This article was downloaded by: [Universite Laval]

On: 07 July 2014, At: 15:44

Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered
office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH, UK

Petroleum Science and Technology

Publication details, including instructions for authors and
subscription information:
http://www.tandfonline.com/loi/lpet20

A Study on the Interaction of Crude

Oil Waxes With Polyacrylate Pour Point
Depressants by Monte Carlo Simulation
a ab a a a
Z. Chen , X. Wang , H. Zhang , C. Yang & H. Shan
a
State Key Laboratory of Heavy Oil Processing, College of Chemical
Engineering of China University of Petroleum (East China), Qingdao,
China
b
Centre for Bioengineering and Biotechnology of China University of
Petroleum (East China), Qingdao, China
Published online: 01 Jul 2014.

To cite this article: Z. Chen, X. Wang, H. Zhang, C. Yang & H. Shan (2014) A Study on the Interaction
of Crude Oil Waxes With Polyacrylate Pour Point Depressants by Monte Carlo Simulation, Petroleum
Science and Technology, 32:17, 2151-2157, DOI: 10.1080/10916466.2013.769571

To link to this article: http://dx.doi.org/10.1080/10916466.2013.769571

PLEASE SCROLL DOWN FOR ARTICLE

Taylor & Francis makes every effort to ensure the accuracy of all the information (the
“Content”) contained in the publications on our platform. However, Taylor & Francis,
our agents, and our licensors make no representations or warranties whatsoever as to
the accuracy, completeness, or suitability for any purpose of the Content. Any opinions
and views expressed in this publication are the opinions and views of the authors,
and are not the views of or endorsed by Taylor & Francis. The accuracy of the Content
should not be relied upon and should be independently verified with primary sources
of information. Taylor and Francis shall not be liable for any losses, actions, claims,
proceedings, demands, costs, expenses, damages, and other liabilities whatsoever or
howsoever caused arising directly or indirectly in connection with, in relation to or arising
out of the use of the Content.

This article may be used for research, teaching, and private study purposes. Any
substantial or systematic reproduction, redistribution, reselling, loan, sub-licensing,
systematic supply, or distribution in any form to anyone is expressly forbidden. Terms &
Conditions of access and use can be found at http://www.tandfonline.com/page/terms-
and-conditions
 Petroleum Science and Technology, 32:2151–2157, 2014
Copyright 
C Taylor & Francis Group, LLC
ISSN: 1091-6466 print / 1532-2459 online
DOI: 10.1080/10916466.2013.769571

A Study on the Interaction of Crude Oil Waxes

With Polyacrylate Pour Point Depressants by
Monte Carlo Simulation
Z. Chen,1 X. Wang,1,2 H. Zhang,1 C. Yang,1 and H. Shan1
1
State Key Laboratory of Heavy Oil Processing, College of Chemical Engineering of China
University of Petroleum (East China), Qingdao, China
Downloaded by [Universite Laval] at 15:44 07 July 2014

2
Centre for Bioengineering and Biotechnology of China University of Petroleum (East China),
Qingdao, China

The interaction of crude oil waxes with polyacrylate pour point depressants (PPDs) bearing different
structures was investigated in detail by Monte Carlo simulation, using n-hexadecane as representative
component of wax crystal. It was demonstrated that during wax precipitation the mixed energy was low
when the side chain length of polyacrylate was close to that of n-hexadecane. Meanwhile, the mixed
energy between polyacrylate PPDs and n-hexadecane was shown to be closely related with the polarity
of building blocks of polyacrylate. Our results indicated that it is easier for polyacrylate polymers with
polar building blocks to interact with n-alkanes, which would effectively inhibit wax-crystal precipitation
and improve crude oil low-temperature fluidity. The simulation results provide with some knowledge for
guiding the molecular design and synthesis of polyacrylate PPDs.

Keywords: crude oil waxes, Monte Carlo simulation, n-hexadecane, polyacrylate, pour point depressants

1. INTRODUCTION

Wax precipitation from crude oils is a major problem faced by the petroleum industry during
production, processing and transportation. When the temperature approaches the pour point, the oil
may gel completely and causing the cold flow problems such as blockage of flow pipes or production
lines (Derakhshan and Shariati, 2012). In order to improve the low-temperature flowability of crude
oils, polymer additives, such as vinyl acetate copolymer, acrylate copolymer, and their derivatives,
have been widely used as so-called pour point depressants (PPDs). Among all PPDs, the polyacrylate
(PA) was widely used because of its low cost and strong competence (Chastek, 2011; Neveu et al.,
2012).
In general, inhibition of wax crystallization has been considered to occur in the presence of PPDs
by nucleation, co-crystallization, or adsorption. Many theoretical and experimental studies have
been put forward to explain the action mechanism of PPDs for the control of wax crystallization
(Zhang et al., 2003; Ashbaugh et al., 2005; Marie et al., 2005). The molecular design of PA is
mainly based on adsorption co-crystallization theory (Mohamad, et al., 2012). However, it should

Address correspondence to H. Shan, No. 66, Changjiang West Road, Huangdao District, Qingdao, China 266580. E-mail:
tingyvxuan@126.com
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/lpet.

2151
 2152 Z. CHEN ET AL.

be pointed out that a universal explanation for the role of PA has not been satisfactorily achieved.
The choice of acrylate monomer structure only relies on empirical and semi-empirical methods.
Thus, much work of trying different structures is needed to obtain a competent PA PPD. This
approach is time-consuming, resource-wasting and in low efficiency (Mohamad et al., 2012). Up
to now, few simulation methods have been reported to guide the molecular design of PA PPD.
The interaction between the PPDs and the wax is still an interesting theme of scientific research at
present.
In this work, Monte Carlo simulation was employed to study the interaction of crude oil waxes
and PAs with different structures, such as acrylate monomer structure, secondary monomer polarity
and the copolymer fragments formed by the two monomers, with the goal of guiding the molecular
design and synthesis of PA PPDs.
Downloaded by [Universite Laval] at 15:44 07 July 2014

2. EXPERIMENTAL

2.1 Theoretical Model

From the point of view of petroleum chemistry, the main components of waxes are n-alkanes whose
carbon number is more than 16, especially C16–C36 hydrocarbons (Chen et al., 2010; Dai et al.,
2011). Due to the complexity of crude oil systems, n-hexadecane was used as the representative
component of wax-crystal to investigate the interaction between waxes and PAs with the side chain
carbon number of acrylate monomer, as well as different polar fragments. The lowest energy state of
the interaction between n-hexadecane and the copolymer of octadecyl acrylate with maleic anhydride
was shown in Figure 1, which was predicted by Monte Carlo simulation.
Dreiding force field was used to optimize the energy of the molecular model system that is
composed of the building block of PA PPDs and the hydrocarbon fraction in crude oil. Meanwhile,
density functional theory (DFT) was used to optimize the structures of chosen building block and
hydrocarbon fraction, in which the building block took the no mutual collision pattern of initial
and ending atoms. The optimization method is GGA-PBE function along with DNP basis set. Full
electronic method was employed to process atomic nucleus. DIIS and smearing methods were
employed to accelerate the convergence of self-consistent field. The chain of random self-avoiding
walks (SAW) on 3D cubic lattice was also adopted in simulation. The model is composed of the
building block of PA PPDs and n-hexadecane. When these two components are a lattice apart, they
are regarded to form a close contact and thus denoted as a pair of interaction energy. In simulation,
one million molecular interaction conformations were collected and the interaction energy of every
pair of conformations was calculated. One hundred conformations with the lowest energy were

FIGURE 1 Ball and stick model of the interaction between copolymer of octadecyl acrylate with maleic anhydride
and n-hexadecane obtained from Monte Carlo simulation.
 INTERACTION OF CRUDE OIL WAXES 2153

returned and analyzed. The mixed energy (Emix) of the two components can be derived from
Eq. (1):

(1)
In which Zij stands for the conformation numbers of molecule j around molecule i and Eij stands for
the interaction energy between molecule i and j.

3. RESULTS AND DISCUSSION

3.1 Influence of the Side Chain Carbon Number of Acrylate Monomer

Downloaded by [Universite Laval] at 15:44 07 July 2014

Monte Carlo simulation method enables rapid calculation of the interaction energy between PA unit
and different wax-crystal fractions in the absence of any experimental data, thus providing theoretical
basis for developing universal PPDs (Wang et al., 2000). Herein, Monte Carlo simulation was used to
investigate the interactions in the acrylate (AA)/n-hexadecane or methacrylate (MAA)/n-hexadecane
system. The influence of the side chain carbon number on the interaction energy between acrylate
monomer of PA PPDs and hexadecane was studied and the results were shown in Figure 2.
It can be seen from Figure 2 that the mixed energy between acrylate monomer and hexadecane
decreased first and then increased with the side chain carbon number increasing from 1 to 20.
When the side chain carbon number varies between 14 and 18, the interaction energy between
acrylate monomer and hexadecane was lower than those of other acrylate monomer; the interaction
energy was the lowest when the side chain carbon number is 16. The interaction energy between
acrylate monomer and hexadecane was always lower than that of methacrylate. It can be seen from
the above results that when the side chain carbon number of acrylate or methacrylate is close to
n-alkane carbon number, their compatibility becomes better and it becomes easier for acrylate or
methacrylate monomer to go into wax-crystal lattice.
Based on the view that the PPDs should have both lipophilic group with a certain length and
hydrophilic group, the alkyl chain length of PAs is crucial for lowering pour point. It is widely

FIGURE 2 Emix between hexadecane and MAA or AA with different side carbon numbers.
 2154 Z. CHEN ET AL.

believed that only PAs with side chain longer than 12 carbons can work better (Song et al., 2006).
Yu et al. (2006) synthesized the copolymer of long chain alkyl acrylate with maleic anhydride to
improve the low-temperature fluidity of crude oil with bulk wax. Our simulation results demonstrated
the previous points. Thus, the acrylate or methacrylate monomer with side chain number close to
the averaged carbon number of crude oil wax-crystal should be chosen in the structural design of
PPDs (Zhang et al., 2004). In the light of the interaction energy divergence between acrylate and
methacrylate monomer when mixed with hexadecane and the better compatibility between acrylate
monomer and hexadecane, acrylate-like monomer should be the first choice in the structural design
of PPDs.

3.2 Influence of Building Block Polarity

Downloaded by [Universite Laval] at 15:44 07 July 2014

Polar building block in PPD can effectively inhibit wax-crystal growth upon adsorption and make
wax-crystals mutually exclusive, thus improving the dispersity, stability, and low-temperature flu-
idity of the whole system (Wu et al., 2005). The interaction of different polar monomers, such as
styrene (ST), vinyl acetate (VA), maleic anhydride (MA), acrylonitrile (AN), acrylamide (AM), with
hexadecane was studied at 283 K. Figure 3 shows the mixed energies of different polar building
blocks with hexadecane.
According to Figure 3, it is obvious that the mixed energies of different polar building
blocks with hexadecane varied dramatically. The magnitude order of the mixed energies is:
ST>VA>MA>AN>AM, while the order of polarity is reverse. With the building block polarity
increasing, the compatibility between building block and hexadecane became worse and it became
more difficult for PPDs to go into wax-crystal lattice. When alkyl chains adsorb on wax-crystal or
crystallize with wax-crystal, the polar group would inhibit crystal growth and change its growth
pattern, and thus lowering pour point. The crystalline lattice structure of wax gels with and without
PPDs had been studied by Srivastava et al. (1995) using XRD. It is reported that the PPDs additive
provide the necessary energy to paraffin molecules to hastened the development of hexagonal planes.
The similar phenomenon was found by Zhang et al. (1995). The structure of waxes was transformed
from orthorhombic into hexagonal phase.

FIGURE 3 Emix between different building blocks and hexadecane.

 INTERACTION OF CRUDE OIL WAXES 2155

Polar building block in PPDs can effectively inhibit wax-crystal growth upon adsorption and
make wax-crystals mutually exclusive, thus improving the dispersity, stability, and low-temperature
fluidity of the whole system. Hence, the polar building block is necessary for PPDs to effectively
inhibit wax-crystal from forming net structure.

3.3 Influence of Polymer Types

According to the mixed energies of different polar monomers with hexadecane, it can be seen that
monomer polarity has a notable effect on wax-crystal stability. As a matter of fact, PPD is usually a
polymer composed of different building blocks (Elsharkawy et al., 2000). In this work, representative
polymer fragments composed of acrylate with different polar building blocks were selected and the
interaction of these polymer fragments with hexadecane was simulated. The simulation results are
Downloaded by [Universite Laval] at 15:44 07 July 2014

as shown in Figure 4.
It can be seen from Figure 4 that with polarity increasing, the mixed energies decreased first
and then increased between the polymer fragments of stearyl acrylate with different polar building
blocks and hexadecane. Furthermore, the mixed energies between the polymer fragments bearing
the VA, MA, and AN building blocks and hexadecane are lower than those of the polymer fragments
bearing the other two building blocks.
Chen et al. (2010) studied the effect of PPDs on wax precipitation from the point of view
of thermodynamics and crystallography by differential scanning calorimetry (DSC) and X-ray
diffraction (XRD). The experimental results showed that the PPDs can have an effect on the amount
of precipitated waxes. From the comparison of mixed energy, it is obvious that polymer fragments
with quite high or low polarity are not favorable for the interaction between PPDs and waxes. PPDs
do not completely prevent the wax from precipitating, but just shift the precipitation toward a lower
temperature (Wang and Zhao, 2001).
In general, the interaction of every constituent fragment with wax-crystal should be consid-
ered in the structural design of PPDs (Chen et al., 2009; Aiyejina et al., 2011; Al-Sabagh et al.,
2012). Meanwhile, the overall performance should also be considered. According to our results, the

FIGURE 4 Emix between different copolymer fragments and hexadecane.

 2156 Z. CHEN ET AL.

introduction of VA, MA, or AN polar building block facilitates the interaction between PPDs and
crude oil wax-crystal.

4. CONCLUSIONS

This work studied the interaction of crude oil waxes and PAs with different structures using Monte
Carlo simulation method. According to the simulation results, some important principles of guiding
the PA PPDs molecular design have been identified. The waxes compatible fragments of PPDs should
consist of acrylate monomers with side chain carbon numbers close to the averaged carbon number
of crude oil waxes. Besides, the waxes repellent fragments of PPDs should consist of building blocks
with strong polarity. Specifically, in the structural design of PPDs, the introduction of polar building
block in polyacrylate, such as vinyl acetate, maleic anhydride, and acrylonitrile, can effectively
Downloaded by [Universite Laval] at 15:44 07 July 2014

facilitate the interaction between PPDs and crude oil waxes.

REFERENCES

Aiyejina, A., Chakrabarti, D. P., and Pilgrim, A. (2011). Wax formation in oil pipelines: A critical review. Int. J. Multiphase
Flow 37:671–694.
Al-Sabagh, A., Sabaa, M., and Saad, G. (2012). Synthesis of polymeric additives based on itaconic acid and their
evaluation as pour point depressants for lube oil in relation to rheological flow properties. Egyptian J. Pet. 21:
19–30.
Ashbaugh, H. S., Guo, X., Schwahn, D., Prudhomme, R., Richter, D., and Fetters, L. (2005). Interaction of paraffin wax gels
with ethylene/vinyl acetate copolymers. Energy Fuels 19:138–144.
Chastek, T. Q. (2011). Improving cold flow properties of canola-based biodiesel. Biomass Bioenergy 35:600–607.
Chen, W. H., Zhang, X. D., and Zhao, Z. C. (2009). UNIQUAC model for wax solution with pour point depressant. Fluid
Phase Equilib. 280:9–15.
Chen, W., Zhao, Z., and Yin, C. (2010). The interaction of waxes with pour point depressants. Fuel 89:1127–1132.
Dai, X., Jia, Z., Li, G. (2011). The effect mechanism and research progress of crude oil pour point depressant. Oil Gas Stor.
Trans. 2:86–89.
Derakhshan, T., and Shariati, A. (2012). Prediction of wax precipitation temperature in petroleum reservoirs upon methane
injection. J. Pet. Sci. Eng. 98–99:1–10.
Elsharkawy, A., Al-Sahhaf, T., and Fahim, M. (2000). Wax deposition from Middle East crudes. Fuel 79:1047–
1055.
Marie, E., Chevalier, Y., Eydoux, F., Germanaud, L., and Flores, P. (2005). Control of n-alkanes crystallization by
ethylene–vinyl acetate copolymers. J. Colloid Interface Sci. 290:406–418.
Mohamad, S. A., Ahmed, N. S., Hassanein, S. M. and Rashada, A. M. (2012). Investigation of polyacrylates copolymers as
lube oil viscosity index improvers. J. Pet. Sci. Eng. 100:173–177.
Neveu, C., Sondjaja, R., Stöhr, T., and Iroff, N. (2012). Lubricant and fuel additives based on polyalkylmethacrylates. Poly
Sci: A Comprehensive Refer. 10:453–478.
Song, Z., and Liu, W. (2006). Experimental study on the solution polymerization of octodecyl acrylate. J. Xi’an Pet. Inst.
(Nat. Sci. Ed.). 21:70–73.
Srivastava, S., Tandon, R., Verma, P., Pandey, D., and Goyal, S. (1995). Phase transitions in middle-distillate waxes: effect of
a pour-point depressant additive. Fuel 74:928–931.
Wang, M., and Zhao, J. (2001). Pour point depressants for crude oil and its applications in China. Modern Chem. Ind.
21:58–61.
Wang, Y., Chen, Z., and Cheng, S. (2000). Computer simulation of miscibility of polystyrene and solvents system. Chin. J.
Colloid Poly. 18:24–29.
Wu, C., Zhang, J., Li, W., and Wu, N. (2005). Molecular dynamics simulation guiding the improvement of EVA-type pour
point depressant. Fuel 84:2039–2047.
Yu, H., Qi, B., Wang, L., Cao, Z., and Hu, Z. (2006). Synthesis of alcoholysis depressant and its application for diesel fuel.
Acta Pet. Sin. (Pet. Proc. Sect.) 22:91–96.
 INTERACTION OF CRUDE OIL WAXES 2157

Zhang, F., and Wang, B. (1995). Studies on the mechanisms involved in pour point depressant and viscosity deduction by
some pour point depressants/viscosity reducers. Oilfield Chem. 12:347–352.
Zhang, J., Wu, C., and Li, W. (2004). DFT and MM calculation: the performance mechanism of pour point depressants study.
Fuel 83:315–326.
Zhang, J., Wu, C., Li, W., Wang, Y., and Han, Z. (2003). Study on performance mechanism of pour point depressants with
differential scanning calorimeter and X-ray diffraction methods. Fuel 82:1419–1426.
Downloaded by [Universite Laval] at 15:44 07 July 2014