coating. The pore resistance and shielding performance of
fluorocarbon coating in corrosion environment highlighted actually result from the superior mechanical
properties, super-hydrophobicity, and self-cleaning performance. Furthermore, the low surface energy and
low coefficient of friction of the fluorocarbon interior coating provide the possibility of pipeline wax-
deposition inhibition and drag reduction. The maximum wax-deposition inhibition rate and the maximum
2 SPE-191656-MS

drag reduction rate reached 46.42% and 60.00% respectively for high-viscosity ASP flooding produced
emulsions in this case study. The reasonable coating configurations and process are certainly indispensable
in the potential applications of fluorocarbons surface technology.
The case study contributes to the existing knowledge in the implementation of chemical EOR project for
a green oilfield development, and it is also helpful to accelerate industrialized-application of ASP flooding
and design another emerging pattern-flood pilot.

Introduction
The improvement of oil production from mature oilfields is an important strategy from both technical and
economic points of view (Nurxat et al., 2015; Rui et al., 2017; Du et al., 2018; Rui et al., 2018a). ASP
flooding is an emerging technology to improve production efficiency from mature oilfields and has realized
the industrialized-application successfully in Daqing Oilfield. Results show that incremental oil recoveries
of up to 25% of the original oil in place (OOIP) have been obtained in good-quality reservoirs (Wang et
al., 2013; Guo et al., 2017). The recent progress of development practice in Daqing Oilfield helps enhance
the confidence of chemical flooding under the hovering background of low oil price and indicates that ASP
flooding can potentially be regarded as the most efficient chemical EOR technique (Sheng, 2015; Wang et
al., 2017a). In this flooding technology, a combination of alkali, surfactant, and polymer is used to improve
sweep efficiency and mobilize capillary-trapped oil. Polymer function, as a well-known component, is
considerably enhance the volumetric sweep efficiency of the reservoirs. Surfactant is used to reduce the
interfacial tension (IFT) between the oil phase and displacing fluid. Alkali can induce the generation of in-
situ soaps if a crude oil demonstrates high-acid-value, and it also can decrease surfactant adsorption on the
reservoir rocks. Moreover, the utilization of alkali is also believed to be helpful to crude oil emulsification.
The most common alkali used in ASP formulation is sodium hydroxide (NaOH) and sodium carbonate
(Na2CO3). And the wide application of strong alkali (NaOH) in fields is because of its better interface
activity, stronger emulsifying ability, and wider surfactant range, which can meet the necessities of ultralow
IFT (Guo et al., 2018; Rui et al, 2018b). Both strong alkali (NaOH) and weak alkali (Na2CO3) ASP flooding
with available surfactants are successful and industrially applicable if only the incremental oil recovery is
concerned. However, the practice indicated that serious corrosion and scaling can be formed in the ASP
flooding fields, especially in the strong alkali (NaOH) fields (Wang et al., 2013; Guo et al., 2017). Except
the formation damage caused by scaling in alkaline environment, alkali is capable to produce hydroxide ions
in the injected ASP solution and produced liquid, which results in considerable quantities of the corrosion
and scaling deposition to be emerged on the surface of metal facilities and pipelines (Vazirian et al., 2016;
Mahajan et al., 2018; Cui et al., 2018; Zhu et al., 2018). All of these can be a threaten to the normal operation,
the structural integrity of the facilities, and the effects of energy conservation. Although considerable efforts
were devoted in the previous studies to explore physical and chemical anticorrosion measures (Shchukin et
al., 2008; Veselý et al., 2010; Eremin et al., 2016), the issues of production operation and cost management
for corrosion-scaling in surface system are still the major weaknesses in the promotion of ASP flooding
technique.
As part of the growing need for coating solutions, fluorocarbon surface technologies have always
been given much more attention in many industries in worldwide. Fluorocarbon coating is an organic
coating material consisting of solid lubricant dispersed in an organic binder and dissolved in a specially
formulated mixture of solvents (Kulinich and Farzaneh, 2005). It is also corrosion-resistant due to the
use of a thermally cured thermosetting synthetic binding material. When the coating being applied to the
substrates, it can resist galling, seizure and fretting and exhibit corrosion-resistance. As a lustrous coating,
fluorocarbon surface treatment material has excellent adhesion. The effective optimum film thickness is
generally ranged from 15 to 25 microns, and the load bearing capacity could reach 14000 psi. Since
the discovery of polytetrafluoroethylene (PTFE) more than 60 years ago, a wide series of studies have
SPE-191656-MS 3

been undertaken with the main purpose to develop fluoropolymers which could have superior properties
in terms of thermal and chemical endurance and is also suitable to be processed with the common
techniques (Uhrbrand, 2009; Waterton, 2016; Wang et al., 2016a). A wide range of fluoropolymers such
as PTFE coatings, perfluoroalkoxy (PFA) coatings, ethylene-chlorotrifluoroethylene (ECTFE) coatings and
ethylene tetrafluoroethylene (ETFE) coatings have been regarded as high performance surface coatings
being serviced in some fields. In addition, the fluorine-containing resins have now been widely used
in making coatings include fluoro olefin-vinyl ether (FEVE) copolymer and polyvinylidene fluoride
(PVDF) (Takayanagi and Yamabe, 2000; Parker, 2013). Fluorocarbon surface technologies for chemical
or environmental corrosion protection have gained considerable development in recent years and have
been widely used in construction, chemical, electrical and electronic, mechanical industries and household
products (Wang et al., 2016a). What is worthy to mention is that fluorocarbon coating can perform well
under a great quantity of extreme environmental conditions. As a result, the lubricating ability of the coating
from room temperature to up to 200°C in air and even higher temperatures in non-oxidizing atmospheres
makes it promising for aerospace industry applications (Makhlouf, 2011; Ebnesajjad and Khaladkar, 2017).
This coating is administered in machine parts exposed to corrosion environment and where lubrication is
required. It can be given on any alloy or metal surface, which can be appropriately pretreated by phosphating,
blasting, anodizing or nitrocarburising. There is no doubt that the progresses of fluorocarbon surface
technologies make it own huge market and broad prospect, it is potential to protect steel structures from
corrosion using fluorocarbon coatings in oil & gas industries (Li et al., 2016; Wang et al., 2017b). Moreover,
fluorocarbon surface treatment material may be applied by dip, spray or any one of the conventional painting
methods, but then the prior surface preparation has a marked effect upon the quality of fluorocarbon material
(Reker and Koch, 1992; Price and Laws, 2007; Wang et al., 2016a). It is significant to further pursue accurate
and cost-effective anticorrosion technology and understand mechanism on increasing production facilities
lifecycle, saving energy consumption, and promoting environmental conservation in ASP flooding EOR.
The corrosion behaviors of surface facilities and pipelines that utilized in strong alkali (NaOH) and weak
alkali (Na2CO3) ASP flooding fields were characterized, the general anticorrosion measures used in actual
operation were demonstrated, and the failure of internal coating measures in fields was presented in this
case study. A coating solution for fluorocarbon surface treatment was proposed and tested. The performance
of surface coatings including corrosion-scaling resistance, wax-deposition inhibition and drag reduction
was evaluated with the existence of ASP chemicals, and the mechanism was discussed from both film-
forming and reducing surface energy aspect. The distinct competitive advantage of fluorocarbons interior
coating for anticorrosion in ASP flooding production was presented. Furthermore, the procedure of the
surface treatment was optimized and summarized with the previous operation information from a known
ASP flooding production area and the new understanding from this study. The case study contributes to
the existing knowledge in the implementation of chemical EOR project for a green oilfield development,
and it is also helpful to accelerate industrialized-application of ASP flooding and design another emerging
pattern-flood pilot.

Production Description
Since ASP flooding technique entered commercial-scale application in Daqing Oilfield in 2014, the total
producing reserves reaches 1.72 billion barrels (bbl) and the total oil production reaches 188.5 million
bbl, and the number of injection-production wells reaches 9710 in the oilfield. The oil production of
ASP flooding approached to 30 million bbl in 2017, which accounted for about 35.6% and 12.0% of
the chemical flooding production and total production of the oilfield, respectively. Both strong alkali
(NaOH) ASP system and weak alkali (Na2CO3) ASP system had been successfully applied to EOR, and
the incremental oil recovery reached more than 20% (OOIP) over water flooding. Furthermore, NaCl/
surfactant/polymer system instead of strong alkali (NaOH) and weak alkali (Na2CO3) ASP systems is being
4 SPE-191656-MS

tested. A more universal understanding that weak alkali (Na2CO3) ASP flooding process is both technically
and economically better than strong alkali (NaOH) ASP flooding process under the field conditions in the
Daqing Oilfield was being established (Guo et al., 2018). However, the problems of corrosion and scaling
deserved to concern in ASP flooding production. Although some anticorrosive measures represented by
internal coating had been used in actual operation, the failure of internal coating measures and frequent
maintenance for the coatings are remarkable in fields and restrict the cost-effectiveness of ASP flooding
process. The considerable corrosion, scaling and deposition behaviors of surface facilities covered in the
storage tanks of ASP chemicals, the pipelines for injection, the pipelines for production and the heating
furnaces in the production process of Figure 1.

Figure 1—Schematic illustration of production process in ASP flooding EOR

As can be seen in Figure 2, the excessive formation of corrosion, scaling and deposition was evident in
ASP flooding production, especially in the strong alkali (NaOH) fields. A considerable corrosion behavior
was mainly concentrated in storage tanks of ASP chemicals stock solution and pipelines for injection-
production, and the considerable scaling behavior was mainly concentrated in pipelines, pumps and heating
furnaces, and the serious deposition behavior was mainly concentrated in pipeline for production. The
ferrous sulphide (FeS) and iron oxide (Fe2O3) were the dominated constituents in the corrosion products.
The carbonate scales were the main composition of the precipitated scaling in weak alkali (Na2CO3)
ASP flooding process, and the majority of the precipitated scaling was composed of carbonate scales and
silicates in strong alkali (NaOH) ASP flooding. The wax-deposition dominated deposition behavior in
pipelines for production. These properties could be further verified by the typical changes of divalent-cation
concentration and PH value in the produced fluid, as shown in Figure 3, there was an obvious decrease
of divalent-cation concentration in produced fluid during ASP flooding. It indicated that ionic reactions
were promoted and carbonates and silicates continued to form. Moreover, the PH value of the produced
fluid increased to more than 10, and this revealed that the production facilities entered the corrosion and
scaling period.
SPE-191656-MS 5

Figure 2—Internal corrosion, scaling and deposition characteristics of production facilities

Figure 3—Typical changes of divalent-cation concentration and PH value during ASP flooding

Corrosion-resistant stainless steel facilities are inevitably restricted in fields due to the excessive
investment issues. Therefore, the most common protection measures against corrosion, scaling and
deposition was to use glass fiber reinforced plastics (FRP) as materials for production facilities, perform
epoxy coating treatment, and add chemical inhibitors in the actual operation. However, some challenging
problems still trouble engineers due to the fact that these protection measures have limited service life,
potential environmental threats and unpredictable cost-effectiveness. In particular, as can be seen in Figure
2, the internal coating represented by conventional epoxy coating often just have one-year service life in
strong corrosion environment, and then the coating would show wrinkling, damaging, and even peeling
off. The results of test and evaluation indicated that PVDF coating and phenolic modified epoxy coating
were also unsatisfied. Even in the weak alkali (Na2CO3) ASP flooding with slight corrosion, the injection-
6 SPE-191656-MS

production capacity would decrease, the transportation efficiency would reduce and the maintenance cost
would increase due to the failure of the internal coating. These production features revealed that surface
coatings technology should be developed and extended in ASP flooding production.

Experimental Mechanism
Fluoropolymers have been applied as coating materials since it entered the commercial market in 1930s.
Solubility in solvents and adhesion to substrates should be further concerned when fluoropolymers were
used as the base material of fluorocarbon coatings. As shown in Figure 4, some of the desired physical
properties, such as crosslinking sites, good adhesion performance, hardness and flexibility, can be acquired
because of the solubility, flexibility, crosslinkability and weatherability features shown in the molecular
structure of the film-forming material. Moreover, the hydroxyl groups in the molecular structure functions
as the crosslinking site with special pigments for on-site coatings. It has been demonstrated that a great
number of C-F bonds exist in fluorinated resins, and they have high bond energy. A C-F bond energy of 485
kJ/mol can enhance the stability of the structure, and the strong chemistry inertia can prevent the structure
from being destroyed (Wang et al., 2016a; Kuwamura and Hibi, 1997). Additionally, the low polarity and the
low surface energy will weaken the adhesion of corrosion medium on fluorocarbon coatings after the film-
forming process is completed. The role of low surface energy in surface treatment using fluorocarbon will
be highlighted with the increase of adhesion between the coating and the metal base. It is promising to use
fluorocarbon surface treatment as coating solutions based on the mentioned mechanism in ASP chemicals
environment, and the excellent anticorrosive properties could be achieved in ASP flooding production in
theory.

Figure 4—The molecular structural formula of fluoropolymers for film-forming

Electrochemical Impedance Spectroscopy (EIS) is a perturbative characterization of the dynamics of

an electrochemical process. As a powerful means, EIS is widely used to identify corrosion processes as
well as protective performances of surface coatings (Cavalcanti et al., 1993). When a weak amplitude
sinusoidal perturbation is generally superimposed to the corrosion potential or open circuit potential, this
perturbation will induce a sinusoidal current superimposed to the stationary current, and generate a phase
shift with respect to the potential. Then, the impedance data can be represented in Nyquist spectrum and
Bode spectrum, and unlike the former, the latter can show necessary frequency information.
The wax-deposition inhibition rate can be defined as the ratio of reduction in the wax-deposition rate
between without using surface coatings and using surface coatings to the wax-deposition rate without using
surface coatings at the same operating conditions:

(1)

where, Wb is the wax-deposition rate in uncoated pipeline and Wsc is the wax-deposition rate in pipeline
with fluorocarbon surface treatment.
SPE-191656-MS 7

Similarly, the drag reduction rate can be defined as the ratio of reduction in the frictional pressure drop
between without using surface coatings and using surface coatings to the frictional pressure drop without
using surface coatings at the same operation conditions:

(2)

where, ΔPf is the pressure drop in uncoated pipeline and ΔPfdrag is the pressure drop in pipeline with
fluorocarbon surface treatment.

Experimental Material and Setup

Experimental Materials
ASP system. Both the strong alkali (NaOH) and the weak alkali (Na2CO3) ASP system were employed
in this case study. The experimental concentrations of NaOH solution and Na2CO3 solution were 20 wt.%,
30 wt.% and 12 wt.%, 24 wt.%, respectively. The used surfactant in strong alkali (NaOH) ASP system was
alkylbenzene sulfonate (ABS), and the experimental concentrations of the stock solutions were 30 wt.% and
50 wt.%, respectively. The used surfactant in weak alkali (Na2CO3) ASP system was petroleum sulfonate
(DPS), and the experimental concentrations of the stock solutions were 8 wt.% and 20 wt.%, respectively.
The polymer used in the experimental ASP system was a salt-tolerant partially hydrolyzed polyacrylamide
(HPAM), with an original concentration of about 5000mg/L and a relative molecular weight of 2500×104 Da.
Produced fluid. The produced fluid (mixture of oil, water, and well chemicals) that water fractions
were 57.3% and 88.6%, was sampled from strong alkali (NaOH) ASP flooding fields. The wax content
and freezing point of the crude oil were measured as 25.7% and 32.8 °C, respectively. The average
concentrations of ABS and HPAM in the produced fluid were 75.2 mg/L and 560.4 mg/L, respectively. And
the average pH value of the produced fluid was 10.6. The total salinity of produced water was 5240 mg/L,
and the average sulphides content was 9.6 mg/L. The produced fluid was employed in deposition inhibition
and drag reduction experiments with various surface treatment for pipelines.
Film-forming material. As mentioned above, the ultra-weatherable resins, fluoro olefin-vinyl ether
(FEVE) copolymer, was selected as the main film-forming material. This solvent-based fluorocarbon paint
can be collected in the commercial coating market. In addition, the conventional epoxy paint was also
employed in this case study to make a comparison of experiments. Additionally, some other materials such
as special pigments, fillers and additives were employed in experiments.

Experimental Setup
As proposed, the coating solution for fluorocarbons surface treatment was tested in both strong alkali
(NaOH) ASP system and weak alkali (Na2CO3) ASP system. The flexibility and adhesion of fluorocarbons
interior coating were characterized by the tests of adhesion and mechanical properties. The superior
surface properties of fluorocarbons interior coating were verified by the measurements of contact angle.
The anticorrosion properties were evaluated by means of EIS measurements. Furthermore, the unique
performance of fluorocarbons interior coating including wax-deposition inhibition and drag reduction was
concerned and simulated in a small-scale flow loop.
Mechanical and adhesion performance characterization. The mild steel panels of 150 mm×50 mm×0.5
mm were chosen and processed as substrates. The chemical composition of the substrates was 0.193%
C, 0.744% Mn, 0.082% P, 0.027% S, 0.334% Si and 98.620% Fe. Degreasing was first performed using
ultrasonic cleaning. Next, fluorocarbons surface treatment was carried out on these substrates. Then these
coated mild steel panels were exposed in air for 2h at room temperature. After that, the coating thickness
8 SPE-191656-MS

was determined and coated panels were cured at temperature of 150°C and 250°C. Finally, the mechanical
properties including impact resistance and flexibility were characterized, and the grade of adhesion was
identified according to the relative standard methods.
Surface properties test. Contact angle is one of the most basic and important surface properties, which is
measured as the angle where a liquid interacts with a solid surface. A low contact angle indicates that the
surface has high wetting, and a high contact angle indicates that the surface has low wetting. The contact
angles of surface with different treatment patterns were tested by means of sessile drop method using strong
alkali (NaOH) ASP system as probe liquids.
Chemical resistance test. Chemical resistance of the fluorocarbon coating was tested in ASP chemicals
environment using immersion experiments. In experiments, the alkali concentrations of NaOH solution
and Na2CO3 solution were 20 wt.%, 30 wt.% and 12 wt.%, 24 wt.%, respectively, and the surfactant
concentrations of ABS solution and DPS solution were 30 wt.%, 50 wt.% and 8 wt.%, 20 wt.%, respectively.
Expect for periodic visual examinations were performed every day, corrosion rates were also measured
during the immersion period. As a contrast experiment, corrosion test of the conventional epoxy paint was
also carried out in the same corrosion environments.
Anticorrosion properties measurements. The valuable coating performance parameters usually can be
obtained from EIS measurements, and the anticorrosion properties can also be identified. Some predictive
parameters for evaluating anticorrosion properties can be obtained using EIS method in organic-coated steel
systems. A three electrode-cell was selected to evaluate anticorrosion performance of the fluorocarbons
interior coating. In measurements, a saturated calomel electrode was employed as the reference electrode,
the working electrode was coated steel panels (50 mm×50 mm×2.0 mm), and stainless steel was selected
as the counter-electrode. The surfaces of mild steel panels were degreased with toluene and alcohol before
coating treatment. The average thickness of fluorocarbon coating was 45 μm. The electrolytes were 30 wt.%
NaOH solution, 50 wt.% ABS solution and 24 wt.% Na2CO3 solution, 20 wt.% DPS solution, respectively.
All impedance spectra in potentiostatic pattern were carried out in the frequency range of 10−2 Hz~105 Hz,
and the applied sinusoidal alternating potential signal was ±10 mV. Immersion time in these solutions all
was 180 days, EIS measurements were made periodically throughout up to three months of immersion time,
and the measurements were performed at room temperature
Wax-deposition inhibition and drag reduction experiments. Except for primary concern of corrosion
resistance of the fluorocarbons interior coating in ASP flooding production facilities, wax-deposition
inhibition and drag reduction performance in pipelines with fluorocarbons surface treatment are another
concern in this case study, and dominates the potential application of fluorocarbons interior coating in
oilfields which locates in extremely cold area. A small-scale flow loop used to simulate wax-deposition
during transporting process of ASP flooding produced fluid was improved on the basis of previous work
(Wang et al., 2016a). As illustrated in Figure 5, both the test steel tubing section and the reference steel
tubing section have the same length of 16 feet and the same internal diameter of 2 in. The reference section
was uncoated mild steel tubing. Mild steel tubings with fluorocarbons interior coating and epoxy interior
coating were employed respectively and replaced by each other in the test section. Differential pressure
transducers and temperature transducers were installed in the test steel tubing section and the reference
steel tubing section. The external environment of wax-deposition was created through temperature bath
and refrigeration system in device. Flow characteristic parameters of the ASP flooding produced fluid in
the test steel tubing section and the reference steel tubing section were recorded by the data acquisition
system. During a typical run, the produced fluid mentioned above was pumped into the small-scale flow
loop device to carry out the cycle flow under the wax-deposition environment. Wax-deposition rate in
steel tubings with different surface treatment was determined reasonably according to differential pressure
methods which were presented somewhere else (Liu et al., 2012; Wang et al., 2016b). Then, the inhibition
SPE-191656-MS 9

of wax-deposition behavior in pipelines with surface treatment would be evaluated and identified. The drag
reduction performance could also be determined and compared by the frictional pressure drop variations of
ASP flooding produced fluid in flow simulation experiments.

Figure 5—Schematic illustration of the small-scale flow loop device

Results and Discussion

Mechanical and Adhesion Performance
Although adhesion is not a fundamental performance of a material, the mechanical properties of coating
are closely related to the adhesion performance, and there is a positive correlation between them. A coating
with excellent adhesion to the substrate will have superior mechanical properties and corrosion resistance.
As shown in Table 1, impact resistance, flexibility and adhesion performance of these substrates with
fluorocarbons surface treatment all meet the specifications when they are cured at different temperature
and time. Moreover, the mechanical and adhesion performance of the coating do not decrease with the
degradation of coating thickness, and the potential coating problems of wrinkling, damaging, puncturing
and peeling off would be avoided or alleviated. These results indicates that the fluorocarbons coating owns
superior mechanical properties, and it is promising to deal with limited service life of the conventional
epoxy coating.

Table 1—Results for the mechanical and adhesion performance of the fluorocarbon coating

Surface Properties
Compared with conventional epoxy coating surface treatment pattern, the results indicated that contact angle
could increase by nearly 10° and up to 112° when surface treatment was performed by fluorocarbon coating.
High contact angle of the surface was equivalent to achieve low surface energy and low interfacial tension.
10 SPE-191656-MS

After performing fluorocarbons surface treatment, a low wetting surface was created, and the surface energy
was weaker than the surface tension of the liquid, that is to say, the liquid could better keep its droplet shape.
As shown in Figure 6, the droplet basically keep its original shape after fluorocarbon surface treatment,
but the droplet spread out over the solid surface treatment with conventional epoxy coating to a certain
extent. Furthermore, these surface properties reveal that the fluorocarbon coating has superior self-cleaning
performance resulted from the low surface energy.

Figure 6—Contact angle of the droplet under different surface treatment

Chemical Resistance
Although the differences of corrosion appearances were not evident in different surface treatment patterns
of the case study, some features of blistering, cracking, rusting and peeling off highlighted on the container
walls with conventional epoxy coating treatment. As shown in Figure 7, the visual inspection found the
fluorocarbon coating was unaffected in any alkali and surfactant solutions at high and low concentrations
during the two months immersion period of the case study. It indicates this coating has good resistance
to corrosion environment, especially for strong alkali (NaOH) with higher concentration of 30 wt.%. As
shown in Table 2, corrosion rate can reduce more than 98% when fluorocarbons surface treatment is used
as interior coating solution. The chemical resistance grade of the fluorocarbon coating can be identified
as "0" (None), and the chemical resistance grade of the conventional epoxy coating can be identified as
"1" (Less than few) in various chemicals systems. This finding is also in agreement with the corrosion rate
data obtained in the tests.

Figure 7—Corrosion appearances in different surface treatment patterns

SPE-191656-MS 11

Table 2—Results for the chemical resistance performance of the fluorocarbon coating

Anticorrosion Performance
The advantage of EIS measurements is that it can probe the electrochemical interface of the coated metal
and provide the necessary information about the influence of corrosive medium on protective coatings and
substrates. In long-term constant immersion experiments, EIS measurements were performed at varying
time increments from 0 hour to 180 days, and the anticorrosion performance of fluorocarbons surface
treatment was assessed. The EIS spectra exhibited a capacitive behavior of the low surface energy coating.
As shown in Figure 8(a), the low-frequency impedance of fluorocarbon coating in various ASP systems
was above 109 Ω•cm2, and the high resistivity was in agreement with the performance of other organic
coating systems (Schmidt et al., 2005). Nyquist plots for the fluorocarbon coating immersed in 24 wt.%
Na2CO3 solution and 20 wt.% DPS solution exhibited higher impedance values. The capacitance features
showed a certain degree of shrink after a certain period of immersion in 30 wt.% NaOH solution and 50 wt.
% ABS solution, and this shrinking shape was more significant in the duration of the constant immersion
test period in NaOH solution. However, the shape of Nyquist plots still exhibited a single capacitance
characteristic after immersion time reached three months in various corrosive medium. This proved that
strong alkali system in ASP flooding production is more challenging than weak alkali system in the corrosion
protection, which correlated well with the visual observations of coating damage or failure mentioned above
in actual production. These properties revealed that the fluorocarbons surface treatment was potential to deal
with the corrosion issues of metal substrates in aggressive and corrosive chemical environments. The ESI
measurements data was extracted and Bode plots were obtained, as can be seen in Figure 8(b), there was a
frequency independent plateau region at low-frequency (< 0.8 Hz) region in Bode plots during the duration
of the constant immersion test period. It indicated that pore resistance of the coating would be reduced,
shielding performance of the coating would be improved, and the penetration threat of corrosive chemicals
would be eliminated. The phase angles approached 90° for all immersion environments at high-frequency,
and they ranged from 50° to 75° after immersion for three months in both strong alkali and weak alkali
ASP systems at low-frequency of 0.01 Hz, this further proved the super-hydrophobicity and anticorrosion
performance of the fluorocarbons surface treatment process.
12 SPE-191656-MS

Figure 8—EIS spectra for fluorocarbon coating in ASP system

Wax-Deposition Behavior Inhibition and Drag Reduction

Considering the phase inversion point of the experimental strong alkali (NaOH) ASP flooding produced
fluid was in the water fraction of approximately 65%, the flow behaviors of the produced emulsions
with 58.3% and 75.6% water fractions in pipelines could reveal the potential corrosion protection and
flow assurance issues. The multiple efficacy of surface treatment technology including anticorrosion,
weatherability, deposition behavior inhibition and drag reduction were expected in actual operation. As
shown in Figure 9, wax-deposition behavior exhibited similar characteristics in different surface treatment
tubing. When the external temperature was constant, the wax-deposition rate first had a slight increase and
then gradually decreased with the increase of the temperature difference between the bulk fluid and the wall.
And the maximum wax-deposition rate appeared near the freezing point of the crude oil. This was because
the molecular concentration gradient of paraffin hydrocarbon between the bulk fluid and the wall decreased
at higher temperature difference, and the role of thermal diffusion mechanism in wax-deposition behavior
was highlighted with the continuous decrease of temperature difference. Thermal diffusion became the main
driving force for deposition behavior, especially when the temperature was below the freezing point of crude
oil. However, there was a remarkable decrease of wax-deposition rate in tubing with fluorocarbons surface
treatment, the maximum wax-deposition inhibition rate was up to 51.57% (Figure 9(a)) for strong alkali
(NaOH) ASP flooding produced emulsion with water fraction of 58.3%, and the maximum wax-deposition
inhibition rate was up to 46.42% (Figure 9(b)) for the produced emulsion with water fraction of 75.6%.
The average inhibition rate was more than 25% higher than tubing with epoxy interior coating. This could
be attributed mainly to low surface energy of the fluorocarbon coating. The aggregation of wax crystals
and other particles on the tubing wall was relieved due to the unique surface property, and the adhesion
for the deposition was not sufficient to resist the shearing force in the flow field. The results indicated that
the fluorocarbon interior coating in pipelines could effectively inhibit the wax-deposition in the process
SPE-191656-MS 13

of produced fluid transportation. The surface treatment of fluorocarbons could solve the issues of intense
corrosion, coating failures as well as flow assurance in multiphase environment.

Figure 9—Wax-deposition rate as a function of temperature difference between bulk fluid and wall

Consistent with the threat to the safety and efficiency of pipeline operation caused by wax-deposition
in the process of produced fluid transportation, pipelines pressure losses and energy consumption were
responsible for cost-effective production in fields. This fact can be described through the well-known drag
reduction effect. The efficacy of various interior coatings for drag reduction in production pipelines was
investigated. As can be seen in Figure 10(a), the flow pressure gradient of ASP flooding produced fluid
with different water fractions was related to the flow rate, and it increased with the increase of the flow
rate. However, compared with the uncoated and the epoxy interior coating tubing, the pressure losses of
the fluorocarbon interior coating tubing were lower at the same flow temperature. The curve slope of the
pressure drop gradient decreased with the increase of flow rate, and thus the flow property of the produced
fluid would be significantly improved. The amount of required energy for pumping would decrease and the
desirable energy saving was achievable. A maximum drag reduction of 60% for high-viscosity ASP flooding
produced emulsions flow in tubing could be obtained with the fluorocarbons surface treatment process,
which was 20% higher than that of the conventional epoxy interior coating. This could be attributed to the
low surface energy of fluoropolymer materials and self-cleaning of interior coating after the film-forming.
Furthermore, the flow pressure drop characteristics of ASP flooding produced fluid with different water
fractions at different flow temperatures exhibited the superior performance of fluorocarbon interior coating
in drag reduction. There was a slight increase of the pressure drop gradient when the flow temperature was
reduced from 50 °C to 30 °C, the average increments of flow pressure drop of uncoated and epoxy interior
coating tubing were 56% and 42%, respectively. As shown in Figure 10(b), the adaptability of fluorocarbons
surface treatment pipelines for waxy crude oil emulsions transportation in low-temperature environment
was further revealed. It indicated fluorocarbon interior coating owned low coefficient of friction and the
low friction effect was independent of flow conditions such as flow rate and temperature. It is potential to
employ this kind of surface treatment technology in production pipeline, which was lack of heat-tracing
facilities, to reduce friction effects, increase drag reduction rate and improve the cost-effectiveness in
ASP flooding production. The results are in agreement with the inhibition effect of fluorocarbons surface
treatment on wax-deposition behavior discussed above. Although the diffusion mechanism activated by
thermal conditions dominates wax-deposition behavior at any time, low wetting property and low surface
energy of fluorocarbon interior coating can not only suppress the formation of paraffin-crystal nucleation
on pipe wall, but also can greatly reduce the friction resistance of oil-water two-phase in low-temperature
environment which is favorable to wax-deposition.
14 SPE-191656-MS

Figure 10—Flow pressure drop gradient as functions of flow rate and temperature

Coating Configurations and Process for Facilities

Despite the promotion of fluorocarbons interior coating is shelved in fields after it has been successfully
tested in chemicals stock solution tanks and pipelines of an actual injection station, however, the surface
treatment technology still attracts the interests of engineers who are engaged in EOR. Except for these basic
properties of great adhesion, chemical resistance performance, low surface energy, super-hydrophobicity
and low friction coefficient, the perfect corrosion protection also depends on coating configurations and
process. Therefore, coating configurations and process were further optimized combining the previous
practices and the further understanding from this case study. As shown in Figure 11, after the necessary
pretreat for the steel surface that can contact with the corrosive medium of ASP chemicals was completed,
the epoxy zinc rich primer was first coated, and then epoxy micaceous iron oxide primer was coated.
Next, the main layers of fluorocarbon paint and fluorocarbon cover varnish were coated. The total
coating thickness was approximately 200 μm, and the necessary maintenance for the coating was finally
implemented. The steel substrate and each layer were inspected with scanning electron microscopy (SEM)
during the coating process, the SEM images showed that crosslinking density of the coating increased and
the dense impermeable layer formed after fluorocarbon paint was coated. It indicated the fluorocarbon paint
layer dominated protection within the coating configuration as a result of its uniformity and great adhesive
properties. Under this coating configurations, these functions of decoration, impermeability, shield, and
corrosion inhibition could be achieved. Moreover, these phenomena of fading, powdering and wrinkling
of the interior coatings would be alleviated. The good protection would be provided by the fluorocarbons
interior coatings along with the increased thickness added by the primer.

Figure 11—Schematic of fluorocarbon interior coating configurations

Conclusions
Considerable corrosion and scaling were created and covering the surface facilities such as the storage
tanks of ASP chemicals, the pipelines for injection and production, and the heating furnaces in ASP
SPE-191656-MS 15

flooding production. Both of the applied physical and chemical protection measures are facing to the
challenges of service life, potential environmental threats and unpredictable cost-effectiveness. Especially
the wax-deposition behavior that relates to corrosion-scaling and emulsification in pipelines for transporting
produced fluid draws unprecedented concerns in current energy-saving and cost-reducing background. We
proposed and concerned a coating solution that using fluorocarbons coating to treat the surface of metal
substrates, which can be used in ASP chemicals environment.
1. The film-forming process in fluorocarbons surface treatment can be achieved based on the
available solvent-based film-forming materials. High bond energy and strong chemistry inertia of
fluorinated resins can prevent the coating structure from being destroyed and develop flexibility and
weatherability of the coating.
2. A favorable low-wetting surface could be created after performing fluorocarbons surface
treatment, and a typical capacitive behavior would be exhibited in EIS spectra for anticorrosion
performance evaluation. The pore resistance and shielding performance of fluorocarbon coating
in corrosion environment highlighted actually result from the superior mechanical properties,
super-hydrophobicity, and self-cleaning performance. The excellent corrosion-scaling resistance of
fluorocarbon coating is attractive both in strong alkali (NaOH) and weak alkali (Na2CO3) ASP
system. The reasonable coating configurations and process are certainly indispensable in the potential
applications of fluorocarbons surface technology.
3. Low surface energy and low coefficient of friction of the fluorocarbon interior coating provide the
possibility of pipeline wax-deposition inhibition and drag reduction. The maximum wax-deposition
inhibition rate and the maximum drag reduction rate reached 46.42% and 60.00% respectively for
high-viscosity ASP flooding produced emulsions in this case study.

Acknowledgements
This work was financially supported by China Postdoctoral Science Foundation (Grant no. 2017M611349)
and the State Key Program of National Natural Science Foundation of China (Grant no. 51534004). The
University Nursing Program for Young Scholars with Creative Talents in Heilongjiang Province of China
(Grant no. UNPYSCT-2017033) is also gratefully acknowledged.

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