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The Preparation of a Polyether

Demulsifier Modified by Nano-SiO2 and
the Effect on Asphaltenes and Resins
a b a a
F. H. Wang , L. B. Shen , H. Zhu & K. F. Han
a
State Key Laboratory of Organic-Inorganic Composites, Department
of Organic Chemistry, Institute of Modern Catalysis, School of
Science, Beijing University of Chemical Technology, Beijing, P. R.
China
b
Beijing No. 4 High School, Beijing, P. R. China
Published online: 25 Oct 2011.

To cite this article: F. H. Wang , L. B. Shen , H. Zhu & K. F. Han (2011) The Preparation of a Polyether
Demulsifier Modified by Nano-SiO2 and the Effect on Asphaltenes and Resins, Petroleum Science and
Technology, 29:24, 2521-2529, DOI: 10.1080/10916460903393997

To link to this article: http://dx.doi.org/10.1080/10916460903393997

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 Petroleum Science and Technology, 29:2521–2529, 2011
Copyright © Taylor & Francis Group, LLC
ISSN: 1091-6466 print/1532-2459 online
DOI: 10.1080/10916460903393997

The Preparation of a Polyether Demulsifier

Modified by Nano-SiO2 and the Effect
on Asphaltenes and Resins

F. H. WANG,1 L. B. SHEN,2 H. ZHU,1 AND K. F. HAN1

Downloaded by [Washington University in St Louis] at 23:22 21 September 2013

1
State Key Laboratory of Organic-Inorganic Composites, Institute of Modern
Catalysis, Department of Organic Chemistry, School of Science, Beijing
University of Chemical Technology, Beijing, P. R. China
2
Beijing No. 4 High School, Beijing, P. R. China

Abstract In order to enlarge the range of applications of nanomaterials and improve

the performance of macromolecular polymer demulsifier, nano-SiO2 was integrated
with polyether demulsifier TA1031 to form nanomodified demulsifier using an in
situ synthesis method. Analysis of the polyether demulsifier modified by nano-SiO2
was performed using transmission electron microscopy (TEM) and Fourier transform
infrared (FTIR) spectroscopy. The result showed that applying nanomaterials to crude
oil demulsifier greatly improves the performance of the original demulsifier. When
the ratio of nano-SiO2 and TA1031 is 1:10, the performance of the nanomodified
demulsifier was best, and the ratio of demulsification was improved by about 20%.
The time of demulification and dewatering was also greatly shortened by about 30
min. The influence of nanomodified demulsifier on the asphaltenes and resins was
studied by FTIR.

Keywords analysis, asphaltenes, nanomodified, polyether demulsifier, resins

1. Introduction
Petroleum is one of the most important energy sources all over the world. Petroleum is
exploited and formed emulsion including different amounts of water (Wei and Zhang,
1995), which could not be directly applied, transported, and processed. It is necessary
to separate the water completely from the petroleum emulsion before transporting or
refining (Marit et al., 1999). Methods for demulsification include physical and chemical
methods. Because the physical method is awkward for widespread industrial applications,
chemical agents (demulsifier) are widely used to separate the water completely from
emulsion (Wang et al., 2004).
The characteristics of the crude oil, which should play a role in determining the
solubility of asphaltenes, include the resin-to-asphaltene ratio, the aromaticity ratio of
the crude medium and resins with respect to the asphaltenes, and the concentration of

Address correspondence to Hong Zhu, State Key Laboratory of Organic-Inorganic Composites,

Institute of Modern Catalysis, Department of Organic Chemistry, School of Science, Beijing
University of Chemical Technology, No. 15 North Third Ring Road, Chaoyang District, Beijing
City 100029, China. E-mail: zhuho128@126.com

2521
 2522 F. Wang et al.

polar functional groups in the resins and asphaltenes. Resins and asphaltenes play a key
role in stability of emulsion interfacial film (Xia et al., 2004).
Nanotechnology has been applied successfully in various fields (Ngomsika et al.,
2005; Zhang and Wang, 2006). The present study makes nanomaterial modified using
polyether demulsifier (TA1031, Binzhou Chemical Plant, Shandong Province, China) and
researches the effect of nanomodified demulsifier on resins and asphaltenes.

2. Experimental

2.1. Materials
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Sodium silicate (analytical reagent; Beijing Chemical Plant, P. R. China), polyether

demulsifier TA1031 (Binzhou Chemical Plant, Shandong Province, P. R. China), and
hydrochloric acid (AR; Beijing Chemical Plant, P. R. China). A scanning electron micro-
scope (SEM; model S-530, Hitachi, Hitachi, Japan), Fourier transform infrared (FTIR)
spectroscope (Nicolet, Madison, WI), rotational viscometer (model NXS-11A, Chengdu
Instrument Factory, Sichuan Province, P. R. China), and interfacial tension meter (model
TX-500C, Bowing Industry Corp., Manassas, VA).

2.2. Nano-SiO2 Modified in situ TA1031

TA1031 solution was prepared in proper mass ratio by TA1031, ethanol, and deionized
water; then the sodium silicate solution was added into the solution above under stirring.
After the two solutions were mixed into a homogeneous solution, HCl was added into
the mixed solution to adjust the pH value to 7. The reaction was kept for 6–8 hr under
stirring to form the new demulsifier in which the nano-SiO2 was dispersed.

2.3. Preparation of Crude Oil Emulsion

The water-in-oil (W/O) emulsion was prepared by oil:water D 3:2 (volumetric ratio)
using an automatic mixer at 60ı C.

2.4. Asphaltenes and Resins Separation from Crude Oil

Asphaltenes and resins were separated from crude oil by the industry standards (Chen
et al., 2004).

3. Results and Discussion

3.1. Demulsification Performance Testing

The demulsification performance test was conducted by placing 40 mL emulsion into a
capped 50-mL graduated cylinder, which was then placed into water bath and heated to
65ı C. The demulsifier was added via a microliter syringe, to obtain a concentration in
the emulsion of 100 mg/L. The cylinder was recapped, manually shaken 100 times, and
placed back in the water bath. The volume of water that separated from the emulsion
was monitored as a function of time. The demulsification performance of the demulsifier
with different contents (mass ratio) of nano-SiO2 is shown in Table 1.
 Modified Polyether Demulsifier 2523

Table 1
Dewatering rate of different concentrations of demulsifiers

Dewatering rate (%)

at different times, min
Type of Oil–water Water separated
demulsifier 15 30 60 90 120 interface from emulsion

No demulsifier 0 0 12.90 19.35 54.84 Irregular Yellow

TA1031 0 38.71 64.52 70.97 77.42 Regular Buff
SiO2 :TA1031 D 1:1 0 3.23 25.81 77.42 89.03 Regular Clear
SiO2 :TA1031 D 1:5 0 64.52 84.52 90.32 91.62 Regular Clear
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SiO2 :TA1031 D 1:10 0 64.52 90.32 96.77 96.78 Regular Clear

SiO2 :TA1031 D 1:20 0 70.97 77.4 80.64 90.32 Regular Clear

The data in Table 1 clearly illustrate that the demulsification performance of demul-
sifier with nano-SiO2 was better than the TA1031, and the demulsification performance
was related to the content of nano-SiO2 . The demulsification performance increased at
first and then decreased with increasing nano-SiO2 content. When nano-SiO2 :TA1031 D
1:10 (mass ratio), the demulsification performance was the best, and the dewatering rate
increased by 20% with regular oil–water interface and clear, separated water.

3.2. Characterization by SEM

SEM was used to characterize the TA1031 and the new demulsifier with nano-SiO2 shape
and size distribution.
Contrast Figures 1 and 2, the nano-SiO2 particle with the size of 10–60 nm was
well dispersed in demulisifer product, and a crosslinked network chain covered the nano-
SiO2 particle surface. According to the reaction materials’ compositions, the crosslinked
network chain should be TA1031. So, the nano-SiO2 dispersed in TA1031 may bond or
absorb on the surface of nano-SiO2 particles.

Figure 1. SEM image of TA1031.

 2524 F. Wang et al.
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Figure 2. SEM image of the new demulsifier.

3.3. Characterization by FTIR

The FTIR of TA1031 and new demulsifier is shown in Figure 3.
From Figures 3 and 4, we can see that the new demulsifier had some additional
absorption peaks besides the absorption peaks that the TA1031 had. The peak of the
infrared (IR) spectra of –CH3 –, –CH2 – appeared at 2,971, 2,869, and 1,454 cm 1 for
–CH3 –, –CH2 –; those of the adsorbed water on nano-SiO2 particle surface appeared
at 1,636 cm 1 ; and those of the ester, cycle ether, and ether bond in aliphatic ether
appeared at 1,373, 1,244, and 1,117 cm 1 . The strong absorption peak of Si-O-C and
Si-O-Si appeared at bond of 1,000–1,180 cm 1 ; the absorption peak that appeared at
1,064 and 944 cm 1 was caused by the stretching vibration and bending vibration of
Si-O-Si, respectively. So, there must have nano-SiO2 in the new demulsifier.

Figure 3. FTIR spectra of TA1031.

 Modified Polyether Demulsifier 2525
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Figure 4. FTIR spectra of the new demulsifier.

3.4. Effect of Demulsifier on Asphaltenes

Asphalt, a kind of mixture that includes many different structures of nonhydrocarbon
compounds, whose major chemical components are variable and whose properties are
different, is an aggregate composed of many kinds of matter. Asphaltenes have some the
same properties, such as multi-aromatic core, high-content heteroatom (N, O, S, etc.),
and alkyl side-chain groups. The effect of demulsifier on asphaltenes was studied by
FTIR (Figure 5).
The assignment of the different peaks in Figure 5a are listed in Table 2.
From Figure 5b, we can see that after the asphaltenes reacted with TA1031 the peaks
3,600–3,100 and 1,600 cm 1 become weak. This shows that the TA1031 must react with
some -OH groups in asphaltenes. From Figure 5c, we can see that after the asphaltenes
reacted with nanomodified demulsifier the peaks 3,600–3,100 and 1,600 cm 1 continued
to become weak, and the strong absorption peak of Si-O-C and Si-O-Si appeared at bond
of 1,000–1,180 cm 1 . The peak of the IR spectra of the adsorbed water on nano-SiO2
particle surface appeared at 1,636 cm 1 . The absorption peak that appeared at 1,064 and
944 cm 1 was caused by the stretching vibration and bending vibration of Si-O-Si. So,
the nanomodified demulsifier must react with asphaltenes.

3.5. Effect of Demulsifier on Resin

From Figure 6 (Quan, 1996), 4-6-methylene connects aromatic cyclic to form resin
molecule that contain some heteroatoms, such as oxygen (O), nitrogen (N), and sulfur
(S). The average molecular weight of resin was about 600–3,000.
The assignment of the different peaks of resin in Figure 7 are listed in Table 3.
Comparing the three IR spectrum in Figure 7, we can see that after reaction with the
demulsifier, many peaks become weak, and some disappeared, especially at 1,600–1,100
cm 1 . When some become weak or disappear, some new peaks appear. The TA1031
marker peaks appear at 1,103 cm 1 in Figure 7b and become weak in Figure 7c. The
Downloaded by [Washington University in St Louis] at 23:22 21 September 2013

(a)

(b)

(c)
Figure 5. FTIR spectra of asphaltenes sample: (a) FTIR spectra of asphaltenes; (b) FTIR spectra
of asphaltenes reacted with polyether TA1031; and (c) FTIR spectra of asphaltenes reacted with
nanomodified demulsifier.

2526
 Modified Polyether Demulsifier 2527

Table 2
FTIR analysis of asphaltenes

Asphaltenes
(KBr Pellet) Assignment Possible functional groups

3,600–3,100 (width) OH, NH -OH, -COOH, NH2

3,000–2,850 (strong) CH CH3 , CH2
1,690 (weak) CDO COOH, COOR
1,598 (middle) CDC, ˇ NH Aromatic cyclic, heterocycle, NHR
1,457 (strong) ı() CH2 -CH2 -
1,374 (middle) ıCH3 -CH3
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1,220 (weak) C-O, C-N COOH, ArOH, Ar-NH

1,190 (weak) C-O R1 -O-R2
1,040 (weak) C-O, C-N R-OH, Ar-O-R, RCH2-NH2
865 (weak), 811 (weak) CH Aromatic cyclic, heterocycle
745 (weak), 721 (weak) CH2 -CH2 -

Figure 6. Sketch map of resin.

strong absorb peak at 1,000–1,180 cm 1 was caused by vibration of Si-O-C and Si-O-Si.
The absorption peak that appeared at 1,064 and 944 cm 1 was caused by the stretching
vibration and bending vibration of Si-O-Si. So, the nanomodified demulsifier must react
with resin.

4. Conclusion
Asphaltenes and resin were characterized after reacting with demulsifier. The results show
that the nanomodified demulsifier must reacted with asphaltenes and resin and reduce
the membrane stabilizing action of asphaltenes and resin in emulsion interfacial film,
the interfacial film rupture was sped up and the time of demulsification and dewatering
would be greatly shortened.

Acknowledgment
The authors acknowledge the assistance of the Science and Technology Cooperation
Project (2006DFA61240) and the Fundamental Research Funds for the Central Univer-
sities (ZY1119).
 2528 F. Wang et al.
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(a)

(b)

(c)
Figure 7. FTIR spectra of resin sample: (a) IR spectrum of resin; (b) IR spectrum of resin after
reaction with TA1031; (c) IR spectrum of resin after reaction with nanomodified demulsifier.
 Modified Polyether Demulsifier 2529

Table 3
FTIR analysis of resins

Resin Assignment Possible functional groups

3,600–3,100 (width) OH, NH -OH, -COOH, NH2

3,000–2,850 (strong) CH CH3 , CH2
1,730 (weak) CDO COOH, COOR
1,602 (middle) CDC, ˇ NH Aromatic cyclic, heterocycle, NHR
1,462 (strong) ı() CH2 -CH2 -
1,377 (middle) ıCH3 -CH3
1,260 (weak), 1,220 (weak) C-O, C-N COOH, ArOH, Ar-NH
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1,191 (weak) C-O R1 -O-R2

1,030 (weak) C-O, C-N R-OH, Ar-O-R, RCH2-NH2
867 (weak), 811 (weak) CH Aromatic cyclic, heterocycle
722 (weak) CH2 -CH2 -

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