Hydrophilic Nanoparticles Facilitate Wax Inhibition
Hydrophilic Nanoparticles Facilitate Wax Inhibition
Hydrophilic Nanoparticles Facilitate Wax Inhibition
pubs.acs.org/EF
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
■ 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, CC absorption peaks appear at 810, 900, and 1630. For hybrid particle dispersion and (c) microscopic image of hybrid
POA, however, CC 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
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.
Figure 4. Effect of POA and hybrid particles on the yield stress of the
model fluid at 18 °C.
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
Energy Fuels 2015, 29, 1368−1374
Energy & Fuels Article
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.
■
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).
■
macrocrystalline wax dissolved in dodecane, which emulates the
essential characteristics of waxy petroleum fluids. The hybrid REFERENCES
particles affect a reduction in gelation point as well as yield
(1) Rønningsen, H. P.; Bjørndal, B. Wax precipitation from North
stress of the model wax−oil gels. An optimal performance is Sea crude oils: 1. Crystallization and dissolution temperatures, and
obtained at a dosage of 100 ppm for the nanohybrid system. Newtonian and non-Newtonian flow properties. Energy Fuels 1991, 5,
Beyond this optimal dosage, additional particles result in 895−908.
increased gel strength, analogous to the directionality of the (2) Edwards, R. T. Crystal habit of paraffin wax. Ind. Eng. Chem.
Einstein equation for viscosity. 1957, 49, 750−757.
DSC solubility studies indicate that solely the polymer (3) Yang, F.; Li, C.; Li, C.; Wang, D. Scaling and structural
content of the hybrid system governs the effective increase in characteristics of gelled waxy model oils. Energy Fuels 2013, 27, 3718−
wax solubility. Hence, a majority of the polymer likely becomes 3724.
solubilized in the continuous oil phase upon dispersion. (4) Wardhaugh, L. T.; Boger, D. V. Flow characteristics of waxy
The comb-like POA appears to favor the formation of island crude oils: Application to pipeline design. AIChE J. 1991, 37, 871−
885.
defects on the wax surface, which have weak interactions with
(5) Yang, F.; Zhao, Y.; Sjöblom, J.; Li, C.; Paso, K. G. Polymeric wax
the surrounding crystal and, therefore, act as impurity sites for inhibitors and pour point depressants for waxy crude oils: A critical
blocking growth steps.30,31 The silica particles act as anchoring review. J. Dispersion Sci. Technol. 2015, 36, 213−225.
points, with many POA molecules bound to the particle surface, (6) Al-Sabagh, A. M.; El-Hamouly, S. H.; Khidr, T. T.; El-Ghazawy,
creating a localized higher concentration of POA. Therefore, R. A.; Higazy, S. A. Preparation the esters of oleic acid−maleic
the wax molecules co-crystallize with POA on the particle, anhydride copolymer and their evaluation as flow improvers for waxy
leading to the formation of large and compact wax crystals. The crude oil. J. Dispersion Sci. Technol. 2013, 34, 1585−1596.
compact structure and large size of wax crystals are adverse to (7) Soldi, R. A.; Oliveira, A. R. S.; Barbosa, R. V.; César-Oliveira, M.
the formation of network structures, thus modulating the A. F. Polymethacrylates: Pour point depressants in diesel oil. Eur.
rheology of the waxy oil further. Polym. J. 2007, 43, 3671−3678.
The fact that there is an optimum dosage and that particle (8) Xu, J.; Xing, S.; Qian, H.; Chen, S.; Wei, X.; Zhang, R.; Li, L.;
Guo, X. Effect of polar/non-polar groups in comb-type copolymers on
concentrations above 100 ppm do not increase the effect can
cold flowability and paraffin crystallization in waxy oils. Fuel 2013, 103,
possibly be explained by the fact that not all silica particles are 600−605.
fully covered in POA (dark patches in Figure 7d are silica (9) Farag, R. K. Poly(cinnamoyloxy ethyl methacrylate-co-octadecyl
particles). These silica particles would then act as additional acrylate) as flow improver for Egyptian waxy crude oils. Int. J. Polym.
suspended particles and increase the viscosity in accordance Mater. 2008, 57, 189−202.
with the Einstein equation. This could possibly be avoided in (10) Machado, A. L. C.; Lucas, E. F. Poly(ethylene-co-vinyl acetate)
further work by increasing the binding of POA to the (EVA) copolymers as modifiers of oil wax crystallization. Pet. Sci.
underlying substrate, by either pretreating the silica or chemical Technol. 1999, 17, 1029−1041.
grafting of POA to the silica, thus avoiding the neat silica (11) Machado, A. L. C.; Lucas, E. F.; González, G. Poly(ethylene-co-
particles in the solution. vinyl acetate) (EVA) as wax inhibitor of a Brazilian crude oil: Oil
The more relevant activity mechanism of the nanohybrid viscosity, pour point and phase behavior of organic solutions. J. Pet. Sci.
Eng. 2001, 32, 159−165.
PPDs is the impact upon crystal morphology. The hybrid
(12) Ashbaugh, H. S.; Guo, X.; Schwahn, D.; Prud’homme, R. K.;
particles provide heterogeneous nucleation sites for paraffin Richter, D.; Fetters, L. J. Interaction of paraffin wax gels with ethylene/
wax crystallization, causing the formed wax crystals thus vinyl acetate co-polymers. Energy Fuels 2005, 19, 138−144.
attained to have a modified morphology characterized by (13) Borthakur, A.; Chanda, D.; Choudhury, S. R. D.; Rao, K. V.;
compact, spherical-like structures, which hinder and suppress Subrahmanyam, B. Alkyl fumarate−vinyl acetate copolymer as flow
the gelation process. The low dosage of these systems is improver for high waxy Indian crude oils. Energy Fuels 1996, 10, 844−
promising and indicates that they are a good candidate as the 848.