Fuel 166 (2016) 96–105

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Fuel
journal homepage: www.elsevier.com/locate/fuel

Organically modified nano-clay facilitates pour point depressing activity

of polyoctadecylacrylate
Bo Yao a, Chuanxian Li a, Fei Yang a,⇑, Johan Sjöblom b, Ying Zhang a, Jens Norrman b, Kristofer Paso b,
Zuoqu Xiao a
a
College of Pipeline and Civil Engineering, China University of Petroleum, Qingdao, Shandong 266580, People’s Republic of China
b
Ugelstad Laboratory, Department of Chemical Engineering, Norwegian University of Science and Technology, NO-7491 Trondheim, Norway

h i g h l i g h t s g r a p h i c a l a b s t r a c t

We introduce organic nanoclay to Introduction of nanomaterials constitutes a novel and efficient means to enhance the performance of
prepare nanocomposite pour point polymeric pour point depressants (PPDs). Based on the specific layered structure and favorable cationic
depressant. exchange characteristics of nano-clay particles in the presence of charged organic compounds, an original

POA/clay nanocomposite could hydrophilic nano-clay is first modified by octadecyltrimethyl ammonium chloride (OTAC) and then
further improve the rheological bypolyoctadecylacrylate (POA). The modified nano-clay serves as an effective nanocomposite PPD.
properties of crude oil. Compared to an identical content of POA, addition of POA/clay nanocomposite PPD to Changqing waxy

The addition of nanoclay fosters the crude oil improves the rheological properties while elevating the wax appearance temperature of the
precipitation of wax crystals. oil. Polarized microscope observation shows that POA/clay nanocomposites provide wax nucleation sites

Adding nanocomposite PPD results in upon which wax molecules assemble and precipitate. Addition of POA/clay nanocomposite PPD results in
the formation of larger and compact larger and more compact crystal morphology, thus inhibiting the formation of a network structure, and
wax crystals. further improving rheological properties of waxy crude oil.

A possible heterogeneous nucleation
mechanism for POA/clay
nanocomposite is proposed.

a r t i c l e i n f o a b s t r a c t

Article history: Introduction of nanomaterials constitutes a novel and efficient means to enhance the performance of
Received 19 July 2015 polymeric pour point depressants (PPDs). Based on the specific layered structure and favorable cationic
Received in revised form 8 October 2015 exchange characteristics of nano-clay particles in the presence of charged organic compounds, an original
Accepted 28 October 2015
hydrophilic nano-clay is first modified by octadecyl trimethyl ammonium chloride (OTAC) and then by
Available online 3 November 2015
polyoctadecylacrylate (POA). The modified nano-clay serves as an effective nanocomposite PPD.
Compared to an identical content of POA, addition of POA/clay nanocomposite PPD to Changqing waxy
Keywords:
crude oil improves the rheological properties while elevating the wax appearance temperature of the
Pour point depressant
oil. Polarized microscope observation shows that POA/clay nanocomposites provide wax nucleation sites

⇑ Corresponding author.
E-mail address: [email protected] (F. Yang).

http://dx.doi.org/10.1016/j.fuel.2015.10.114
0016-2361/Ó 2015 Elsevier Ltd. All rights reserved.
 B. Yao et al. / Fuel 166 (2016) 96–105 97

Waxy crude oil upon which wax molecules assemble and precipitate. Addition of POA/clay nanocomposite PPD results in
POA larger and more compact crystal morphology, thus inhibiting the formation of a network structure, and
Nano-clay further improving rheological properties of waxy crude oil.
Nanocomposite
Ó 2015 Elsevier Ltd. All rights reserved.

1. Introduction Montmorillonite (MMT) nano-clay is a layered silicate mineral

with a 2:1 type layer structure, i.e., it has two tetrahedral sheets sand-
Precipitation of paraffin waxes with carbon numbers C16–C40 wiching a central octahedral sheet [17]. Due to isomorphous substitu-
from waxy crude oils greatly complicates the low temperature flow tion, the nano-clay is negatively charged and some hydrated Na+ or K+
properties of the oils, generating difficulties in pipeline transporta- species exist in the interlayer in order to balance the negative charge
tion of the oils [1,2]. A well-recognized and efficient solution to [18]. Surfactants such as quaternary ammonium salt surfactants, are
these problems is deployment of polymeric additives such as pour often used to modify nano-clay such that organic cations replace the
point depressants (PPDs) and flow improvers (FIs) [3]. PPDs/FIs interlayer hydrated Na+ or K+, i.e., cation exchange, enlarging layer
doped in waxy crude oils could modify crystal growth habits by spacing and enhancing lipophilicity of the nano-clay. In this way,
nucleation, adsorption and co-crystallization effects, effectively the organically modified nano-clay (abbreviated as organic nano-
inhibiting the tendency of wax crystals to interconnect into fixed clay) is easier to disperse in a polymer matrix. In past decades, organic
three-dimensional networks [4,5]. Consequently, pour point, vis- nano-clay has been introduced into polymer matrices to form poly-
cosity and yield stress values of waxy crude doped with PPDs/FIs mer/clay nanocomposites (PCN) [19,20]. Due to imbibed nano-clay,
are substantially reduced. PCN properties such as mechanical strength and thermal tolerance
Comb-like polymers, such as polyacrylates and alkyl maleic anhy- are superior to those of pristine polymers. Because of the specific lay-
dride copolymers, have been thoroughly studied as PPDs of waxy ered structure and simple organic modification of MMT nano-clay, a
crude oils and diesel oils. Effects of alkyl side chain length, polar group POA/MMT clay nanocomposite PPD is developed in this work.
type and content, molecular weight, oil phase composition on the effi- Rheological beneficiation for Changqing waxy crude oil is evaluated.
ciency of comb-like PPDs have been elucidated [6–9]. Results show The nano-clay is first organically modified by cation exchange to
that alkyl chain length is a crucial factor influencing the efficiency improve its lipophilicity and to enhance the interaction between
of comb-like PPDs. In addition, some researchers added polar groups nano-clay and POA. Subsequently, POA/clay nanocomposite is pre-
and benzene rings to structure of comb-like PPDs to enhance interac- pared by solvent blending. The effect of POA/clay nanocomposite
tions with asphaltene, which is shown to increase the field perfor- PPD on wax appearance temperature (WAT), rheological parameters,
mance of the PPDs [10]. Poly (octadecyl acrylate) (POA) is an and morphology of precipitated wax crystals of Changqing waxy
effective comb-like PPD for waxy crudes, appearing to favor forma- crude oil is thoroughly investigated by DSC, rheometry and micro-
tion of island defects on paraffin wax surfaces, which exhibit weak scopic observation. The beneficiation mechanism of nanocomposite
interactions with the surrounding crystal and, therefore, act as impu- PPD on crude oil rheology is also discussed.
rity sites for blocking growth steps [11,12]. Although the poly
(octadecyl acrylate) has been widely applied in pipe transport of waxy 2. Experimental section
crude, its efficiency needs further improvement [5].
With the recent development of nanotechnology, polymer/inor- 2.1. Materials
ganic nanocomposites or nano-hybrid materials have become the
focus of significant R&D endeavors in the 21st century [13,14]. Deionized water was purified by reverse osmosis. Dodecane,
By introducing inorganic nanoparticles into polymeric matrices, toluene, ethanol, octadecyl acrylate, octadecyl trimethyl ammo-
resultant properties (i.e. mechanical, thermal, magnetic, and elec- nium chloride (OTAC) and 2,20 -Azobis(2-methylpropionitrile)
trical) are vastly improved. Enlightened by advances in polymer/ (AIBN) were purchased from Sinopharm Chemical Reagent Co. of
inorganic nanocomposites, researchers developed nano-hybrid China. Chemical purities were all analytical or chemical pure grade
PPDs by dispersing nanoparticles into polymeric PPD matrices. (with the purity P98 wt%). The comb-like POA PPDs were synthe-
Wang et al. [15] prepared a nano-hybrid PPD and compared its effi- sized by solvent free-radical polymerization of octadecyl acrylate
ciency with traditional ethylene vinyl acetate (EVA) PPDs. Rheolog- under a nitrogen atmosphere with AIBN as the initiator and
ical results showed that nano-hybrid PPD exhibits improved pour toluene as the solvent [16]. The average molecular weight of POA
point depression efficiency in comparison to the corresponding tested by gel permeation chromatography (GPC) was 20,000 Da.
EVA. Yang et al. [16] prepared a nano-hybrid PPD by directly MMT nano-clay was purchased from Hengshi Mineral Processing
dispersing hydrophilic nano-silica into POA PPDs. Compared with Co. in China. The cation exchange capacity (CEC) of nano-clay is
POA-based PPDs, nano-hybrid PPD further reduces gelation point, 98 mmol/100 g.
viscosity and yield stress of synthetic waxy oils. Microscopic The crude oil was kindly provided by Changqing oilfield in
images of precipitated wax crystals demonstrate that POA/nano- China. As shown in Table 1, the crude oil contains a large content
silica hybrids provide spherical-like templates for wax precipita- of saturates (66.89 wt%) and aromatics (23.51 wt%), while the con-
tion, imparting a large and compact morphology of precipitated tent of resins (8.78 wt%) and asphaltenes (0.82 wt%) are relatively
wax crystals, suppressing gelation and improving flowability of small. The initial boiling point of the crude oil is relatively low
the oil. The authors also observed in the experiment that the effi- (56 °C), while the wax content (15.35 wt%) and pour point (28 °C)
ciency of nano-hybrid PPD was not stable and decreased with rest is relatively high. Fig. 1 shows the crude oil has a wide n-alkane
time to the efficiency of pure POA in the end. This was perhaps distribution (C8–C45) with the peak carbon number around C18.
because POA molecules adsorbed on the surface of silica desorb
into oil phase due to the incompatibility of hydrophobic POA 2.2. Preparation of organic nano-clay
molecules and hydrophilic nano-silica. Therefore, the surface of
nano-particles should be properly modified so as to strengthen Hydrophilic nano-clay was modified by OTAC via cationic
interaction between polymeric PPDs and nano-particles. exchange. According to previous research [21,22], the OTAC
98 B. Yao et al. / Fuel 166 (2016) 96–105

Table 1 undoped crude samples were sealed in glass bottles and preheated
Physical properties of Changqing waxy crude oil. at 60 °C for 20 min; subsequently, the samples sealed in glass bot-
Saturates content Aromatics Resin content Asphaltene tles were cooled slowly to 50 °C at a cooling rate of 0.5 °C/min. The
(wt%) content (wt%) (wt%) content (wt%) oil samples were then loaded into the rheometer for testing.
66.89 23.51 8.78 0.82
Initial boiling Wax content Pour point q20 2.4.1. Gelation point test
4
point (°C) (wt%) (°C) A temperature ramp test from 50 °C to 10 °C was utilized to
56 15.35 28 0.8548 probe the gel point of crude oil doped/undoped with PPD. The
sample was cooled at a rate of 0.5 °C/min while a constant shear
Note: the saturates, aromatics, resin and asphaltene were obtained by normal SARA
stress of 0.01 Pa was imposed during cooling. Variation of shear
fractionation method; the pre-heat treatment temperature was 60 °C in the pour
point measurement.
rate with temperature was monitored and the gelation tempera-
ture is ascribed to a break to zero in the shear rate-temperature
curve.
concentration was fixed at 1.5 times the nano-clay CEC. A defined
amount of unmodified nano-clay was first dispersed into deionized 2.4.2. Flow curve test
water. Subsequently, OTAC was added into the dispersion and the Crude oil doped/undoped with PPD was first cooled quiescently
dispersion was stirred vigorously at 60 °C for 6 h. Resultant white from 50 °C to 5 °C at a fixed cooling rate 0.5 °C/min, and then main-
sediments were separated by centrifugation and washed several tained isothermally at 5 °C for 20 min. Subsequently, flow curves of
times with deionized water (pH = 7) to ensure complete removal the crude oil were measured at 5 °C by ramping the shear rate from
of free OTAC. Finally, the white sediments were vacuum dried at 5 s1 to 200 s1 in a time span of 10 min. The measured variation of
80 °C overnight and the obtained dried white sediments were the apparent viscosity with shear rate was recorded.
organic nano-clay. The composition and structure of the organic
nano-clay were analyzed by FT-IR spectroscopy (Thermo Nicolet 2.4.3. Yield stress test
Co., USA) and X-ray diffraction (Nanotec Technology Co., Nether- Crude oil doped/undoped with PPD were first cooled quies-
lands), respectively. The degree of modification of organic nano- cently from 50 °C to 10 °C at a fixed cooling rate 0.5 °C/min, and
clay was measured using a Q50 TGA thermogravimetric analyzer then maintained isothermally at 10 °C for 20 min. Subsequently,
(TA Instruments, USA) under an oxygenic atmosphere. Stability of the yield stress was measured by ramping the imposed shear
organic nano-clay particles dispersed in dodecane (0.2 wt%) was stress. The stress uploading rate was fixed at 5 Pa/min.
evaluated by direct microscope observation (OLYMPUS BX51,
Olympus, Japan) as well as particle size distribution assessment 2.5. DSC test of Changqing waxy crude oil
(Marlvern Mastersizer 2000, UK).
Exothermic phase changes occurring in undoped/doped crude
oil were studied by a DSC 821e calorimeter (Mettler-Toledo Co.,
2.3. Preparation of POA/clay nanocomposite PPD
Switzerland) to determine the WAT of crudes [23,24]. The temper-
ature scanning range is 85 to 20 °C. A fixed cooling rate of 10 °C/
POA/clay nanocomposite was prepared by toluene solvent
min was utilized, which was the most sensitive test rate of the
blending. The solvent blending procedure is presented elsewhere
instrument, due to the large associated heat flow.
[16]. The POA/nano-clay mass ratio was retained at 1:1 in order
to facilitate intuitive comparison with neat POA. Composition
2.6. Microscopic observation of Changqing waxy crude oil
and structure of the nanocomposite PPD were analyzed by FT-IR
and XRD. Stability of POA/clay nanocomposite dispersed in dode-
A polarizable microscopic OLYMPUS BX51 (Olympus Co., Japan)
cane (0.2 wt%) was also evaluated.
fitted with a Linkam LTS350 automatic thermal stage (Linkam
Scientific Instruments Ltd, UK) was used to observe wax crystals
2.4. Rheological measurement of Changqing waxy crude oil precipitated from the crude oil [25,26]. After being pre-heated to
60 °C for same time, one droplet of the crude oil sample was trans-
Rheological properties of crude oil samples were assessed using ferred to a glass slide covered by a coverslip. The loaded crude oil
an AR-G2 rotational rheometer (TA Instruments, USA) equipped samples were cooled from 50 °C to 0 °C in the stage with a fixed
with a coaxial cylinder system. To inhibit evaporation, doped/ cooling rate 0.5 °C/min. The observed morphology of the precipi-
tated wax crystals was recorded during the cooling process. Quan-
titative analysis of microscopic images were carried out by the
7 software OLYCIA p3 (OLYMPUS professional image analyzer) and
three key parameters, total number of wax crystals (Nwc), average
6 equal-area-circle diameter of wax crystals (Deac) and fractal dimen-
n-alkane content / wt%

sion of wax crystals (D) were obtained. Nwc and Deac represent the
5
number and size of precipitated wax crystals, respectively. D rep-
4 resents structural complexity and space-filling (occlusion) ability
of the wax crystals, and was quantified by the box counting
3 method [23,27].
2
3. Results and discussion
1
3.1. Characteristics of organic nano-clay
0
10 15 20 25 30 35 40
Carbon number distribution of n-alkane 3.1.1. Composition and structural analysis
Based on electric charge properties of nano-clay, OTAC serves to
Fig. 1. The carbon number distribution of Changqing waxy crude oil. fix a long chain alkyl group onto the outer surface and interlayer of
 B. Yao et al. / Fuel 166 (2016) 96–105 99

(a) POA/clay nanocomposite PPD nano-clay via electric interaction, resulting in expansion of the
interlayer spacing and accompanying reduction in interaction

474
925
forces between platelets [28]. FT-IR spectra of original and organic

1465

1175
nano-clay are presented in Fig. 2a. The original nano-clay spectrum

1735
Organic nanoclay
displays characteristic absorption bands at 1100 cm1 (SiAOASi

2855
2920
antisymmetric stretching vibration peak), 474 cm1 (SiO2 stretch-
ing), and 3400–3230 cm1 (RAOAH stretching), respectively. In

1250
Original nanoclay the FT-IR spectrum of the organic nano-clay, appearance of a
CAN absorption band at 1250 cm1 confirms that OTAC is present
on the outer surface and interlayer of nano-clay via ion exchange.
Fig. 2b displays X-ray powder diffraction patterns of original and
organic nano-clay (Cu Ka, with a scanning rate of 1°/min (2h)

1100

474
3750 3000 2250 1500 750 and scanning range of 3° to 15° (2h)). The Bragg equation,
Wave Number / cm-1 2dsin h = nk, is used to calculate d spacing values. The d001 spacing
of original nano-clay is determined to be 1.513 nm, while the d001
(b) spacing of organic nano-clay increases to 1.964 nm as d002 peaks
d001 ,2θ=4.4981°
4000 d001 ,2θ=4.2330° start to appear. The measured increase in the d001 spacing value
d001 ,2θ=5.8426°
confirms successful intercalation of cationic surfactant OTAC mole-
3000 cules with eighteen side alkyl chains into the nano-clay layers.
Original nanoclay Organic nano-clay was also examined by TGA in order to
Intensity

Organic nanoclay
POA/clay nanocomposite PPD quantify the degree of organic modification. An organic
2000
nano-clay was heated to 105 °C to eliminate the influence of
d002,2θ=6.8062° adsorbent water, and the residual weight was recorded as M1.
1000 The sample was then heated to 400 °C until a constant weight
M2 was attained. The same experiment was carried out for
0 original nano-clay. Mass loss rates was quantified specifically as
2 4 6 8 10 12 14 16 M1M2
M1
 100%. Results show that subsequent to intercalation, the
2θ / ° organic content of nano-clay, that is the mass loss rate at
Fig. 2. FT-IR spectra (a) and X-ray powder diffraction patterns (b) of original nano- 400 °C, reaches 37.51 wt%. In comparison, unmodified nano-clay
clay, organic nano-clay and POA/clay nanocomposite PPD. has an organic content of only 2.93 wt%.

(a) (b)

6
Fraction / %

0
1 10 100
d / μm
(c) (d)

Fig. 3. Original nano-clay (a) and organic nano-clay (b) dispersed in water and dodecane, the microscopic image of organic nano-clay dispersed in dodecane (c) and particle
size analysis of organic nano-clay dispersed in dodecane (d) (with a concentration of 0.2 wt%).
100 B. Yao et al. / Fuel 166 (2016) 96–105

(a) (b)

16
Fraction / %

12

0
1 10
d / μm
(c)

Fig. 4. POA/clay nanocomposite dispersed in dodecane (a), its microscopic image (b) and particle size analysis in dodecane (c) (with a concentration of 0.2 wt% at room
temperature).

3.1.2. Dispersibility of organic nano-clay 3.2. Characteristics of POA/clay nanocomposite PPD

Original and organic nano-clay were dispersed in water and
dodecane solvents, respectively, at a concentration of 0.2 wt%. 3.2.1. Composition and structural analysis
The dispersed samples were maintained quiescently at room tem- FT-IR spectra of the POA/clay nanocomposite PPD is shown in
perature for 1 h; subsequently, the stability of the samples was Fig. 2a, which displays characteristic absorption bands at
evaluated. As shown in Fig. 3a, unmodified nano-clay is well dis- 2920 cm1 (ACH3 characteristic peak), 925 cm1, 1465 cm1 and
persed in water but sediments quickly in dodecane, in accordance 2855 cm1 (ACH2A characteristic peak), 1735 cm1 (C@O stretch-
with the hydrophilic nature of clay. In contrast, organic nano-clay ing in ester), and 1175 cm1 (CAOAC stretching). Absorption
is well dispersed in dodecane but sediments quickly in water bands associated with original nano-clay at 1100 cm1 and
(Fig. 3b), consistent with an oleophilic nature. Fig. 3c and d show 474 cm1 are well retained. X-ray diffraction spectra associated
that organic nano-clay is dispersible in dodecane in the form of with POA and POA/clay nanocomposite PPD are shown in Fig. 2b.
flocs with sizes in the range of 8–80 lm and mean size of 30 lm. In the diffraction angle region of 3°–15° (2h), a sharp peak at
It may be concluded nano-clay changes nature from hydrophilic 4.2330° is evident from the POA/clay nanocomposite, indicating a
to oleophilic after OTAC intercalation. d001 spacing of 2.087 nm. In comparison to the d001 value
(1.964 nm) of organic nano-clay, the interlayer spacing of nano-
clay in POA/clay nanocomposite is slightly increased. Therefore,
3.1.3. Effect of organic nano-clay on rheology of crude oil
an intercalated or hierarchical morphology of POA/clay nanocom-
The influence of solely organic nano-clay on the gelation point
posite was obtained [29].
and measured flow curves (at 5 °C) of Changqing crude oil was
assessed by rheometric means. As illustrated in Supporting Infor-
mation Fig. S4, both the gelation point (from 25.2 °C to 25.5 °C) 3.2.2. Dispersibility of POA/clay nanocomposite PPD
and the apparent viscosity at 5 °C increases slightly upon addition When POA/clay nanocomposite is dispersed into dodecane at
of 400 mg/kg organic clay. In addition, the effect of solely organic 0.2 wt%, the resulting fluid state is a homogeneous dispersion with
nano-clay on the morphology of precipitated wax crystals (at no apparent sedimentation observed after 3 h at room temperature
0 °C) is shown in Fig. S5. It is obvious that the organic nano-clay (see Fig. 4a). From Fig. 4b and c, it is evident that POA/clay
alone brings little influences to the wax crystals morphology. nanocomposite is dispersed in dodecane as small particles with
Despite the large presence of OTAC molecules (with C18 alkyl sizes ranging from 2 to 12 lm and a mean size of 6 lm. In compar-
chains) fixed on the outer surface and interlayer of the organic ison to organic nano-clay-dodecane dispersion, POA/clay
nano-clay, the organic clay is not able to function as a pour point nanocomposite dispersed in dodecane are smaller and more stable.
depressant nor change the precipitation habit of the wax crystals. It is deduced that POA molecules adsorb on the outer surface and
Addition of organic nano-clay alone slightly aggravates the rheol- interlayers of nano-clay and further increase the nano-clay particle
ogy of the crude oil. lipophilicity.
 B. Yao et al. / Fuel 166 (2016) 96–105 101

3.3. Effects of POA/clay nanocomposite PPD on rheology Fig. 5c and d. Apparent viscosity values measured at various shear
rates are shown in Table 2 (the average viscosity reducing rate I is
3.3.1. Gelation point compared with oil undoped and II is compared with oil doped with
The influence of POA and POA/clay nanocomposite PPD on the same content of POA). The apparent viscosity is substantially
gelation point of Changqing crude is shown in Fig. 5a and b and reduced after addition of POA or POA/clay nanocomposite PPD.
Table 2. The gelation point is reduced in a conventional manner At comparable POA content, POA/clay nanocomposite PPD has a
with increasing POA concentration. The gelation point of undoped much stronger viscosity reduction performance than neat POA.
crude oil is 26.2 °C. The measured gelation point decreases to The average viscosity reduction after addition of 50 mg/kg POA is
25.2 °C upon addition of 50 mg/kg POA and is further depressed 6.43%, while the average viscosity reduction after addition of
to 24.6 °C at a POA concentration of 100 mg/kg. The gelation point 100 mg/kg nanocomposite PPD (containing 50 mg/kg POA and
is 21.4 °C at 200 mg/kg POA and is 19.0 °C at 400 mg/kg POA. 50 mg/kg organic nano-clay) is 27.06%. Compared to 50 mg/kg
Prepared POA/clay nanocomposites consist of 50 wt% POA and POA, 100 mg/kg nanocomposite PPD further reduces crude oil vis-
50 wt% organic nano-clay. Therefore, crude oil doped with cosity by 21.99%. The dramatic observed flowability beneficiation
200 mg/kg POA is appropriately comparable to crude oil doped of nano-clay becomes even more evident at POA contents of
with 400 mg/kg nanocomposite (200 mg/kg POA + 200 mg/kg 200 mg/kg and 400 mg/kg, with additional viscosity reduction
organic nano-clay), as the overall POA contents are identical. In ascribed to the presence of nano-clay quantified as 25.50% and
comparison to neat POA, the POA/clay nanocomposite PPD demon- 33.75%, respectively.
strates a stronger ability to depress the gelation point. The gelation The effect of rest time on viscosity reduction performance of the
point is 23.7 °C upon addition of 100 mg/kg nanocomposite PPD. At PPDs was evaluated by an equilibrium viscosity test at 50 s1 and
200 mg/kg nanocomposite PPD, the gelation point is further 5 °C. As seen in Supporting information Table S1, the observed rhe-
reduced to 23.0 °C. The gelation point is 18.0 °C at 400 mg/kg ological beneficiation of POA/clay nanocomposite is more persis-
nanocomposite PPD and is 17.2 °C at 800 mg/kg nanocomposite tent and lasting than pure POA, at comparable overall POA
PPD. contents.

3.3.2. Flow curves 3.3.3. Yield stress

Measured flow curves of waxy crude undoped/doped with POA The yield stress of crude oil undoped/doped with POA and
and POA/clay nanocomposite PPD at 5 °C are illustrated in POA/clay nanocomposite PPDs at 10 °C is shown in Table 2. The

1.0 1.0
waxy crude oil undoped waxy crude oil undoped
doped with 50 mg/kg POA doped with 200 mg/kg POA
0.8 doped with 100 mg/kg POA 0.8 doped with 400 mg/kg POA
doped with 100 mg/kg POA/clay doped with 400 mg/kg POA/clay
-1

doped with 200 mg/kg POA/clay doped with 800 mg/kg POA/clay
Shear Rate / s
Shear Rate / s -1

0.6 0.6

0.4 0.4

0.2 0.2

0.0 0.0

22 24 26 28 30 16 20 24 28 32
Temperature / °C Temperature / °C
(a) (b)

10 waxy crude oil undoped

doped with 50 mg/kg POA doped with 200 mg/kg POA
Apparent Viscosity / Pa·s
Apparent Viscosity / Pa·s

doped with 100 mg/kg POA 1 doped with 400 mg/kg POA
doped with 100 mg/kg POA/clay doped with 400 mg/kg POA/clay
doped with 200 mg/kg POA/clay doped with 800 mg/kg POA/clay

0.1

0 50 100 150 200 0 50 100 150 200

-1 -1
Shear Rate / s Shear Rate / s
(c) (d)
Fig. 5. Gelation point (a and b) and flow curves at 5 °C (c and d) of Changqing waxy crude oil undoped/doped with POA and POA/clay nanocomposite PPDs.
102 B. Yao et al. / Fuel 166 (2016) 96–105

Table 2
Effects of POA and POA/clay nanocomposite PPDs on the gelation point, apparent viscosity and yield stress of Changqing waxy crude oil.

Condition of PPD dosage Gelation point (°C) Apparent viscosity at 5 °C (Pa s) Average viscosity Average viscosity Yield stress at 10 °C (Pa)
1 1 1 1 reducing rate I (%) reducing rate II (%)
10.23 s 49.45 s 101.6 s 152.1 s
Original crude oil 26.2 4.873 1.897 1.362 1.121 – – 725.3
50 mg/kg POA 25.2 4.526 1.780 1.228 1.009 6.43 – 463.7
100 mg/kg POA/clay 23.7 3.102 1.451 1.018 0.859 27.06 21.99 220.1
100 mg/kg POA 24.6 3.342 1.469 1.032 0.860 26.21 – 233.8
200 mg/kg POA/clay 23.0 2.445 1.092 0.709 0.553 38.70 16.81 89.5
200 mg/kg POA 21.4 0.775 0.262 0.192 0.164 85.03 – 16.3
400 mg/kg POA/clay 18.0 0.480 0.206 0.156 0.136 88.88 25.50 8.5
400 mg/kg POA 19.0 0.622 0.227 0.169 0.147 87.39 – 9.6
800 mg/kg POA/clay 17.2 0.431 0.147 0.109 0.094 91.67 33.75 1.7

yield stress of the original crude oil gel is high (725 Pa). Addition of
POA or POA/clay nanocomposite PPD effects a substantial yield Doped with 800ppm POA/clay
WAT=35°C
stress reduction. At equivalent POA content, POA/clay nanocom-
posite PPD provides a greater yield stress reduction than neat
POA. For instance, addition of 200 mg/kg and 400 mg/kg POA Doped with 400ppm POA/clay
depresses the yield stress to 16.3 Pa and 9.6 Pa, respectively. In WAT=34°C
comparison, 400 mg/kg and 800 mg/kg POA/clay nanocomposite

Heat Flow
Doped with 400ppm POA
PPD depresses the yield stress to 8.5 Pa and 1.7 Pa, indicative of
WAT=32°C
outstanding PPD performance at sparse dosage amounts. Addi-
tional yield stress reduction ascribed solely to the presence of Doped with 200ppm POA
nano-clay is quantified as 47.9% and 82.3% at overall dosages of
WAT=33°C
400 mg/kg and 800 mg/kg, respectively.
Undoped
WAT=36°C
3.4. DSC curves

DSC curves of waxy crude undoped/doped with POA and 0 10 20 30 40

POA/clay nanocomposite PPDs are shown in Fig. 6, providing a Temperature / °C
quantitative measure of the WAT. As temperature is progressively
Fig. 6. DSC curves of Changqing waxy crude oil undoped/doped with POA and
reduced, the heat flux signal gradually decreases and then
POA/clay nanocomposite PPDs.
increases sharply due to the paraffin wax precipitation phase
change. The WAT is quantitatively defined as the temperature at
which the heat flow signal deviates from the liquid state heat 3.5. Microscopic observation
capacity trend. From the DSC curves, the WAT of the original crude
oil is measured at 36 °C. When 200 mg/kg and 400 mg/kg POA are Microscopic images of crude oil undoped/doped with POA and
added, the WAT drops to 33 °C and 32 °C, respectively. When POA/clay nanocomposite PPD at 20 °C and 0 °C are shown in
400 mg/kg and 800 mg/kg POA/clay nanocomposite are added, Fig. 7. In the unmodified crude oil, precipitated wax crystals are
the WAT increases to 34 °C and 35 °C, respectively. POA reduces small and highly abundant, but exist in a haphazard arrangement
the WAT, while POA/clay nanocomposite PPD exhibits an opposing (Fig. 7a and b).
effect. Based on crystallization theory, a waxy crystal may exist in a After addition of 400 mg/kg POA, the wax crystal morphology
stable condition with growth only when its nucleus radius exceeds changes into larger flocs and becomes more regular while the crys-
the critical nucleation radius rk, which may be expressed as tal number density is substantially reduced, thus, the solid–liquid
follows: interfacial area decreases (Fig. 7c and d). When wax crystals are
modified by POA, continuous network formation is hindered, pro-
2rls MT e moting rheological beneficiation at temperature conditions below
rk ¼ ð1Þ
qDHp DT WAT. However, at 400 mg/kg POA, the structure of the wax crystal
flocs appear to be quite loose (occluding oil) instead of compact
where rls is the interfacial tension between new wax crystals and and also a large number of fine wax crystals are evident in the
liquid phase, M is the molecular mass of wax, T e is the equilibrium images.
transformation temperature, q denotes the paraffin wax crystal After addition of 800 mg/kg POA/clay nanocomposite PPD
density, DHp denotes wax precipitation enthalpy and DT is the (Fig. 7e and f), the size of the precipitated wax crystals in the crude
super-cooling degree. As reported in several literatures [3,8,10,30], oil continuously increases, and the structure of the wax crystal
polymeric PPDs serve to simultaneously increase rls and decrease flocs may become more compact and regular, occluding a smaller
DHp , effectively increasing the critical nucleation radius as well as fraction of oil. In addition, there is an almost complete absence
the nucleation potential barrier of wax crystals, promoting the of fine wax crystals in the oil benefitted with nanocomposite
effective (but not equilibrium) solubility of wax molecules in the PPD. The increased size and compactness of wax crystals favor
oil phase, thereby inhibiting wax precipitation. The presence of the further improvement of crude oil rheology.
organic nano-clay promotes wax crystal nucleation by providing Based on Fig. 7, characteristic parameters of the precipitated
heterogeneous nucleation sites, thereby circumventing the effective wax crystals are obtained and shown in Table 3. These characteris-
solubilizing effect relevant to neat POA. Hence, the observed tic parameters elucidate morphological variation of the wax
WAT value recovers with an increasing additive concentration of crystals before/after the addition of PPDs. For the original crude
POA/clay nanocomposite PPD. oil, precipitated wax crystals are present in large amounts at
 B. Yao et al. / Fuel 166 (2016) 96–105 103

Fig. 7. Microscopic images of Changqing waxy crude oil undoped/doped with POA and POA/clay nanocomposite PPDs: undoped at 20 °C (a) and 0 °C (b); doped with 400 mg/
kg POA at 20 °C (c) and 0 °C (d); doped with 800 mg/kg POA/clay nanocomposite PPDs at 20 °C (e) and 0 °C (f).

20 °C (Nwc = 7968) and are of small size (Deac = 1.722 lm). At a the complexity and space filling ability of wax crystal microstruc-
temperature of 0 °C, the number of precipitated wax crystals ture increases with decreasing temperature, as well as substantiat-
decreases slightly (Nwc = 6886) while the crystal size increases sig- ing incorporation of small crystals into larger crystals during the
nificantly (Deac = 2.989 lm). Wax crystal formation occurs in two continuing crystallization process. When the crude oil is doped
steps, nucleation and growth. Nucleation is dominant at the rela- with 400 mg/kg POA, the number of precipitated wax crystals
tively higher temperature (20 °C), leading to large amounts of decreases (Nwc = 4552 at 20 °C and 1494 at 0 °C) while the size of
small crystals. With the further reduction in temperature, growth the precipitated wax crystals increases (Deac = 2.079 lm at
becomes dominant and the existed wax crystals grow into larger 20 °C and 4.422 lm at 0 °C). When the crude oil is doped with
crystals due to continuous precipitation of wax crystals with 800 mg/kg POA/clay nanocomposite PPDs, the number of
decreasing temperature. Therefore, larger crystals are observed at precipitated wax crystals is further reduced and the crystal aggre-
0 °C. In addition, the fractal dimension of wax crystals at 20 °C gate size is further increased. Nwc is 1418 at 20 °C and 670 at 0 °C.
(D = 1.407) is smaller than that at 0 °C (D = 1.534), meaning that The formed wax crystal size increases in the presence of 800 mg/kg
104 B. Yao et al. / Fuel 166 (2016) 96–105

Table 3
Microscopic images analysis of Changqing waxy crude oil undoped/doped with POA and POA/clay nanocomposite PPDs.

Temperature condition (°C) Condition of PPD dosage Total wax crystals number (Nwc) Average equal-area-circle diameter Fractal dimension (D)
of wax crystals (Deac) (lm)
20 Undoped 7968 1.722 1.407
Doped with 400 mg/kg POA 4552 2.079 1.457
Doped with 800 mg/kg POA/clay 1418 2.442 1.503
0 Undoped 6886 2.989 1.534
Doped with 400 mg/kg POA 1494 4.422 1.653
Doped with 800 mg/kg POA/clay 670 6.646 1.700

Fig. 8. Possible mechanism of POA/clay nanocomposite PPD for improving the flowability of waxy crude oil.

nanocomposite PPD. Deac increases to 2.442 lm at 20 °C and result in larger and more compact wax morphologies (average size
6.646 lm at 0 °C. After the addition of POA/clay nanocomposite around 10 lm, see Fig. 7). The large size (reduction of solid–liquid
PPDs, the wax crystals become more compact and regular, and interfacial area) and compact structure (less occluded oil) of the
the solid–liquid interfacial area is also greatly reduced, favoring wax crystals are adverse for the formation of a strong gel network
rheological beneficiation. Meanwhile, the value of the fractal structure. Therefore, the rheological flowability properties of waxy
dimension D increases to 1.503 at 20 °C and 1.700 at 0 °C, indicat- crude oil are further improved.
ing that the complexity and space filling ability of wax crystal
microstructure is further enhanced upon addition of POA/clay
4. Conclusions
nanocomposite PPD.
The microscopic observation at the same conditions was
In this article, POA/clay nanocomposite PPD is successfully pre-
repeated in order to make sure the reproducibility of the test,
pared by dispersing the organic nano-clays in POA PPD matrix. It is
obtained results of which were shown in Support Information file
found that POA molecules increase the lipophilicity of nano-clay
(Fig. S9 and Table S2). Comparing Fig. 7 and Table 3 with Fig. S9
further and POA molecules strongly interact with the organic
and Table S2, it could be concluded that the reproducibility of
nano-clay and are hard to desorb from the surface of clay particles.
the microscopic observation is good.
The effect of the POA/clay nanocomposite PPD on the rheology and
wax crystal precipitation habit of Changqing waxy crude oil are
well studied. A possible heterogeneous nucleation mechanism for
3.6. Mechanism of POA/clay nanocomposite PPD
the POA/clay nanocomposite PPD is proposed here that the POA/-
clay nanocomposite particles dispersed in crude oil effectively pro-
Neat POA acts as an effective PPD for waxy crude oil by promot-
vide micro sized solid–liquid interface sites as wax precipitation
ing the solubility of wax molecules in oil phase and modify the wax
templates, which results in larger and more compact wax mor-
crystal morphology to larger flocs through adsorption and co-
phologies. And the large size (reducing the wax crystal/oil inter-
crystallization effects.
face) and compact structure (less liquid oil is entrapped in the
According to Table S1, POA/clay nanocomposite PPD shows
wax crystal structure) of the wax crystals are adverse for the for-
improved viscosity reduction than pure POA at various rest times,
mation of a network structure and favor the rheological properties
indicating that POA molecules interact strongly with the organic
improvement of waxy crude oil.
nano-clay and are difficult to desorb. A possible heterogeneous
nucleation mechanism for the POA/clay nanocomposite PPD is pro-
posed in the current work (see Fig. 8). It appears that the POA/clay Acknowledgments
nanocomposite particles dispersed in crude oil may effectively pro-
vide nano/micro sized solid–liquid interface sites (average size This work was financially supported by National Natural
around 6 lm, see Fig. 4) as wax precipitation templates, which Science Foundation of China – China (51204202), Natural Science
 B. Yao et al. / Fuel 166 (2016) 96–105 105

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