Hydrophilic Nanoparticles Facilitate Wax Inhibition

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Hydrophilic Nanoparticles Facilitate Wax Inhibition


Fei Yang,† Kristofer Paso,*,‡ Jens Norrman,‡ Chuanxian Li,† Hans Oschmann,§ and Johan Sjöblom‡

College of Pipeline and Civil Engineering, China University of Petroleum, Qingdao, Shandong 266580, People’s Republic of China

Ugelstad Laboratory, Department of Chemical Engineering, Norwegian University of Science and Technology, NO-7491
Trondheim, Norway
§
Nalco Champion, Langestraat 169, 7491 AE Delden, Netherlands

ABSTRACT: A new class of hybrid pour point depressants (PPDs) are developed on the basis of poly(octadecyl acrylate)
(POA) functionality and POA/nanosilica hybrid particles. Activity performance is demonstrated using a model waxy oil system
consisting of 10 wt % macrocrystalline wax dissolved in dodecane, effectively emulating the essential characteristics of waxy
petroleum fluids. Differential scanning calorimetry (DSC) evidence confirms that POA molecules enhance the solubility of wax
in the continuous oil phase, reducing the wax appearance temperature. The presence of POA also serves effectively to modulate
the crystal morphology to a more regular spherical-like shape, instead of the disc-like morphologies common to pristine paraffin
wax crystals, affecting reduced gelation temperatures in accordance with percolation theory predictions. In addition, rheometric
yield stresses decrease with increasing dosage rates of POA. A solvent-blending protocol is followed to subsequently prepare
POA/nanosilica hybrid particles. Optimal PPD performance of the hybrid particle system is attained at a dosage rate of 100 ppm.
At dosages higher than the optimal dose, the gel strength increases in an analogous manner to the directionality of the Einstein
equation for viscosity. The POA/nanosilica hybrid particle system provides spherical templates for wax precipitation, resulting in
a compact precipitate structure, which suppresses gelation and improves the flowability of the model waxy oil by several orders of
magnitude. DSC data confirm that a vast majority of the POA molecules become solubilized in the continuous oil phase upon
dispersion of the hybrid nanoparticle system. As such, the free POA molecules enhance wax solubility in the continuous oil phase.
Hydrophobic nanoparticles retain a more robust ability to modulate waxy oil rheology at low-dosage rates, as compared to purely
polymeric functionality. The primary mechanism of hybrid particle PPDs involves heterogeneous nucleation activity. The hybrid
particles effectively provide solid−liquid interface sites as wax precipitation templates, which result in spherical-like spherical wax
morphologies. The compact morphologies hinder and suppress the percolation process necessary to form a volume-spanning
network of wax crystals. As such, the hybrid nanoparticles constitute effective and economic PPD additives and may serve as the
basis for next-generation environmentally friendly wax inhibition agents, by reducing the amount of additives needed.

■ INTRODUCTION
Crude oil often contains substantial amounts of paraffin wax,
poly(ethylene−vinyl acetate) (EVA), and comb polymers, such
as polyacrylate. Effects of alkyl side chain length,6,7 polar group
which constitutes the saturated aliphatic fluid fraction.1 When type8,9 and content,10,11 molecular weight,12,13 and oil-phase
the crude oil temperature falls below the wax appearance composition14,15 have been widely studied. PPD activity
temperature (WAT), the paraffin wax precipitates in an mechanisms include crystal habit alteration and entropic
orthorhombic unit cell as needle- or plate-like crystals.2 repulsion.5 Interactions between polymeric PPDs and asphal-
Because of large aspect ratios, precipitated wax crystals often tene molecules also influence the efficiency of PPDs.16
form a “house of cards” network structure at very low With recent progress in nanotechnology, many nanomateri-
precipitated amounts (∼1 wt %),3 thus imparting high pour als have been prepared and applied in industry. Research and
point, high viscosity, high yield stress, and non-Newtonian flow development efforts17−20 have resulted in new polymer/
behavior to waxy crude oils. For pipe transport of waxy crude inorganic nanocomposites or nanohybrids. With introduction
oil and gas condensate fluids, precipitation of paraffin wax from of inorganic nanoparticles into polymer matrixes, resultant
the continuous oil phase not only increases viscosity and properties (ie. mechanical, thermal, magnetic, and electrical)
associated pressure losses but also endangers restart of shut-in are modulated. In the field of the crude oil industry,
pipelines.4 Effective management of paraffin wax precipitation, nanomaterials have been used as lubricants,21 catalysts,22 oil
gelation, and deposition is a large challenge for flow assurance, recovery agents,23 and paving asphalt improvers.24 Recently,
risk abatement, integrity management, and emergency inter- Wang et al.25 developed nanohybrid PPDs and compared
vention planning. performance efficiencies between nanohybrid PPDs and
Standard industrial practice for improving flowability is to traditional EVA PPDs. Nanohybrid PPDs exhibit superior
dose the waxy crude oil with an oil-soluble pour point pour point depression than EVAs. Microscopic images of
depressant (PPD). PPDs are highly interfacially active precipitated wax crystals demonstrate that nanohybrid PPDs
polymers, which serve to modulate crystal morphology as
well as intercrystal interactions. Various types of polymeric Received: October 23, 2014
additives have been developed and used as PPDs.5 The most Revised: February 23, 2015
widely used types are linear copolymerized ethylene, such as Published: March 2, 2015

© 2015 American Chemical Society 1368 DOI: 10.1021/ef502392g


Energy Fuels 2015, 29, 1368−1374
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result in smaller and more dispersed wax crystals, improving the


rheology of waxy crude oil, confirming a synergistic effect of
hybrid EVA nanoparticles. The previous art corroborates
multiple PPD activity mechanisms. Possible mechanisms for
these non-hybrid PPDs include nucleation (functioning as
additional dispersed nucleation sites, resulting in the formation
of a larger number of smaller crystals), adsorption (adsorbing
on the surface of wax crystals, hindering crystal growth), and
co-crystallization (incorporating into the forming wax crystals,
thereby hindering or changing the crystal growth).
In the current work, nanohybrid particles composed of
nanosilica and poly(octadecyl acrylate) (POA) are prepared via
a solvent-blending protocol. Effects of POA and hybrid particles
on the gelation point and yield stress of a model fluid system
are investigated. Differential scanning calorimetry (DSC) Figure 1. Fourier transform infrared (FTIR) curves of octadecyl
measurements and microscopic observation of the treated acrylate and POA.
and untreated systems are performed. Hybrid systems are
shown to retain a robust ability to impart fluid flowability at low
dosages (e.g., 100 ppm). The hybrid particles appear to
modulate the crystal morphology, resulting in more spherical
and compact shapes, serving to reduce the gelation point and
rheological yield stress.

■ EXPERIMENTAL SECTION
Chemical agents used in this work were purchased from Sigma-Aldrich
Co. The mass fraction purity of dodecane, toluene, ethanol, octadecyl
acrylate, and 2,2′-azobis(2-methylpropionitrile) (AIBN) were all ≥99
wt %. Macrocrystalline paraffin wax used (Sasolwax 5405, primarily
composed of linear paraffin components) was supplied by Sasol Wax
Co. Nanosilica used was hydrophilic fumed silica with a specific surface
area of 200 m2/g (Aerosil 200, Evonik Industries Co.). Model waxy oil
was used for the experiments, prepared by dissolving 10 wt % Sasolwax
5405 in dodecane. The model fluid WAT (38.7 °C) is not close to the
gelation point (24.7 °C), and the model fluid also retains the essential
compositional characteristics of waxy petroleum fluids and has
successfully been used in previous work on waxy petroleum.26−29
This model system was used to obtain more insight into the effect of
the nanohybrid particles on the waxy oil without having to try to
include the effect of native surface-active species of crude oil (such as
asphaltenes and resins). The carbon number distribution of the wax
used, as obtained from the high-temperature gas chromatography
(HTGC), is given in ref 29. The carbon number distribution of linear
alkane components ranges from n-C20 to at least n-C44, with a
maximum at n-C26. A long “tail” in the distribution exists from n-C34 to
n-C44, imparting large disparities in “apparent WAT” values obtained
by isothermal versus non-isothermal techniques. The carbon number
distribution of branched and cyclic components ranges from i-C20/c-
C20 to i-C41/c-C41, as categorized on a boiling point fractionation basis.
POA was synthesized by solvent free-radical polymerization of
octadecyl acrylate under a nitrogen atmosphere with constant stirring.
The polymerization was conducted in toluene solution (30 wt %) at 70
°C for 8 h using AIBN as an initiator. The polymer was precipitated in
excess ethanol, filtered, and dried under vacuum at 60 °C, with the
final state of POA being a white solid. Figure 1 shows infrared (IR) Figure 2. Dispersion state of 0.1 wt % nanosilica and 0.1 wt % hybrid
curves of octadecyl acrylate and POA used in this work. For octadecyl particles in dodecane after 1 h: (a) nanosilica dispersion and (b)
acrylate, CC absorption peaks appear at 810, 900, and 1630. For hybrid particle dispersion and (c) microscopic image of hybrid
POA, however, CC absorption peaks disappear, confirming particles in dodecane.
successful POA synthesis. The mean molecular weight of POA as
assessed by gel permeation chromatography (GPC) was ∼18 000 Da.
POA/nanosilica hybrid particles were prepared using a solvent- nanosilica particles do not disperse in dodecane and sediment quickly
blending protocol. A specified amount of POA was first dissolved in to the bottom of the vial. No evident sedimentation is observed after 1
toluene; subsequently, an identical amount of nanosilica was dispersed h for the 0.1 wt % hybrid particle-in-dodecane solution (Figure 2b).
in the POA/toluene solution though ultrasonic treatment and vigorous The microscopic image (Figure 2c) shows that hybrid particles
stirring. The solution was carefully evaporated at 70 °C under dispersed in dodecane retain a spherical-like morphology and have a
continuous stirring to remove toluene. Finally, dried POA/nanosilica particle size of ∼10 μm.
hybrid material was ground into small particles. The POA/nanosilica Rheology of the 10 wt % model waxy oil system was assessed using
mass ratio was maintained at 1:1. As shown in Figure 2a, the original a Physica 301 rheometer (Anton Paar Co., Germany) equipped with a

1369 DOI: 10.1021/ef502392g


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2° cone-and-plate geometry with a diameter of 4 cm. The sample


temperature is Peltier-controlled, and a plastic cover is placed over the
cell to minimize evaporation.
The gelation point was assessed as follows: the oil sample was first
maintained at 60 °C for 5 min and cooled quiescently to 40 °C at a
rate of 20 °C/min. Subsequently, the oil sample was cooled at 0.5 °C/
min and sheared under an imposed shear stress of 0.01 Pa. The
variation in shear rate with the temperature was monitored; the
gelation point is ascribed to a break in the shearing curve.
Yield stress was assessed as follows: the oil sample was first
maintained at 60 °C for 5 min and cooled quiescently to 40 °C at a
rate of 20 °C/min. Subsequently, the oil sample was quiescently
cooled at a rate of 0.5 °C/min to 18 °C; the temperature was
maintained at 18 °C for 10 min under quiescent conditions. Finally,
flow curves were measured with a shearing protocol ranging from
0.001 to 10 s−1. The yield stress was obtained from the flow curves.
The reproducibility of the different rheology experiments was in
general very good (data not shown).
Exothermic characteristics of the model fluid system, in untreated
and treated states, were investigated using a Q2000 differential
scanning calorimeter (TA Instruments). The temperature scanning
range was between −10 and 60 °C; a fixed cooling rate of 5 °C/min
was employed during the crystallization process. The DSC curves
provide a measure of the crystallization onset temperature, which is
evidenced by a sharp increase in the exothermic heat flux signal.
Wax crystal morphology was investigated using a light microscope
TE 2000-S (Nikon Eclipse, Japan) in phase contrast and cross-
polarized mode. Treated and untreated model fluid samples were
initially heated to 60 °C for 5 min, and then one droplet was
transferred to a glass slide covered by a coverslip. The samples were
viewed with the microscope at a cooling rate of 5 °C/min in the
temperature range from 60 to 40 °C and then cooled a rate of 0.5 °C/
min in the temperature range from 40 to 10 °C. The oil samples were
maintained at 10 °C for 5 min, and then images of the wax crystal
structure were recorded manually.

■ RESULTS AND DISCUSSION


The effect of POA on the gelation point is illustrated in Figure
Figure 3. Effect of (a) POA and (b) hybrid particles on the gelation
3a. The shear rate initially decreases upon temperature point of the model waxy oil.
reduction in accordance with an Arrhenius relation. At the
wax precipitation onset (see Table 1), the shear rate deviates
from the Arrhenius trend. A sharp break in the curve is point, these two opposing forces come to a minimum, such
observed at the gelation point. Below the gelation point, that, at and below this minimum, the change in wax
creeping flow continues. The gelation point of the untreated crystallization has a greater effect on the gelation point than
model fluid system is 24.7 °C. The gelation point decreases the additional volume of added particles, but above this optimal
gradually with an increasing POA concentration. The gelation concentration, the additional volume of solid particles instead
point is 23.2 °C at 50 ppm, 22.6 °C at 100 ppm, 22.1 °C at 200 counteracts this effect and the gelation point rises again. A
ppm, and 21.2 °C at 500 ppm. POA molecules are present at possible complication could be if the attached POA detaches
the wax crystal interface, altering the crystallization habit and and solubilizes in the bulk phase, leaving behind naked silica
affording entropic repulsion between the wax crystals. particles. These naked or partially naked silica particles could
As observed in Figure 3b, the hybrid particle system retains a then become incorporated within the growing paraffin wax
stronger ability to decrease the gelation point of the crystal network, further adding to the effect described above.
representative model fluid system at 100 ppm. The gelation Figure 4 illustrates the yield stress of the treated and
point is 21.7 °C at 50 ppm, 18.7 °C at 100 ppm, 19.5 °C at 200 untreated model fluid systems. In the untreated state, the yield
ppm, and 21.0 °C at 500 ppm. A minimum value of the gelation stress is ∼100 Pa at a temperature of 18 °C. When 100 ppm of
point is achieved at 100 ppm of hybrid particles. A further POA is added, the yield stress is reduced to ∼1 Pa. The
increase in the hybrid particle concentration causes the gelation traditional additive affords 2 orders of magnitude reduction in
point to increase. At concentrations of hybrid nanosilica gel strength. In comparison, after the addition of 100 ppm of
particles higher than this optimum, the additional particles the hybrid particle system, the yield stress is reduced to 0.2 Pa.
added to the solution work as additional suspended particles, The nanohybrid system provides nearly 3 orders of magnitude
thus strengthening the gel structure (in accordance with the reduction in gel strength. It is evident that the addition of POA
Einstein equation). At low concentrations of nanohybrid and hybrid particles greatly decreases the strength of the wax−
particles, the dispersed particles modulate the wax crystal- oil gel. The hybrid particles maintain a robust ability to reduce
lization in such a way that the gelation point is lowered. At the the yield stress.
same time, adding solid particles to the suspension adds DSC curves obtained with the model waxy fluid system are
additional particles to potentially form a network. At some shown in Figure 5. Upon temperature reduction, the heat flow
1370 DOI: 10.1021/ef502392g
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Table 1. Wax Precipitation Onset (WPO, by DSC at 5 °C/min) and Gelation Point of 10 wt % Model Waxy Oil at Various
POA/Hybrid Particle Concentrationsa
concentration (ppm) 0 50 100 200 500
WPO POA 25.6 °C 24.1 °C 23.6 °C 23.0 °C 22.1 °C
hybrids 25.6 °C 24.5 °C 24.0 °C 23.6 °C 23.1 °C
gelation point POA 24.7 °C 23.2 °C 22.6 °C 22.1 °C 21.2 °C
hybrids 24.7 °C 21.7 °C 18.7 °C 19.5 °C 21.0 °C
a
For reference, the system WAT is 38.7 °C.

reduction is induced solely by POA; additional silica particles


do not reduce the precipitation onset point.
The WAT of Salsol wax 5405 in dodecane was further
investigated by visual observation. This was performed by
placing a sealed sample vial with known wax content at a
temperature at least 25 °C above the WAT. This sample was
then placed in a water bath (with internal circulation) at a lower
temperature and maintained at isothermal conditions for 24 h.
After this time, the sample was compared to a clear sample
(dodecane) to see if any wax had precipitated. This was
repeated (with a precision of 0.1 °C) until the temperature at
which the sample became turbid was narrowed down and
determined within 0.1 °C, establishing the WAT. The results
are shown in Figure 6. The WAT by this method of 10 wt %

Figure 4. Effect of POA and hybrid particles on the yield stress of the
model fluid at 18 °C.

Figure 6. Solubility of Sasol wax 5405 in dodecane as a function of the


temperature, as determined by visual observation, establishing the
WAT. The symbol “x” denotes the mole fraction of paraffin wax in the
system.
Figure 5. DSC curves of 10 wt % model waxy oil undoped/doped with
POA and hybrid particles. Sasol 5405 wax in dodecane is 38.7 °C and is governed by the
high-molecular-weight “tail” of paraffins in wax composition.
signal decreases initially and then increases sharply with wax The difference between the high turbidity observation and the
precipitation. The temperature at which the heat flow signal lower WAT determined by DSC illustrates the strong impact of
deviates from the liquid state heat capacity trend establishes the nucleation kinetics for this system and can be explained by the
WAT. The observed wax precipitation onset of the untreated high cooling rate of the DSC experiment in conjunction with
system is 25.6 °C. When 100 ppm of POA is added to the the high-molecular-weight tail of n-alkanes in the wax
model fluid system, the observed wax precipitation onset of the composition, which are subject to highly nonlinear nucleation
waxy oil decreases to 23.6 °C, corroborating a small solubility kinetics.
enhancement with the presence of POA. When 100 ppm of Figure 7 shows microscopic images of the untreated and
hybrid particles are added to the model fluid system, the wax treated model waxy oil system at a temperature of 10 °C.
precipitation onset is 24.0 °C. Hence, the hybrid particles do Because small wax crystals (see panels a1 and a2 of Figure 7) in
not provide the same solubilization efficacy as pure POA. the pristine waxy oil are not easily observed under polarized
Moreover, the precipitation onset at 50 ppm of POA is nearly light, the image is presented in phase contrast mode. Small
the same as the onset at 100 ppm of hybrid particles crystals exhibit large relative surface areas and disc-like
(composed by half POA and half silica particles). A similar morphologies, which readily form network structures, resulting
comparison may be drawn at 100 ppm of POA and 200 ppm of in a physical colloidal gel. When a small amount of POA (100
hybrid particles, indicating that the wax precipitation point ppm; see Figure 7b) is added to the waxy model oil, the crystal
1371 DOI: 10.1021/ef502392g
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Figure 7. Microscopic images of 10 wt % model waxy oil undoped/doped with POA and hybrid particles at 10 °C. Without polarized light: (a1 and
a2) non-added. With polarized light: (b) 100 ppm of POA, (C) 500 ppm of POA, and (d) 100 ppm of hybrid particles.

size increases and the crystal morphology likely becomes more in the continuous oil phase, reducing the WAT. In addition,
compact. The gelation point is reduced to 22.6 °C, and the POA effectively modulates the crystal morphology to a more
yield stress is reduced to 1 Pa. As the POA concentration regular spherical-like shape. The data are consistent with overall
increases from 100 to 500 ppm, the morphology of precipitated percolation theory predictions of lower gelation temperatures
wax crystals becomes even more spherical-like and the size of for lower aspect ratio morphologies. Assuming free crystal
the particles increases to ∼20 μm in diameter (see Figure 7c). rotation, the theoretical percolation threshold φg for ellipsoidal
The more regular morphology (spherical-like) interferes with discs is φg = 0.295/α, where α denotes the aspect ratio. Hence,
the gelation process, thus further decreasing the gelation point reduced crystal aspect ratios affected by added chemicals
(21.2 °C) of the waxy oil. directly increase the solid fraction necessary for formation of a
Upon addition of 100 ppm of hybrid nanosilica particles, the volume-spanning solid-phase network. Hybrid particles retain a
wax crystals have a size of ∼20 μm and a regular shape more robust ability to modulate waxy oil rheology at 100 ppm,
(spherical-like) with a compact structure (see Figure 7d). The as compared to traditional PPD functionality. According to the
regular morphology serves to reduce the volume fraction of DSC results, hybrid particles induces the same degree of
occluded oil and increase the precipitated solid fraction solubilization as the inherent polymer content within the
required for percolation conditions, thereby suppressing the nanohybrid. However, the primary function of hybrid particle
overall gelation process. The suppressed gelation process in the PPDs is to provide large amounts of nucleation sites with
presence of hybrid nanoparticles is corroborated by a measured interfaces that provide regular (spherical-like) templates upon
gelation temperature of 18.7 °C. which wax molecules can precipitate. These precipitated wax
POA suppresses the gelation process and improves the crystals have a more regular shape (spherical-like) and a
flowability of the model waxy oil by several mechanisms. DSC compact structure, which hinders the percolation process
data confirms that POA molecules enhance the solubility of wax necessary to form a volume-spanning network of wax crystals,
1372 DOI: 10.1021/ef502392g
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as shown in Figure 8. The presence of a hybrid nanoparticle basis for next-generation environmentally friendly wax inhibitor
additive results in free wax crystals of a modified morphology, additive agents.
Further investigation into how these nanohybrid systems
behave under realistic production conditions and, more
importantly, with real waxy crude oils together with all of the
different components in addition to the waxes is an important
step forward, and such investigations are currently underway.

Figure 8. Schematic of the morphological modulation mechanism.


■ AUTHOR INFORMATION
Corresponding Author
*E-mail: kristofer.paso@chemeng.ntnu.no.
Notes
providing a mechanistic impact of morphological modulation The authors declare no competing financial interest.


on PPD performance.

■ CONCLUSION
POA and corresponding nanosilica hybrid particles are
ACKNOWLEDGMENTS
This work was financially supported by the National Natural
prepared and demonstrated as effective PPD additive agents, Science Foundation of China (51204202) and the Natural
with potential for use in industry. Activity performance is Science Foundation of Shandong Province of China
demonstrated using model waxy oil consisting of 10 wt % (ZR2012EEQ002).


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1374 DOI: 10.1021/ef502392g


Energy Fuels 2015, 29, 1368−1374

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