Fuel 218 (2018) 213–217

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Fuel
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Short communication

Characteristics of a crude oil composition and its in situ waxing inhibition T

behavior
⁎
Gang Chena, , Jiao Lina, Weimin Hua, Chao Chenga, Xuefan Gua, Weichao Dua, Jie Zhanga,
⁎
Chengtun Qua,b,
a
College of Chemistry and Chemical Engineering, Xi’an Shiyou University, Xi’an 710065, China
b
State Key Laboratory of Petroleum Pollution Control, CNPC Research Institute of Safety and Environmental Technology, Beijing 102206, China

A R T I C L E I N F O A B S T R A C T

Keywords: A crude oil containing high paraffin from Yanchang Oilfield was studied for the situ waxing inhibition as an
Crude oil example in this work. The components were separated using silica gel column chromatography by different
Saturated hydrocarbon eluent and were named A1 to A14, and the characteristics of each component and their influence on wax
Component crystallization were studied. It was found that the separated components could interact with each other to
In situ waxing inhibition
decrease the temperature of the wax point to 0.2–1.64 °C, but the effect on the amount of wax was relatively
small. Polarized micrographs showed that the components also affect the morphology and distribution of the
wax crystals. For example, the component A5 make the wax crystals of A1 larger and make the distribution of
wax crystals in a certain direction and more dispersed.

1. Introduction
Crude oil, a complex multi-component homogeneous organic mix-
ture, consists essentially of saturated hydrocarbons, aromatic hydro-
carbons, resins, asphaltenes and heterofunctionalized organic com-
pounds containing nitrogen, sulfur and oxygen [1]. Some compounds
extracted from crude oil have been investigated at the molecular level.
For example, the aromatic hydrocarbon fractions generally includes a
range of very low polar heterocompounds, such as benzothiophenes,
dibenzothiophenes, and dibenzofurans [2,3]. Individual nitrogen,
sulfur and oxygen compound groups occurring in the resin and as-
phaltene fractions have porphyrins and carboxylic acids [4,5]. How-
ever, few researches have been conducted on the interaction between
crude oil components, especially the effect of crude oil components on
the crystallization of crude oil waxes.
Waxes are a complex mixture of solid (at ambient temperature)
hydrocarbons which consist mainly of paraffin hydrocarbons with a
small amount of naphthenic and aromatic hydrocarbons as well as polar
compounds [6]. The composition of the crude oil varies to varying
degrees of the low temperature rheological properties of the crude oil
(e.g., pour point, viscosity, etc.). When the temperature decreases to a
certain extent, the crude oil will precipitate wax crystals. Wax crystals
are combined with each other to form a three-dimensional network
structure, the liquid components of crude oil are wrapped, so that the
fluidity of crude oil worse or even lost [7]. Resin and asphaltenes are
the average relative molecular mass of the largest and the most polar
components in crude oil, the hydrogen bonds between molecules of
resin and asphaltenes make the crude oil viscosity high[8], which is the
extraction of crude oil and transportation more difficult. Asphaltenes
are the heaviest and polar compounds in crude oils with the highest
aromaticity and polarity, which consist of fused polynuclear aromatic
systems, heteroatoms (S, N, and O), alkyl chains, and heavy metals
(e.g., Ni, V). Asphaltenes exist as three-dimensional aggregates due to
the strong intermolecular forces such as hydrogen bonding and π-
bonding [9] and even at very low concentration as 50–150 mg/L in a
good solvent such as toluene [10]. However, resin and asphaltenes are
natural surfactants that can be adsorbed on the surface of wax crystals
to prevent the growth of wax crystals [11].
The interaction between crude oil components is of great sig-
nificance to the exploitation and transportation of crude oil. If the re-
lationship between the crude oil components was studied and make
clear, the producer can predict the flow of crude oil and the wax pre-
cipitation, which can avoid the poor fluidity of crude oil problems and
make timely preventive measures.
In this work, the crude oil components were separated by column
chromatography, and the main structures of the crude oil were ana-
lyzed by UV spectrophotometry and IR spectrophotometry. In addition,
differential scanning calorimetry and polarized microscopy were used
to study the effect on the wax precipitation, which may be useful to
predetermines the change of viscosity and the wax precipitation.

⁎
Corresponding authors at: College of Chemistry and Chemical Engineering, Xi’an Shiyou University, Xi’an 710065, China (C.T. Qu).
E-mail address: gangchen@xsyu.edu.cn (G. Chen).

https://doi.org/10.1016/j.fuel.2017.12.116
Received 4 September 2017; Received in revised form 11 December 2017; Accepted 24 December 2017
0016-2361/ © 2017 Elsevier Ltd. All rights reserved.
G. Chen et al. Fuel 218 (2018) 213–217

Table 1 adsorbed on the surface of the silica gel. The silica gel was dried,
The physical parameters of crude oil from Yanchang Oilfield. grinded and then analyzed by infrared spectroscopy. FTIR spectra were
recorded in KBr pellets with a Bruker Tensor 37 spectrometer in the
Pour ρ20 (g·cm−3) Saturated Aromatic Resin (%) Asphaltene (%)
point HC (%) HC (%) 400–4000 cm−1 region. FTIR spectrometer was calibrated by 1.5 mil
(°C) and 55 µm thick polystyrene (PIKE Technologies) as reference standard
before the analysis.
28.2 0.836 70.2 19.7 9.7 0.4

2.5. UV analysis of the crude oil components

2. Experimental
The separated crude oil constituents were solve in trichloromethane
2.1. Materials respectively at a concentration of 10 mg/L. Electronic spectra were
recorded in the range 200–400 nm, with spectral on as standard, on a
Petroleum ether, ethyl acetate, methanol, trichloromethane were UV-2600 spectrophotometer.
purchased from Xi’an Chemical Reagent Co., Ltd (at AR reagent grade)
and were used without further purification. The crude oil sample was 2.6. Differential scanning calorimetry analysis
obtained from Yanchang Oilfield with no suspended sand particles. The
physical parameters of this crude oil was shown in Table 1. The differential scanning calorimetry (DSC) analysis of the samples
are performed using a Mettler-Toledo DSC822e DSC apparatus. The
chemicals, suppliers and purities used for the DSC calibration were: n-
2.2. Thermogravimetric analysis conditions
C7 (Scharlau, 99%), n-C8 (Panreac, 99%), n-C12 (Alfa-Aesar, > 99%),
n-C16 (Alfa-Aesar, > 99%), n-C18 (Fluka, P99.8%) and Indium (Mettler
The TGA (Thermogravimetric Analysis) was carried out using a
Toledo). Repeatability and reproducibility tests shows that this calori-
TGA/SDTA851 instrument over the temperature range of 35–600 °C, at
meter is capable of producing data of enthalpies of fusion with an un-
a heating rate of 20 °C/min, nitrogen flow 20 mL/min and other para-
certainty of 1.5%, temperatures of fusion between 0.1 and 0.2 K, and
meters. The quality of the test oil samples ranges from 3 to 6 mg.
heat capacities with an uncertainty of 1.5%, all at a 95% confidence
level. The temperature profile follows two steps: (1) Previous step:
2.3. Separation of crude oil components
Sample is heated at 3 °C/min from room temperature to 40 °C to com-
pletely dissolve possible solid phase and to remove any thermal history;
10 g of the crude oil weighed accurately, dissolved in chloroform
(2) Cooling step: Sample is cooled down from 40 °C to −20 °C at 3 °C/
and fully adsorbed on the quality of 150–200 mesh silica gel, and then
min.
drying at the appropriate temperature. The prepared crude oil sample
was loaded into 200 g of the upper layer of the column chromatography
2.7. Optical microscopy analysis
silica gel. They were treated with petroleum ether, a mixture of pet-
roleum ether and ethyl acetate, a mixture of chloroform and methanol,
The saturated hydrocarbon component was separated from the
and methanol successively. The eluates were collected respectively, the
crude oil using the standard method for the optical study. Wax crystal
solvent was evaporated, and the corresponding fractions were obtained.
morphologies were observed using a BX41-P OLYMPUS polarizing mi-
The components’ names and their contents were shown in Table 2. Due
croscope. Samples were initially heated to 50 °C and then cooled to
to the strong polar components of crude oil adsorption on the silica gel,
10 °C for 5 min. A small amount of wax crystal was loaded onto the
the final eluted part is less than 100%.
glass slide inside a copper stage with a central window. During the
measurement, the temperature of the copper stage was controlled at
2.4. IR analysis 10 °C in a circulating bath.

After the separation of the crude oil by the column separation 3. Results and discussion
method, some of the components in the crude oil were deposited or
3.1. Thermogravimetric analysis of crude oils
Table 2
Components and contents of the crude oil.
In order to understand the content of the crude oil, thermogravi-
Eluents Labels of component w/% metric analysis was carried out. The plots of mass fraction (W/%)
versus the temperature (T/°C) yield curve as shown in the Fig. 1. As can
Petroleum ether A1 65.01 be seen from the data in the Fig. 1, from 35 to 500 °C, the oil sample is
Petroleum ether: Ethyl acetate (volume ratio A2 8.42
100:1)
continuously evaporated to lose weight, until the temperature reaches
Petroleum ether: Ethyl acetate (volume ratio A3 4.26 to 500 °C, it almost becomes a horizontal line, only 0.1% residue left.
50:1) When the temperature rises from 40 °C to 200 °C, the weight loss rate of
Petroleum ether: Ethyl acetate (volume ratio A4 2.18 the crude oil reaches 44.28%, which corresponds to the petrol in-
30:1)
gredients of the crude oil. As the temperature ranges from 150 °C to
Petroleum ether: Ethyl acetate (volume ratio A5 1.39
20:1) 350 °C, the weight loss rate is 61.04%, which corresponds to the diesel
Petroleum ether: Ethyl acetate (volume ratio A6 1.39 ingredients [12]. The TGA result shows that this crude oil is a good
15:1) feedstock for oil refining.
Petroleum ether: Ethyl acetate (volume ratio A7 2.38
10:1)
Petroleum ether: Ethyl acetate (volume ratio 3:1) A8 1.59
3.2. IR analysis
Petroleum ether: Ethyl acetate (volume ratio 2:1) A9 0.79
Petroleum ether: Ethyl acetate (volume ratio 1:1) A10 2.97 After the separation of the crude oil in 2.2, the silica gel turned from
Methanol: Trichloromethane (volume ratio 30:1) A11 1.29 white to gray, because some of the components in the crude oil were
Methanol: Trichloromethane (volume ratio 10:1) A12 1.39
deposited or adsorbed on the surface of the silica gel. The silica gel with
Methanol: Trichloromethane (volume ratio 5:1) A13 0.40
Methanol A14 0.50 the sediments were dried and then analyzed by infrared spectroscopy
(IR), and it was shown in Fig. 2. As can be seen, the absorption at

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G. Chen et al. Fuel 218 (2018) 213–217

100 shown in Fig. 3. The maximum absorption wavelength of the A1–A14

component of the crude oil sample shifts to long wavelength gradually.
The maximum absorption wavelength of A1, A2 and A3 is about
80 215 nm, which indicates that the components may be containing
(200,65) naphthalene hydrocarbon compound. The components of A4, A5, A9,
A10 and A11 in the range of 220–235 nm have different intensity of the
60
absorption peak, and A5, A9 and A10 have absorption peaks near
W (%)

256 nm, indicating that these components may contain compounds

40 such as naphthalene and 2-methylanthracene. The components of A7,
A12 and A13 show absorption peak at 250 nm, which indicates that
they may contain the anthracene and phenanthrene compounds.
20
3.4. Effect of the component on wax crystallization in situ
(500,0.1)
0
In the process of the crude oil extraction and transportation, as the
100 200 300 400 500 temperature decreases, the wax in the crude oil will precipitate. The
T (°C) precipitated wax will gradually deposit on the wall of the tube, re-
Fig. 1. Thermogravimetric analysis of the crude oil.
sulting in a significant reduction in the flow of crude oil, which makes
the decline in the pipeline transport capacity of the crude oil and dif-
ficulties of the extraction and transportation of the crude oil [15]. In
100 order to study the effects of the components in the crude oil on the
crystallization of wax in situ, the interaction of A1 (mainly the satu-
rated hydrocarbon) and other components was studied using differ-
80 ential scanning calorimetry (DSC) respectively. The corresponding wax
precipitation point, wax precipitation peak and the amount of wax were
60 shown in Table 4. The amount of wax calculation formula is as follows
[16]:
T/%

40
20
0 lization heat of crude oil, the value is 210 J/g.
4000 3500 3000 2500 2000 1500 1000
-1
į/FP
Fig. 2. IR spectrum of adsorption sediments on silica gel.
3600–3400 cm−1 is width and strong, which corresponds to the ab-
sorption of amino or associative hydroxyl stretching vibration. The two
sharp peaks at 2600 and 2550 cm−1 may be the stretching vibration
absorption peaks of the mercapto groups. The strong and narrow ab-
sorption peaks at 1630 cm−1 can be attribute to the delocalized π bond
of the aromatic ring, the stretching vibration absorption peak of C]O
bond in the heterocyclic ring and amide or bending vibration absorp-
tion peak of NeN bond in nitrogen heterocyclic structure. The results
show that the sediment of the crude oil contains N, O, S and other
heteroatoms, and the sediment belongs to the strong polar compounds.
Based on the analysis of the IR of the crude oil, it indicates that the
components adsorbed on the silica gel column may be strong polar
components such as colloid or asphaltene [13].
3.3. UV analysis of the crude oil components
For the polycyclic aromatic hydrocarbon compounds, the number of
the benzene ring and structure of the compound will cause the UV
absorbance characteristic peaks of the corresponding compounds to be
different. Therefore, it is possible to determine that the core structure of
the polycyclic aromatic hydrocarbon compound by UV, which may be
present in the crude oil. The wavelengths of the maximum UV ab-
sorption characteristic peaks of several polycyclic aromatic hydro-
carbons were shown in Table 3 [14].
The fourteen components separated from the crude oil by silica gel
column were subjected to UV spectrum analysis, and the results were
20
∫0 Qdt
w=
Q
where dQ is the heat released from the wax crystallization in the oil
samples at the temperature t ∼ (t + dt), J/g; Q is the average crystal-
Compared with the single component of A1, the wax precipitation
500 points of the mixtures of A1 and other component (A2–A14) reduce
with varying degrees, but the reduction is relatively small amplitude.
Wax precipitation peaks temperature also decrease, except A1 + A7
and A1 + A9. The amount of wax content changes more complex, even
some components lead the wax precipitation of A1 to increase. When
the high polar components, such as A2–A14, were added, the wax
precipitation point of A1 is reduced by the adsorption, eutectic and
solubilizing effects of these polar components on paraffin wax [17]. The
results suggest that the other components in the crude oil can inhibit or
promote the wax crystallization of saturated hydrocarbon in situ.
3.5. Effect of crude oil component on wax morphology
The effects of other components on the wax crystal morphology of
saturated hydrocarbon were studied by optical microscopy. In Fig. 4, it
can be seen that the wax crystal of A1 is needle-like, and is irregularly
distributed, which connect to a three-dimensional network to inhibit
the flowing of the liquid phase. Compared with (1), the wax crystal
morphology and wax content of (2) changed little, while the wax
crystals are thinner, and the wax amount decreases in (3). The needle-
like wax crystal is obviously larger, the amount of wax crystals in-
creases, and the distribution of wax crystal has a certain direction and is
more scattered in (4). The needle-like wax crystal in (5) and (6) is
thinner than that of (1), and the amount of wax increases, but the wax
crystal distribution is relatively dispersive.
The main component of this crude oil sample is the saturated hy-
drocarbon, and it also contains a suitable amount of high polar com-
ponents and colloids. The long chain of saturated hydrocarbon mole-
cules can co-crystal with the side chain of high polar components and
colloids, and the exposed polar groups play a role in surrounding and
disperse wax crystals, and weaken the connection strength between

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G. Chen et al. Fuel 218 (2018) 213–217

Table 3
The characteristic ultraviolet absorption of several polycyclic aromatic hydrocarbons.

Compound The ring number λmax/nm Compound The ring number λmax/nm

2 220 4 286–290

3 250 4 332–338

3 250 5 308

3 257 5 329–334

4 278 5 382–388

4 287–291 5 406

A14 Table 4
DSC analysis results of the interaction of A1 and 1% other components.
A13
The component T1/°C T2/°C w/% T1/°C T2/°C Δw/%
A12
A1 29.42 25.83 0.14 – – –
A11 A1 + A2 28.76 25.88 0.07 −0.66 0.05 −0.06
A1 + A3 29.22 26.67 0.14 −0.20 0.84 0.00
A1 + A4 28.58 25.97 0.14 −0.84 0.14 0.00
A10 A1 + A5 28.69 26.39 0.12 −0.73 0.56 −0.02
A1 + A6 29.21 25.97 0.18 −0.21 0.14 0.04
A9 A1 + A7 29.06 25.64 0.16 −0.36 −0.19 0.02
A1 + A8 28.64 26.47 0.13 −0.78 0.64 −0.01
A8 A1 + A9 27.78 25.63 0.15 −1.64 −0.20 0.01
A1 + A10 28.42 26.38 0.17 −1.00 0.55 0.03
A7 A1 + A11 28.45 26.14 0.18 −0.97 0.31 0.04
A1 + A12 28.65 25.97 0.15 −0.77 0.14 0.01
−1.44
A6 A1 + A13 27.98 25.87 0.17 0.04 0.03
A1 + A14 28.71 26.64 0.16 −0.71 0.81 0.02

A5
lgİ

T1—Wax precipitation point; T2—Wax precipitation peak; w—Amount of wax;

ΔT1—Change of wax precipitation point; ΔT2—Change of wax precipitation peak;
A4 Δw—Changes of wax content.

A3
wax crystals, thus hindering the accumulation of wax crystals [21,22].
A2 Although the wax crystal needle becomes larger, it is not easy to be
polymerized settlement. So the reasonable proportion of resin and as-
A1 phaltenes of the crude oil contribute to improving fluidity of the crude
oil, thereby enhancing the efficiency of extraction and transport of
200 250 300 350 400 crude oil [23].
Ȝ (nm)
Fig. 3. The UV spectrum of the components from the crude oil. 4. Conclusions

The other components of the crude oil on the component A1 has the
wax crystals [18]. It has been known that resin is a surface active
effect of reducing the temperature of the wax point, the decline in the
material that can be adsorbed on the waxy crystal surface to prevent
range of 0.2–1.64 °C, which indicate that components of the crude oil
wax crystals from growing up, and asphaltenes, a further polymeriza-
could inhibit the crystallization of wax. The influence of the other
tion of resin, is insoluble but very small particles dispersed in the oil,
components of the crude oil on the amount of wax in the component A1
which play a good dispersion on the wax crystal [19]. Asphaltenes and
is enhanced, weakened and almost little effect, but the overall impact
resin form a stable spatial layer of asphaltenes through the hydrogen
on the amount of wax is relatively small. The other components of the
bonds between molecules, van der Waals forces between resins, and the
crude oil on the wax form and size of A1 also have varying degrees of
repulsive force of the side chains of the alkanes [20]. Under the action
impact. Therefore, we can extract crude oil components of the wax
of co-crystallization, resin and asphaltenes adsorb on the surface of wax
crystallization of large components to improve the efficiency of crude
crystals, which reduces the surface energy and structural strength of the
oil transport.

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G. Chen et al. Fuel 218 (2018) 213–217

(1) (2) (3)

(4) (5) (6)

Fig. 4. The wax crystal morphology of saturated hydrocarbon with other component (1) A1; (2) A1 + A4; (3) A1 + A5; (4) A1 + A7; (5) A1 + A9; (6) A1 + A11.

Acknowledgments
This work was financially supported by the grants from National
Science Foundation of China (21763030), Natural Science Foundation
of Shaanxi Province (2017JQ2041) and Postgraduate Innovation
Project of Xi’an Shiyou University (YCS16211025).
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