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Polymeric Wax Inhibitors and Pour Point Depressants for Waxy Crude Oils: A
Critical Review
Article in Journal of Dispersion Science and Technology · March 2014

DOI: 10.1080/01932691.2014.901917
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Polymeric Wax Inhibitors and Pour Point Depressants

for Waxy Crude Oils: A Critical Review
a b b b b
Fei Yang , Yansong Zhao , Johan Sjöblom , Chuanxian Li & Kristofer G. Paso
a
College of Pipeline and Civil Engineering, China University of Petroleum , Qingdao ,
Shandong , People's Republic of China
b
Ugelstad Laboratory, Department of Chemical Engineering , Norwegian University of
Science and Technology , Trondheim , NO , Norway
Accepted author version posted online: 07 Apr 2014.Published online: 07 Apr 2014.
To cite this article: Fei Yang , Yansong Zhao , Johan Sjöblom , Chuanxian Li & Kristofer G. Paso (2014): Polymeric Wax
Inhibitors and Pour Point Depressants for Waxy Crude Oils: A Critical Review, Journal of Dispersion Science and Technology,
DOI: 10.1080/01932691.2014.901917
To link to this article: http://dx.doi.org/10.1080/01932691.2014.901917
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Polymeric Wax Inhibitors and Pour Point Depressants for Waxy Crude Oils: A
Critical Review
Fei Yang1, Yansong Zhao2, Johan Sjöblom2, Chuanxian Li2, Kristofer G. Paso2
1
College of Pipeline and Civil Engineering, China University of Petroleum, Qingdao,
Shandong, People’s Republic of China, 2Ugelstad Laboratory, Department of Chemical
Engineering, Norwegian University of Science and Technology, Trondheim, NO,
Norway
Address correspondence to Fei Yang, College of Pipeline and Civil Engineering, China
University of Petroleum, Qingdao, Shandong 266580, P. R. China Email:
Downloaded by [Universitetbiblioteket I Trondheim NTNU] at 00:03 29 April 2014
yf9712220@sina.com
Received 17 February 2014; Accepted 4 March 2014.
Abstract
Paraffin precipitation during pipeline transport of waxy crude oils gives rise to several
challenges, including wax deposition, flow reduction, and gel formation, adversely
impacting pipeline performance. Small dosages of polymeric wax inhibitors or pour point
depressants comprise an effective preventative measure. In this paper, the structural
character, functionality, and mechanisms of the polymeric additives targeting paraffin
wax are reviewed, and factors influencing product efficacy are summarized. Most
polymeric additives contain a nonpolar moiety as well as a polar moiety, with the
exception of crystalline-amorphous copolymers. Via nucleation, adsorption, co-
crystallization and solubilization interactions, polymeric additives alter the morphology
and interface of precipitated wax crystals, inhibiting wax deposition, improving flow, and
impeding gel formation. The presence of asphaltenes significantly impact wax crystal
morphology and interfaces, thus influencing the mechanism of polymeric additives. Most
polymeric additives fall into the categories of crystalline-amorphous copolymers,
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enthylene-vinyl acetate copolymers, comb polymers and nano-hybrids. Factors
influencing polymeric efficacy include molecular structure, fluid composition, and
pipeline transport conditions.

KEYWORDS: Wax inhibitor; pour point depressant; interaction mechanism;
microscopic morphology; influencing factors.
1. INTRODUCTION
Waxy crude oils are encountered throughout the world and have been produced for
several decades in areas such as China, India, Egypt and the North Sea.[1–4] These fluids
contain substantial amounts of petroleum wax (normally ≥ 5 wt%), which complicates
crude oil recovery, processing and transportation[5]. Petroleum wax may be categorized
into two distinct types: macro-crystalline paraffin wax and microcrystalline paraffin
wax.[6,7] Macro-crystalline wax is composed of primarily low molecular weight n-
alkanes (C16-C40), and generally crystallizes as needles or platelets. Micro-crystalline
wax, on the other hand, contains a large proportion of high molecular weight iso-alkanes
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and cyclo-alkanes. Due to the large number of isomer permutations as well as an absence
of large-scale crystals, micro-crystalline paraffin waxes normally precipitate as small
amorphous particles and do not exhibit distinct crystallization regime.
When waxy crude oil is cooled below the wax appearance temperature (WAT), paraffin
waxes precipitate from the oil, leading to technical challenges in the transport pipeline.
Continuous wax deposition may occur when the inner wall temperature is below the
WAT and a negative radial temperature gradient is present.[8–10] Deposition phenomena
serve to reduce the effective pipeline diameter and may cause complete blockage under
severe or synergetic conditions, adversely impacting pipeline operation. Periodic pigging
or chemical/thermal dissolution is required to remediate wax deposition, renewing free
fluid flow conditions in the pipeline. However, pigging and dissolution operations are
costly and should be minimized.[11] In addition, large plate-like or needle-like wax
crystals form house-of-cards structures and impart complex non-Newtonian
characteristics to crude oil rheology, including yielding, thixotropy, rupture and fixation.
Observed pour point values are often higher than ambient conditions.[12–15] Impaired
flow reduces transportation safety and efficiency. Maintaining thermal transport
conditions above pour point is energy consuming, resulting in excess environmental
pollution.
The challenges outlined above may be alleviated by small dosages of polymeric additives.
Polymeric wax inhibitors[5] (WIs) are widely applied in pipeline transportation of waxy
crude oils to alleviate wax deposition. Most of inhibitors may also be used as pour point
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depressants (PPDs) or flow improvers (FIs) for waxy crude oils,[5] vastly improving
safety and economics. In the current article, structural character, type, and mechanisms
relevant to polymeric wax inhibitors and pour point depressants are reviewed. Factors
influencing polymer efficiency are also discussed.
2. STRUCTURAL CHARACTER OF WAX INHIBITORS AND POUR POINT

DEPRESSANTS
Most polymeric wax inhibitors and pour point depressants contain two basic
moieties:[16,17] a polar moiety and a nonpolar moiety. Nonpolar moieties are normally
long alkyl chains which interact with paraffin waxes via nucleation, adsorption or co-
crystallization.[3,18–20] Polar moieties, such as esters, vinyl acetates, maleic anhydrides or
acrylonitriles, may interrupt wax crystal growth, modulate morphology and inhibit
formation of large wax crystals.[21–23] In addition, steric and entropic repulsion
mechanisms are highly relevant but not well documented.
An exception to the standard structural character are crystalline-amorphous
copolymers[24], which self-assemble in the oil phase. These polymeric wax inhibitors and
pour point depressants, such as ethylene/butene copolymers (PEB)[25,26], are composed of
a crystalline nonpolar group (polyethylene) and an amorphous nonpolar group
(polybutene). The crystalline groups form crystalline cores surrounded by amorphous
groups, which effectively disperse the crystalline cores within the oil phase.
3. MECHANISM OF WAX INHIBITORS AND POUR POINT DEPRESSANTS
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3.1 Crystallization Process Of Waxy Crude Oils
Crystallization is a physical process in which such a solid ordinate structure is produced
from a disordered phase. Crystallization of paraffin waxes from crude oil may be divided
into three stages:[16,27] nucleation, growth and agglomeration. In the first stage, nuclei
appear due to super-saturation of paraffin waxes in the oil phase. During growth process,
wax molecules from the solution bulk are transported towards the nuclei, driving an
increase in crystallite size. During agglomeration process, formed wax crystals interlock,
causing network formation.
3.2 Mechanism Of Polymeric Wax Inhibitors And Pour Point Depressants
Although precise mechanisms of polymeric wax inhibitors and pour point depressants are
not evident, the additives are known to modify morphology (size and shape) of wax
crystals through the interaction with paraffin waxes. Thereby, the tendency of wax
crystals to form three-dimensional networks is impeded. The final result is the improved
macroscopic rheology of waxy crude oils.
3.2.1 Interactions Between Polymeric Additives And Paraffin Waxes
According to Gilby[19] and Atta[20], a combination of interactions between polymeric wax
inhibitors and pour point depressants and paraffin waxes involving nucleation, adsorption,
co-crystallization, and solubilization are relevant.
Nucleation. At temperatures well above the WAT, certain polymeric wax inhibitors
and pour point depressants self-assemble into micelle-like aggregates exhibiting a
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crystalline core and soluble hairy brushes surrounding the core[28-33], creating a larger
number of sub-critical size wax nuclei (so-called polynucleation). Partially shielded
nuclei reduce super-saturation, reduce crystal growth rates, and facilitate the formation of
more abundant smaller wax crystals. Wax crystal size reduction facilitates inhibition and
rheological beneficiation.
Adsorption[34–37] and co-crystallization[38–43]. At temperatures near or below the
WAT, many polymeric wax inhibitors and pour point depressants co-crystallize with wax
molecules or adsorb on growing surfaces of precipitated wax crystals. Incorporation of
polymeric wax inhibitors and pour point depressants into wax crystals disrupts growth,
inhibiting wax deposition and improving flowability. Molecular dynamic (MD)
simulation has been used to investigate the effect of polymeric wax inhibitors and pour
point depressants on the growth of wax crystals.[34,35,37,44,45] Figure 1[45] shows the side
view of the morphology of an idealized paraffin wax crystal with the aid of MD. Chain
addition processes proceed faster on (001) facet than on other facets, yielding plate-like
crystals. When polymeric wax inhibitors and pour point depressants are present, the
nonpolar groups may incorporate into the lattice of wax crystal cells, while polar groups
extend outside the (001) facet. The results strongly suggest that the function of wax
inhibitors and pour point depressants is to hinder growth rate on the (001) facet while
facilitating the spiral growth mechanism in the perpendicular direction to (001)
facet[37,39,44,45]. Therefore, the morphology may shift from plate-like to a structure with
more integrity (such as spherulitic-like).
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Solubilization. At temperatures slightly above WAT, polymeric wax inhibitors and
pour point depressants may interact favorably with soluble wax in the oil due to favorable
van der Waals interactions between paraffin chains and long alkyl moieties. The
solubility of paraffin waxes in oil is somewhat improved in the presence of wax inhibitors
and pour point depressants, causing reduction in WAT (see figure 2).[43,46–50] However,
the solubilization effect cannot reduce the amount of precipitated wax, and the reduction
in WAT is quite limited (see figure 2).
3.2.2 Mechanism Of Polymeric Wax Inhibitors And Pour Point Depressants On
Model Waxy Oils
Model waxy oil systems are often selected in research investigations due to
compositional simplicity and definition.[51] The mechanism of polymeric wax inhibitors
and pour point depressants on model waxy oils has been studied by DSC[16,30,43,48,50], X-
ray diffraction (XRD)[16,17,41,52], light scattering[53,54], zeta potential[55,56],
thermodynamics[40,48], and microscopy[32,41-43,57,58]. Based on nucleation, adsorption and
co-crystallization interactions, wax inhibitors and pour point depressants can (a) inhibit
the growth of wax crystals and form smaller crystals with a higher volume to surface
ratio (see figure 3 and 4); (b) disperse wax crystals in the oil phase through steric/entropic
hindrance and electrostatic repulsion[55,56]; (c) change the shape of wax crystals from the
plate-like or needle-like to ordered shapes such as dentric-like or spherulitic-like (see
figure 3 and 4). Therefore, wax deposition is inhibited and rheology is improved due to
morphological modification of wax crystals by polymeric wax inhibitors and pour point
depressants.
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3.2.3 Mechanism Of Polymeric Wax Inhibitors And Pour Point Depressants On
Waxy Crude Oils
Polymeric wax inhibitors and pour point depressants also interact with petroleum waxes
through nucleation, adsorption and co-crystallization mechanisms. Modification of
crystal morphology and modification of crystal-crystals interactions reduces the tendency

of wax crystals to interlock and form three-dimensional networks.[59] Uncertainty in
morphological modulation mechanisms derives from complex fluid compositions as well
as the broad range of molecular structures employed in polymeric wax inhibitors and
pour point depressant products.
Various observations are reported regarding the impact of polymeric additives on the
morphology of crystal aggregates. Many researchers[46,47,60–65] find that addition of wax
inhibitors and pour point depressants in waxy crude oils results in formation of larger
spherulitic-like wax crystal aggregates. In 1964, Birdwell[60] found that most cases of
pour point reduction for waxy crude oils was accompanied by formation of relatively
larger wax crystal aggregates. Yang et al[46,47] studied the effects of poly(ethylene-
vinyl acetate) (EVA) and polyacrylates (PA) PPDs on the morphology of two waxy crude
oils. As shown in Figure 5, waxy crystals become larger compact crystal aggregates after
PPD addition. Pedersen et al.[62] also observed larger wax aggregates in the presence of
inhibitor. Yi and Zhang[63,64] calculated fractal dimensions of wax crystal aggregates
based on polarized microscopic images. Large wax crystal aggregates formed and the
fractal dimension increased after PPDs addition (Figure 6). Wu et al.[65] studied the effect
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of modified maleic anhydride co-polymers on the morphology of Changqing waxy crude
oil. As shown in Figure 7, morphology shifted from small needle-like to large spherulitic-
like after PPDs addition.
Some other researchers[52,66–70] find that polymeric wax inhibitors and pour point
depressants reduce the size of wax crystals in real crude oils, as also documented for
model waxy oils. Borthakur et al[66] investigated the effect of alkyl fumarate-vinyl acetate
copolymers on flow properties of high waxy Borholla crude oil. The presence of
copolymers changes the morphology from large plate-like or needle-like crystals to
smaller crystals. Zhang and Shen[67] synthesized MOA copolymers and evaluated their
efficiency as PPDs for three waxy crude oils. The microscopic observation (see Figure 8)
shows initial large wax crystals aggregates become smaller after MOA addition. Zhang et
al.[68] synthesize octadecyl methacrylate-maleic anhydride-vinyl acetate-styrene (OMVS)
copolymers and test their efficiency as PPDs. OMVS changes the morphology of wax
crystals from the initial large needle-like to smaller spherulitic-like. Soni et al[69,70]
studied the effect of maleic anhydride (MA)-type copolymers on the rheology of waxy
crude oils. MA-type copolymers interact with paraffin waxes by nucleation and change
the morphology of wax crystals from large plate-like to smaller spherulitic-like (see
Figure 9).
The morphological controversy of wax crystals may be induced by dispersed asphaltene
aggregates. Asphaltene aggregates function as natural PPDs, generating more abundant
albeit smaller wax crystals via nucleation.[71–75] Three situations are perhaps existed about
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the morphological alteration of wax crystals. (a) When the crude oils contain very little
asphatenes, the paraffin waxes dissolved in oil phase is liable to grow into large plate-like
or needle like structure. Polymeric wax inhibitors and pour point depressants will
disperse the large crystals into smaller ones, the same as their effect on model waxy oils
system. (b) When the crude oils contain certain amounts of asphatenes, the precipitated
waxy crystals become much smaller due to the nucleation effect of asphatenes aggregates.
If the polymeric wax inhibitors and pour point depressants cannot interact with
asphaltene aggregates, they will take effect by themselves, thus making the waxy crystals
further smaller. (c) If the polymeric wax inhibitors and pour point depressants could
interact with asphaltene aggregates through their polar groups or aromatic groups, the
paraffin waxes will precipitate with both WIs/PPDs and asphaltene aggregates. This will
perhaps lead to the formation of larger wax crystal aggregates.
Addition of wax inhibitors and pour point depressants causes the formation of large wax
crystal aggregates in most cases.[62]
4. TYPES OF POLYMERIC WAX INHIBITORS AND POUR POINT
DEPRESSANTS
4.1 Ethylene Polymers And Copolymers
4.1.1 Crystalline-Amorphous Polymers
Crystalline-amorphous wax inhibitors and pour point depressants normally have
polyethylene (PE) groups as crystalline groups and amorphous moieties, such as
polybutene (PB) and polyethylenepropylene (PEP). PEB and polyethylene-
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polyethylenepropylene (PE-PEP) have been successfully applied as wax deposition
inhibition and rheological modifiers of diesel oils or crude oils.[24,76–78] PEB and PE-
PEP self-assemble into micelle-like structures with a crystalline core and amorphous
brushes surrounding the core (Figure 10). The formed micelles may interact with paraffin
waxes through nucleation effect and co-crystallization, resulting in more abundant albeit
smaller wax crystals.

4.1.2 EVA Copolymers
EVA copolymers are the most commonly used polymeric wax inhibitors and pour point
depressants.[16,32,79–83] As shown in Figure 11, EVA copolymers are comprised of chains
with PE groups of varying length, copolymerized with vinyl acetate (VA). The vinyl
acetate content has a large impact on the effectiveness and activity mechanism.[24] At low
VA contents, the copolymers have higher crystallinity potential and may crystallize from
solution above the WAT, acting as nucleating agents. At high VA contents, the
copolymers interact with paraffin waxes through co-crystallization and/or adsorption. At
very high VA contents, however, the crystallization ability of EVA copolymers becomes
too weak to interact with paraffin wax. Several reports[16,24,35,46] indicate that EVA
copolymers demonstrate optimal performance and efficacy at an optimum VA content of
28wt%. In order to further increase the effectiveness of EVA copolymers, some
researchers[80,84,85] incorporate surface active groups into the copolymer structure,
dispersing and inhibiting the growth of wax crystals.
4.2 Comb Polymers
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As shown in Figure 11, crystalline groups (PE) of EVA copolymers are contained within
the copolymer backbone, while crystalline groups of comb polymers are contained
pendant alkyl chains. Compared to EVA copolymers, comb polymers may show stronger
effectiveness as wax inhibitors and pour point depressants.[45,65] Wu et al[65] synthesized
four modified maleic anhydride comb polymers and compared the efficacy with EVA
copolymers. The comb polymers show larger pour point depression than EVA at dosage
≥ 200 ppm (Table 1).
Comb polymers are generally synthesized from one of two classes of monomers, (meth)
acrylate ester, or maleic anhydride or both. (Meth) acrylate ester polymers, which are
often abbreviated as P(M)A, are widely reported as additives for waxy
crudes.[47,50,52,55,62,86–89] The molecular structure of P(M)A is shown in Figure 11 b. Alkyl
side chains interact with paraffin waxes while ester groups interrupt wax crystal growth.
P(M)A polymers with paraffin side chain lengths ≥ 18 perform well as wax inhibitors and
pour point depressants for waxy crude oils.[5,47,87-89] In many cases, (meth) acrylate ester
is copolymerized with other monomers such as vinyl acetate[19], acrylonitrile[22] and
vinylpyridine[62], to facilitate interaction with paraffin waxes and asphaltenes. Maleic
anhydride (MA) is an additional monomer used to prepare comb copolymers (Figure 11
c). Alkyl side chains are introduced in MA structure by esterification or amidation with
long chain alcohols or alkylamine. MA is often copolymerized with (meth) acrylate
ester,[36,44,65,69,90] α-olefin[41,42,70] and styrene[43,58,91] because MA does not easily self-
polymerize. In addition, n-cinnamates-co-n-hexadecylmaleimidecopolymers[92] and
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octadecyl acrylate-cinnamoyloxy ethyl methacrylate copolymer[93] are also reported as
additives for waxy crude oils.
4.3 Nano-Hybrid Pour Point Depressants
Although traditional polymeric pour point depressants are widely used in pipeline
transport of waxy crudes, several limitations apply: (a) limited pour point depression
effectiveness on high waxy crude oils; (b) effectiveness may depend on crude
composition, thermal and shear history; (c) competitive adsorption in conjunction with
heavy polar colloidal components may reduce the effectiveness; (d) limited applicability
for micro-crystalline waxes containing branched and cyclic components; (e) static long
term stability of treated crudes may not satisfy transport requirements due to
sequestration or depletion processes.
Nanoparticles exhibit potential applications in polymer modification due to unique size,
high surface and quantum tunneling effects. Research has been performed[94,95] on
preparation of polymeric nano-composites via dispersion of nanoparticles into polymer
phase. Compared with pure polymers, nanocomposite properties such as mechanical and
thermal stability, abrasion resistance and tenacity are greatly improved due to
introduction of dispersed nanoparticles. Recently, Zhang et al.[96,97] prepared nanohybrid
pour point depressants based on the traditional polymeric pour point depressants and
nanoparticles. It was found that viscosity/pour point reduction, shear resistance, and
crude flowability with nano-hybrid pour point depressants are much better than with
traditional EVA (Table 2).[96,97] A further work is required to elucidate the mechanism of
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nano-hybrid pour point depressants as well as to prepare new nano-hybrid pour point
depressants with optimal effectiveness.
5. FACTORS INFLUENCING THE EFFECTIVENESS OF POLYMERIC WAX
INHIBITORS AND POUR POINT DEPRESSANTS
5.1 Effect Of Molecular Structure Of Polymeric Additives On Effectiveness

5.1.1 Crystalline-Amorphous Copolymers
Ashbaugh et al.[25] studied the effect of PE-PEP additives of varying PEP brush length (5
and 11 K) on yield stresses of straight chain paraffin gels (ranging in length from 24 to 36
carbons) in decane. The location of the yield stress minimum with respect to polymer
addition depended on the molecular weight of the paraffin and the PEP brush length. For
PEB polymers, several workers[38,53] demonstrate that these copolymers are selective in
paraffin-modification capacity, as governed by the crystalline degree which may be tuned
by the number ‘n’ of ethyl side branches per 100 backbone carbon atoms. Ashbaugh et
al.[38] report the effect of PEB-n (n is in the range of 7.5~15) on model oil rheology. It is
found that copolymers with the highest crystalline tendency are more efficient for heavier
wax molecules while the less crystalline copolymers are more efficient for lighter waxes.
Radulescu et al.[53] identify two mechanisms of PEB polymer-paraffin interaction: on the
one hand, co-crystallization of paraffin and copolymer in thin platelets occurs as a
consequence of a good match between self-assembling properties of the investigated
polymer/paraffin pairs (PEB-7.5/C36 and PEB-11/C24); on the other hand, primordial
polymer aggregates act as a template for subsequent paraffin crystallization when the
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polymer exhibits a higher self-assembling point (PEB-7.5/C24) than the paraffin. Both
mechanisms are found for the PEB-7.5/C30 mixture.
5.1.2 EVA Copolymers
Machado and lucas[16] investigate the performance of EVA as pour point reducer and
organic deposition inhibitor. The authors find that the highest VA content (within the
range analyzed, 28–41 wt%) exhibited the best inhibition performance against organic
deposition. In another investigation[79], the authors evaluate the influence of VA content
of EVA on viscosity and pour point of a Brazilian crude oil. Pour point results reveal that
EVA with 30wt% VA content is most effective. In addition, the molecular weight and
polydispersity of EVA also played an important role in pour point depression. Ashbaugh
et al.[32] studied interactions between paraffin and EVA of various ethylene content in
decane. At high concentrations, ethylene-poor EVA altered the wax crystal habit more
effectively than ethylene-rich EVA. The ethylene-rich EVA grade seemed to form more
wax crystals at low concentrations. Based on molecular dynamic simulation, Wu et al.[45]
deduced that side chains introduced by propylene facilitate the affinity between the EVA-
type molecules and alkanes within the wax plane. Yang et al.[46] ascertained that
rheological improvement of waxy crude oils is obtained for EVA with a VA content of
approximately 28 wt.%. The influence of molecular weight on EVA effectiveness was
relatively small.
5.1.3 Comb Polymers
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Alkyl side chain length is a crucial factor influencing the effectiveness of comb
polymeric wax inhibitors and pour point depressants. Yang et al.[46] evaluate the pour
point depression effectiveness of polyacrylates with various alkyl side chain lengths (PA-
14, PA-16, PA-18, PA-22) on waxy crude oils. PA-18 and PA-22 show good efficacy as
PPDs for waxy crude oils. Wang et al.[49] investigate the effect of polymethacrylate on the
WAT and WDT (wax dissolution temperature) of model paraffin compounds (n-
C24H50(C24) and n-C36H74 (C36)) in n-decane (C10) solutions. Polymethacrylate with the
longest alkyl side-chains (C18) exhibits the most effect on suppressing WAT and
increasing WDT of the binary mixtures. Soldi et al.[88] also observe that polymethacrylate
with C18 alkyl side-chains exhibit the best pour point depression effectiveness on diesel
oils. Al-Sabagh[3] synthesized POMA and found that POMA with alkyl side chain length
C22 shows optimum pour point depression effectiveness. In general, the alkyl side chain
length of comb-type wax inhibitors and pour point depressants should be compatible with
the average length of paraffin waxes in oils to ensure the effectiveness of wax inhibitors
and pour point depressants.
Molecular weight also influences the effectiveness of comb polymeric wax inhibitors and
pour point depressants. Borthakur et al.[98] prepared a number of alkyl fumarate-vinyl
acetate copolymers having a wide range of molecular weights. Additive performance
depends on the polymer Molecular weight. The highest molecular weight copolymers are
most suited for crude oils with a broad range of normal paraffins and a lower mean
carbon number. Addition of the lowest molecular weight copolymer resulted in the best
efficacy for crude oils containing a narrow range of normal paraffins, with a higher mean
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carbon number. Intermediate molecular weight copolymers are best suited for crude oils
containing a broad range of normal paraffins and a higher average carbon number.
Introduction of polar groups within the comb polymer structure may enhance
effectiveness as wax inhibitors and pour point depressants.[86] However, excess content of
polar groups in comb polymers may cause deterioration of effectiveness. Zhang et al.[99]
improved the pour point depression effectiveness of polyacrylate polymer by introducing
large aminate groups within the polymer structure. Farag[93] prepared
poly(cinnamoyloxyethyl methacrylate-co-octadecyl acrylate) (CEMA-ODA) comb
polymers and evaluated effectiveness as PPDs. CEMA-ODA copolymer with a molar
ratio of 1:3 shows excellent ability in dispersing wax crystals and improve flow rheology
of tested crude oils. Xu et al.[17] studied the effect of polar/nonpolar moieties in comb-
type copolymers on cold flowability and paraffin crystallization of waxy oils. The
efficiency of comb-type poly(maleic alkylamide-co-a-octadecene) copolymers (MACs)
was found to correlate to the ratio of polar/nonpolargroup (r). MAC with r = 0.4, is more
effective than other ratios in improving flowability of waxy oil.
5.2 Effect Of Crude Oil Composition On The Effectiveness Of Polymeric Additives
5.2.1 Paraffin Waxes
The composition of paraffin waxes great influence of efficiency of wax inhibitors and
pour point depressants. García et al.[100,101] discovered that heavy n-paraffins (n-
C24+paraffins) were deleterious for the efficiency of a paraffin inhibitor. The authors[102]
also studied the effect of cyclic and branched alkanes on the activity of commercial
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crystal modifier and found that high concentrations of cyclo+branched alkanes enhanced
the activity of the crystal modifier. Wang et al.[87] investigated the effect of selected wax
inhibitors on paraffin deposition. Most commercial wax inhibitors tested reduce
deposition of low molecular weight paraffins (C34 and below), while exhibiting little
effect on deposition of high molecular weight paraffins (C35-C44).

5.2.2 Asphaltenes
Asphaltenes are regarded as natural wax inhibitors and pour point depressants in crude
oils.[71–75] The presence of asphaltenes has potential influence on polymeric wax
inhibitors and pour point depressants, interfering with inhibitor crystal modification
mechanism. Oliveira et al.[80] studied the effect of asphaltenes on an EVA-derived wax
inhibitor named ODI. The ODI presented some efficiency in pour point reduction but, in
the presence of asphaltenes, this efficiency was significantly enhanced. Soni et al.[69]
investigated relations between four comb-type PPDs and asphaltenes. The additive (18-
ABA) attracts asphaltenes on the surface of wax crystals and performs better than other
additives, demonstrating the impact of a complex and synergistic inhibition mechanism.
Ni et al.[65] synthesized four modified maleic anhydride copolymers and found that the
copolymer with benzene groups showed better efficiency as a pour point depressant. The
benzene groups facilitate interactions between PPDs and asphaltenes, thus improving the
efficiency of pour point depressants. Li et al.[17,41] also suggested that polar groups of
comb polymers may interact with asphaltenes, benefitting rheological improvement of
waxy crude oils.
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5.3 Effect Of Pipeline Transportation Conditions On The Effectiveness Of
Polymeric Additives
During long-distance pipeline transportation processes, waxy crude oils are invariably
exposed to continuous shearing (in pumps and near the inner pipeline wall) as well as
thermal changes. In addition, waxy crude oils are maintained quiescently in pipelines
during long-term shutdowns. It is necessary to predict the effects of thermal conditioning,

shear conditioning and aging on the efficiency of polymeric wax inhibitors and pour
point depressants.
Jenings et al.[103] studied the effect of shear on the performance of wax inhibitors through
coldfinger method. The inhibition effectiveness of wax inhibitors increases consistently
with increasing shear. Tinsley et al.[78] also deduced the same conclusion when they
investigated the effect of wax inhibitors on wax deposition from model crude oils using a
novel laboratory cell. The effect of shear on pour point depressants is a complicated
phenomenon. At temperatures above the WAT, shear has little impact on PPDs
effectiveness. However, when PPDs-beneficiated crude oils are sheared below the wax
appearance temperature (especially in the temperature range of the wax-crystallization
peak), shear results in a decline in the effectiveness of the PPDs.[63,104,105] This result may
be understood in the context of crystal-crystal bonds, which when ruptured by forced
shearing do not reform. Hence, shear-stabilized low temperature waxy crude oils do not
show a benefit from chemically modulated interfacial repulsion.
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Repetitive heating at relatively low temperature (below the first heating temperature)
often causes degradation of the effectiveness of PPDs, likely due to complex
sequestration and depletion processes, and the degradation becomes worse with the
lowering of reheating temperature.[104,105] The cooling rate also significantly influence the
effectiveness of PPDs: increasing cooling rate may weaken the interactions between
PPDs and paraffin waxes, thus reducing the effectiveness of PPDs. The cooling rate
dependence of PPDs efficacy likely points to a diffusion limited time dependent
adsorption process for PPD molecules at wax interfaces.
Chanda et al.[2] investigate storage stability of PPDs treated crude oils over a period of 7
days. Crude oil viscosity increased considerably with time after room temperature storage,
demonstrating unsatisfactory long-term stability of treated crude oils. Ostwald ripening
processes are likely attributable to the aging effects. When polymeric pour point
depressants are used with the aid of stable nanoparticles, long-term stability and shear
stability could be well improved.[97]
6. CONCLUSIONS
In this review article, the structural character, the type, the basic mechanisms of
polymeric wax inhibitors and pour point depressants, and factors influencing the
effectiveness of polymeric wax inhibitors and pour point depressants are presented.
Most polymeric wax inhibitors and pour point depressants contain nonpolar groups,
which interact with paraffin waxes, and polar groups, which interrupt the growth of wax
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crystals. An exception is crystalline-amorphous copolymers, which are composed of two
nonpolar parts: a crystalline part (PE) and an amorphous part (PB or PEP).
There are four basic interactions between polymeric wax inhibitors and pour point
depressants and paraffin waxes, which can be described as nucleation, adsorption, co-
crystallization, and solubilization. Based on the interactions, polymeric wax inhibitors

and pour point depressants greatly impact the microscopic morphology of wax crystals
and aggregates, thus effectively inhibiting wax deposition and improving crude oil
rheology. The presence of asphaltenes has significant impact on the morphology of wax
crystals modified by polymeric wax inhibitors and pour point depressants.
Polymeric wax inhibitors and pour point depressants may be categorized into crystalline-
amorphous copolymers, EVA copolymers, comb polymers and nano-hybrids. Crystalline-
amorphous copolymers self-assemble into micelle-like structure with crystalline cores
and amorphous brushes surrounding the cores. The VA content governs the
crystallization ability and interaction mechanism of EVA copolymers. Alkyl side chain
length is a crucial factor influencing the effectiveness of comb polymers. Nano-hybrid
pour point depressants may exhibit improved efficacy, thermal stability and shear
stability due to introduction of nanoparticles in polymer phase.
Molecular structure parameters, such as functionality ratios, length of alkyl side chains
and molecular weight, impact the effectiveness of polymeric wax inhibitors and pour
point depressants. The oil composition, wax structure and distribution, and presence of
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asphaltenes also affect the performance of polymeric wax inhibitors and pour point
depressants. Increasing shear improves the effectiveness of wax inhibitors but reduces the
effectiveness of pour point depressants. Reheating at low temperatures and long-term
aging also deteriorate the effectiveness of pour point depressants.

ACKNOWLEDGMENTS
This work was financially supported by National Natural Science Foundation of China
(51204202) and Natural Science Foundation of Shandong Province of China
(ZR2012EEQ002).
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TABLE 1 Pour Points of CQ Crude Oil Treated withPolymeric Additives and
Commercial EVA[65]
Pour-point depression (°C)
Addictive
concentration POM POMO POMN POMB EVA
(ppm)
50 3 5 5 9 8
100 5 8 9 12 12
200 6 8 10 16 9
300 9 12 13 19 8
500 9 12 13 19 8
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TABLE 2 Comparison of the viscosity depressing effects of EVA and nanohybrid
PPDs[96]
apparent viscocity at 25°C (mPa s)
Samples Loading Time Pour point

10 s-1 20 s-1 30 s-1 40 s-1 50 s-1
(g/t) (d) (°C)
Crude oil 0 0 4333 2420 1978 1366 771.1 30.5

Crude oil + EVA 50 0 133.3 127.4 124.2 120.6 117.7 23.0
PPD
Crude oil + EVA 50 10 193.8 184.3 177.8 172.4 168.6 24.5
PPD
Crude oil+ 50 0 103.1 101.4 99.8 98.4 97.2 16.5
nanohybrid EVA
PPD
Crude oil+ 50 10 113.5 109.2 109.6 108.8 108.8 17.0
nanohybrid EVA
PPD
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FIGURE 1 Side view of the morphology of paraffin crystal.[45]
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FIGURE 2 Effect of Poly(Ethylene-Vinyl Acetate)[46] (a) and Polyacrylate[47] (b) on
crystallization ability of different waxy crude oils.

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FIGURE 3 Optical micrographs of 4% C36 with various amount of EVA-ss: (a) 4% C36,
(b) 0.007% EVA-ss, (c) 0.097% EVA-ss, (d) 0.185% EVA-ss, (e) 0.324% EVA-ss, and (f)
0.827% EVA-ss.[32]
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FIGURE 4 Crystallization morphology of model waxy oil containing0.1 wt % FIs with
various degrees of imidization derived fromSMA2000P with 37.9% MAH fraction.[43]

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FIGURE 5 Effect of EVA addition on morphology of wax crystals in waxy crude oils. (a)
Changqing waxy crude oil, undoped, (b) Changqing waxy crude oil, Doped, (c) Qinghai
waxy crude oil, undoped, (b) Qinghai waxy crude oil, Doped.[46]
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FIGURE 6 Microscopic images of wax crystals of oil 1 at 16 . The fractal dimension of
wax crystals is as follows: (a) 1.3848 and (b) 1.5150.[63]

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FIGURE 7 Photomicrographs of (a) virgin crude oil and (b) crude oil with 500 ppm
concentration of POMB at 25 °C.[65]

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FIGURE 8 Diameter distribution curves of wax crystals from Africa oil and Domestic oil
with and without OMA added: (1) Africa oil+ 300 µg/ g OMA, (2) Domestic oil+ 400 µg/
g OMA,(3) Africa oil, (4) Domestic oil.[67]

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FIGURE 9 Photomicrographs of wax separated from KT crude oil (A) without any
additive and (B) with 1000 ppm of 22-OMR.[70]

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FIGURE 10 Generic structure of the PE-PEP aggregates. The crystallization of the PE
forms extended (R) platelets, the PEP hairs form brushes on both sides.[29]
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FIGURE 11 Molecular structure of EVA copolymers (a), poly(meth) acrylate ester (b),
and (c) monoester of maleic anhydride-(meth) acrylate ester copolymer. R = long alkyl
chain, R′ = H or CH3.
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Article in Journal of Dispersion Science and Technology · March 2014

Fei Yang Yansong Zhao

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Journal of Dispersion Science and Technology

Polymeric Wax Inhibitors and Pour Point Depressants

To link to this article: http://dx.doi.org/10.1080/01932691.2014.901917

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Received 17 February 2014; Accepted 4 March 2014.

depressants comprise an effective preventative measure. In this paper, the structural

character, functionality, and mechanisms of the polymeric additives targeting paraffin

exception of crystalline-amorphous copolymers. Via nucleation, adsorption, co-

crystallization and solubilization interactions, polymeric additives alter the morphology

polymeric additives fall into the categories of crystalline-amorphous copolymers,

influencing polymeric efficacy include molecular structure, fluid composition, and

pipeline transport conditions.

KEYWORDS: Wax inhibitor; pour point depressant; interaction mechanism;

microscopic morphology; influencing factors.

contain substantial amounts of petroleum wax (normally ≥ 5 wt%), which complicates

wax.[6,7] Macro-crystalline wax is composed of primarily low molecular weight n-

alkanes (C16-C40), and generally crystallizes as needles or platelets. Micro-crystalline

of large-scale crystals, micro-crystalline paraffin waxes normally precipitate as small

amorphous particles and do not exhibit distinct crystallization regime.

WAT and a negative radial temperature gradient is present.[8–10] Deposition phenomena

severe or synergetic conditions, adversely impacting pipeline operation. Periodic pigging

or chemical/thermal dissolution is required to remediate wax deposition, renewing free

costly and should be minimized.[11] In addition, large plate-like or needle-like wax

crystals form house-of-cards structures and impart complex non-Newtonian

flow reduces transportation safety and efficiency. Maintaining thermal transport

conditions above pour point is energy consuming, resulting in excess environmental

influencing polymer efficiency are also discussed.

2. STRUCTURAL CHARACTER OF WAX INHIBITORS AND POUR POINT

crystallization.[3,18–20] Polar moieties, such as esters, vinyl acetates, maleic anhydrides or

formation of large wax crystals.[21–23] In addition, steric and entropic repulsion

mechanisms are highly relevant but not well documented.

An exception to the standard structural character are crystalline-amorphous

pour point depressants, such as ethylene/butene copolymers (PEB)[25,26], are composed of

a crystalline nonpolar group (polyethylene) and an amorphous nonpolar group

(polybutene). The crystalline groups form crystalline cores surrounded by amorphous

3. MECHANISM OF WAX INHIBITORS AND POUR POINT DEPRESSANTS

Crystallization is a physical process in which such a solid ordinate structure is produced

causing network formation.

3.2 Mechanism Of Polymeric Wax Inhibitors And Pour Point Depressants

macroscopic rheology of waxy crude oils.

3.2.1 Interactions Between Polymeric Additives And Paraffin Waxes

According to Gilby[19] and Atta[20], a combination of interactions between polymeric wax

co-crystallization, and solubilization are relevant.

and pour point depressants self-assemble into micelle-like aggregates exhibiting a

number of sub-critical size wax nuclei (so-called polynucleation). Partially shielded

Adsorption[34–37] and co-crystallization[38–43]. At temperatures near or below the

molecules or adsorb on growing surfaces of precipitated wax crystals. Incorporation of

inhibiting wax deposition and improving flowability. Molecular dynamic (MD)

facilitating the spiral growth mechanism in the perpendicular direction to (001)

more integrity (such as spherulitic-like).

in WAT is quite limited (see figure 2).

3.2.2 Mechanism Of Polymeric Wax Inhibitors And Pour Point Depressants On

Model Waxy Oils

compositional simplicity and definition.[51] The mechanism of polymeric wax inhibitors

ray diffraction (XRD)[16,17,41,52], light scattering[53,54], zeta potential[55,56],

thermodynamics[40,48], and microscopy[32,41-43,57,58]. Based on nucleation, adsorption and

plate-like or needle-like to ordered shapes such as dentric-like or spherulitic-like (see