Petroleum Science and Technology

ISSN: 1091-6466 (Print) 1532-2459 (Online) Journal homepage: http://www.tandfonline.com/loi/lpet20

The development and evaluation of novel nano-

pour point depressant

Zhiwei Zhen, Guolin Jing, Zhengnan Sun, Chen Zheng & Wei Li

To cite this article: Zhiwei Zhen, Guolin Jing, Zhengnan Sun, Chen Zheng & Wei Li (2018)
The development and evaluation of novel nano-pour point depressant, Petroleum Science and
Technology, 36:3, 208-214, DOI: 10.1080/10916466.2017.1413388

To link to this article: https://doi.org/10.1080/10916466.2017.1413388

Published online: 26 Dec 2017.

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Download by: [Gothenburg University Library] Date: 12 January 2018, At: 04:55
 PETROLEUM SCIENCE AND TECHNOLOGY
, VOL. , NO. , –
https://doi.org/./..

The development and evaluation of novel nano-pour point

depressant
Zhiwei Zhen, Guolin Jing, Zhengnan Sun, Chen Zheng, and Wei Li
Provincial Key Laboratory of Oil & Gas Chemical Technology, College of Chemistry & Chemical Engineering, Northeast
Petroleum University, Daqing, China
Downloaded by [Gothenburg University Library] at 04:55 12 January 2018

ABSTRACT KEYWORDS
Chemical pour point depressant modification is an important means to reduce analytical methods;
pour point and viscosity of waxy crude oil. In recent years, the research on mechanism; Nano-pour
the modification of pour point depressants has made a great progress. This point depressants; wax
crystals; waxy crude oil
paper summarizes the types of novel nano-pour point depressants, prepara-
tion methods, evaluation methods, mechanism of action and influencing fac-
tors. The development of the pour point depressant and the future outlook
made a brief summary.

Due to the difference between the conditions, climate and oil composition of the various regions, the oil
processing will encounter various difficulties. Although some of the wax content and pour point were
not high, because of the low submarine temperature, the wax component of the crude oil were easily
crystallized to form a three-dimensional network structure and results in the crude oil viscosity increases
sharply. It may lead to the oil pipeline blockage or rupture.

1. The development of the novel chemical pour point depressants

Pour point depressant was mainly divided into traditional polymer, block polymer, comb polymer and
nano-pour point depressant.
Soni et al. (Soni H P and Bharambe D P. 2008) used α-olefin maleic anhydride copolymers reacted
with different esters and aromatic compounds to obtain four comb-like polymer pour point depressants
with different side chain functional groups. The effect of the four different types of pour point depres-
sants were evaluated using Indian Nada and Kosamba crude oil. The results showed a better pour point
depression for Kosamba crude oil which have more the number of aromatic groups in the side chain, but
the pour point depression to Nada crude oil were basically the same. Therefore, the pour point depres-
sion was not only related to the number and length of the side chain groups of the pour point depressant
itself, but also related to the type of the crude oil.
Novel chemical pour point depressants were mostly polymerized by small molecule compounds, and
then modified by other compounds to modify their side chains by changing the length of polymer side
chains, the number and type of functional groups to improve the pour point depression and its scope of
application. With the development of nanotechnology, researchers gradually introduced nanoparticles
into the preparation of pour point depressants. Norrman et al. (Norrman, J. et al. 2016) mixed the poly-
octadecylacrylate (POA) with the silica nanoparticles and then sonicated to prepare a new nano-pour
point depressant with different POA contents. The effects of the amount of the POA adsorbed on the
silica surface were analyzed by adding it to the waxy simulated oil.

CONTACT Guolin Jing jglxueshu@yeah.net Provincial Key Laboratory of Oil & Gas Chemical Technology, College of Chemistry
& Chemical Engineering, Northeast Petroleum University, Daqing, , China.
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/lpet.
©  Taylor & Francis Group, LLC
 PETROLEUM SCIENCE AND TECHNOLOGY 209
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Figure . Preparation of Nano-pour point depressant (Yao B. et al. ).

Yang et al. (Yang F et al. 2015a; Yao B et al. 2016) based on the good organic modification properties of
the nano-clay particles, the nano-clay was modified by quaternary ammonium salt cationic surfactant,
and the nano-composite pour point depressants were prepared by blending the modified organic nano-
clay with polyacrylate pour point depressant (Yao B et al. 2016) (Figure 1).
Yang et al. (Yang F et al. 2017) used methyltrimethoxysilane to synthesize different sizes of
polymethylsilses-quioxane (PMSQ) nanospheres in different rotational speeds. Schematic diagram of
the flow improving mechanism of PMSQ microspheres on waxy crude oil in Figure 2. Yao et al.
(Yao B et al. 2017) added the PMSQ to the crude oil, observing the waxy crystals structure in static
cooling condition and dynamic cooling condition. The wax crystals structure under the static cooling
condition were needle-like or rod-like particles. The wax crystal structure under the different dynamic
cooling conditions (Figure 3).

2. Analysis methods
At present, the characterization methods such as rheology, pour point, polarized light microscopy, dif-
ferential scanning calorimetry (DSC), infrared spectroscopy, X-ray diffraction (XRD) and nuclear mag-
netic resonance (NMR) were widely used in waxy crude oil modification (Yang F et al. 2009; Yang F et al.

Figure . Schematic diagram of the flow improving mechanism of PMSQ microspheres on waxy crude oil (Yang F et al. ).
 210 Z. ZHEN ET AL.
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Figure . Microstructure of the waxy oil: static cooling condition: undoped (a) and doped with PMSQ (b); dynamic cooling condition:
undoped (c) and doped with PMSQ (d) (Yao B et al. ).

2015b). The measurement and characterization of rheological parameters mainly include yield stress,
gelation point, apparent viscosity and shear rate curve and storage modulus, energy consumption mod-
ulus (Xu J et al. 2013). Yang et al. (Yang F et al. 2015a) analyzed the effect of the novel chemical pour point
depressants by rheological curves and found that the novel chemical pour point depressants significantly
reduced the yield stress, apparent viscosity and gelation point.
In order to study the adsorption status of the pour point depressant on the nanomaterials Jing et al.
(Jing G et al. 2017). used EVA and nano-silica compound, they used the quartz crystal microbalance
with dissipation monitoring (QCM-D) to study the adsorption of EVA onto silica surface from toluene.
Figure 4 shows the adsorption status of EVA. The dissipation increases when the EVA solution passed
over the silica surface. When the pure toluene solvent passed over the surface, we observed that there

Figure . QCM-D of the EVA adsorption on the silica surface from toluene (Jing G et al. ).
 PETROLEUM SCIENCE AND TECHNOLOGY 211
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Figure . Microscope images of the  wt % model oil in the (a) absence and (b) presence of the PPDs: (b)  ppm of EVA (VA = %),
(c)  ppm of N-SiPPD(), (d)  ppm of EVA(VA = %), (e)  ppm of N-SiPPD(), (f)  ppm of original SiO /EVA (VA = %),
(g)  ppm of N-SiPPD(), (h)  ppm of EVA (VA = %), (i)  ppm of N-SiPPD(), and (j)  ppm of EVA (VA = %)(Jing G et al.
).

was a mass loss on the surface, indicating that there were some loose adsorbent materials on the sensor,
and the dissipation was low (<1 × 10−6), indicating that EVA adsorbed on the surface of nano-silica
was rigid monolayer adsorption. The microscope images in Figure 5.

3. Mechanism
There was no uniform understanding for the mechanism of the pour point depressant. We widely rec-
ognized the mechanism has the following categories: nuclei, eutectic, adsorption, solubilization and
adsorption-eutectic (Gang C and Jie Z 2013) Holder et al. (Holder G A and Winkler J 1965) pointed
 212 Z. ZHEN ET AL.

out that the effect of the pour point depressant on the crude oil depends on the similarity between the
pour point depressant molecules and the wax molecules, they speculated that the interaction between the
similar parts of the pour point depressant molecules with the wax molecules make the wax molecules to
be folded or bent, and the non-similar parts adsorbed on the waxy crystal surface to hinder the growth of
the wax crystals. Jiang et al. (Jiang Q Z et al. 2006) used XRD analysis the wax crystal type of acrylic acid
dodecyl ester pour point depressant on the wax crystal type. They believed that the non-polar molecules
of the pour point depressant can produce eutectic effects with the wax molecules, so that the wax from
the rod to the sheet-like transformation and become more dispersed disorder.
Yang et al. (Yang F et al. 2015a; Yao B et al. 2016) explored the modification mechanism of nano-silica
/ poly octadecyl ester pour point depressants to waxy crude oil, it was found that the modified nano-silica
particles could not only control the pour point depressant aggregation state in the oil phase,but also can
be used as the crystallization core to change the wax crystal morphology. The adsorbed poly octadecyl
ester on the nanoparticles enhances the solubility of the wax molecules by eutectic, adsorption and solu-
bilization. The polar groups of the pour point depressants were adsorbed on the surface of the wax crys-
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tals to prevent the wax crystals aggregation, growth and form the three-dimensional network. Yang et al.
(Yang F et al. 2015c) used Changqing crude oil to evaluate the effect of the new EVA-montmorillonite
nano-pour point depressants and found that nano-compound pour point depressants can significantly
improve the low temperature fluidity of the waxy crude oil, it was due to solubilization and eutectic
effect. Wang et al. (Wang F et al. 2011) based on eutectic, adsorption theory consider that the addition
of nano-hybrid pour point depressant can increase the surface energy and the mutual exclusion between
wax crystals hinder the formation of gel network structure. Song et al. (Song X et al. 2016) analyzed the
effect of silica nanoparticles on the rheological properties of waxy crude oil. When there was no resin
and asphaltene, the silica particles were used as the crystallization core to increase the amount of wax
crystals, wax crystal size decreases and wax precipitation point rise. When the resin and asphaltene exist,
the silica particles have a good dispersion and a large specific surface area, it can play a role to prevent
resin and asphaltene aggregation, stabilize the crude oil.

4. Influencing factors

4.1. Composition of carbon number of crude oil

Petroleum wax can be divided into paraffin wax and microcrystalline wax. Paraffin wax were mainly
composed of the carbon number of C17-C35 and the average molecular weight of n-alkane was from 300
to 450. Microcrystalline wax are mainly composed of naphthenes, the number of carbon of which was
from C30 to C60 and the molecular weight of which is from 500 to 800. Senra et al. (Senra M et al. 2009)
found that the short chain n-alkanes were combined with long chain n-alkanes to produce eutectic effects
as the temperature decreased when the short chain n-alkanes reached a certain level. The presence of
short-chain alkanes prevents the interaction between long-chain alkanes. At this point, the total amount
of wax crystals in the solution increases, but did not form a network structure, so the gelation point and
pour point were still falling. Jin et al. (Jin W et al. 2014) studied the interaction between simulated oil
and waxy crude oil with EVA, and found that the pour point depressant had better pour point depression
with the carbon number distribution of 16–25.

4.2. Pour point depressant structure

The pour point depression increased with the length of carbon chain increase in a certain carbon num-
ber. After reaching a certain carbon number, the solubility of the pour point depressant decreases and
the pour point depression decreases gradually. Soni et al. (Soni H P et al. 2010) pointed out that the waxy
crude oil modification effect will be different when the pour point depressant functional groups contain
benzene ring and unsaturated bond. Yang et al. (Yang F et al. 2015c) discussed the pour point depression
of octadecyl acrylate/vinyl acetate diol from the monomer molar ratio, monomer concentration, rela-
tive molecular weight of the pour point depressants and the reaction conditions. The results show that
 PETROLEUM SCIENCE AND TECHNOLOGY 213

the crystallization effect of the pour point depressant was related to its nonpolar component content.
However, there was a balance point between the polar component and the nonpolar component. The
imbalance between the polar component and the nonpolar component will decrease the solubility of the
pour point depressant and the crystallization effect was greatly reduced.

5. Conclusion
Chemical modification of waxy crude oil has made a great progress. It has been reported that the nano-
technology of the pour point depressants can effectively improve the flow of crude oil. Not only is it
beneficial for long distance transportation of crude oil at normal temperature, but also can reduce the
operating costs of the pipeline and ensure the safe operation of the pipeline. So it has a good application
prospects. The development of the modification method from EVA pour point depressant to a variety
of novel chemical pour point depressants. The essence of waxy crude oil modification is to change the
interaction between wax molecules by eutectic and adsorption, so as to improve the morphology of
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wax crystals, so that it is not easy to form three-dimensional network structure. It is the main research
method of the novel chemical pour point depressants by introducing organic modified nano-particles,
surface grafting and esterification.

Funding
This work was financially supported by the National Natural Science Foundation of China (51490650) and the National
Natural Science Foundation of China 51628902)

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