Dai 2018

Subscriber access provided by Columbia University Libraries
Fossil Fuels
Influence of Resins on Crystallization and Gelation of Waxy Oils
Jialin Dai, Jinjun Zhang, and Chaohui Chen
Energy Fuels, Just Accepted Manuscript • DOI: 10.1021/acs.energyfuels.8b03488 • Publication Date (Web): 11 Dec 2018
Downloaded from http://pubs.acs.org on December 12, 2018
Just Accepted
“Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted
online prior to technical editing, formatting for publication and author proofing. The American Chemical
Society provides “Just Accepted” as a service to the research community to expedite the dissemination
of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in
full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully
peer reviewed, but should not be considered the official version of record. They are citable by the
Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore,
the “Just Accepted” Web site may not include all articles that will be published in the journal. After
a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web
site and published as an ASAP article. Note that technical editing may introduce minor changes
to the manuscript text and/or graphics which could affect content, and all legal disclaimers and
ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or
consequences arising from the use of information contained in these “Just Accepted” manuscripts.
is published by the American Chemical Society. 1155 Sixteenth Street N.W.,

Washington, DC 20036
Published by American Chemical Society. Copyright © American Chemical Society.
However, no copyright claim is made to original U.S. Government works, or works
produced by employees of any Commonwealth realm Crown government in the
course of their duties.
Page 1 of 43 Energy & Fuels
1
2
3
4
5
6
7
8
Influence of Resins on Crystallization and
9
10
11
Gelation of Waxy Oils
12
13
14 Jialin Dai, Jinjun Zhang*, Chaohui Chen
15
16
17
18 National Engineering Laboratory for Pipeline Safety, Ministry of Education
19
20
21 (MOE) Key Laboratory of Petroleum Engineering, Beijing Key Laboratory of
22
23 Urban Oil & Gas Distribution Technology, China University of Petroleum
24
25
26 (Beijing), Beijing 102249, China
27
28
29
30 ABSTRACT: In the present work, we employed model oil systems to examine
31
32
33 the effects of resins upon the gelation and crystallization of waxy oils. Two types
34
35
36 of waxes were explored, namely n-tetracosane (Wax A) and a commercial wax
37
38 with a melting temperature of 52-54 °C (Wax B). The resins were extracted from
39
40
41 a deoiled asphalt from Venezuelan residue by SARA fractionation method. The
42
43
44 results from negative-ion ESI FT-ICR MS suggest that resins consist of 1-4
45
46
47
fused benzenes rings or 1-2 fused naphthalene rings constructed by N1, N1O1,
48
49 N1S1, N1O1S1, N1O2, O1, O1S1 and O2 class species containing stacking
50
51
52 aromatic rings. For both types of waxes examined, adding resins to the waxy
53
54
55 oils suppresses wax precipitation and modifies the morphology of wax crystals,
56
57 which collectively lead to lower gelation temperature and lower yield stress. Up
58
59
60 to 7 °C of reduction in gelation temperature, 60% of reduction in yield stress,
ACS Paragon Plus Environment

Energy & Fuels Page 2 of 43
1
2
3
4 and 6 °C of reduction in wax appearance temperature were achieved when the
5
6
7 waxy oils contain 7 wt% resins. While for the Wax A model oil, the gelation
8
9
10 temperature decreases gradually with increasing resin content, for the Wax B
11
12 model oil the resin effect is pronounced only at the resin concentration below
13
14
15 0.2 wt%. The reduction in yield stress caused by adding resins is also greater
16
17
18 for the Wax A model oil than Wax B model oil. The different resin effects for the
19
20
21
Wax A model oil and Wax B model oil might be caused by the compositional
22
23 variations between Wax A and Wax B.
24
25
26
27
1. INTRODUCTION
28
29
30
31 Wax contained in crude oils is generally the normal alkanes, which have carbon
32
33
34 number ranging from C17 to C55 [1]. When the oil temperature is above WAT (wax
35
36
appearance temperature), wax is dissolved in waxy oils. When the oil
37
38
39 temperature is below the WAT, dissolved wax starts to precipitate out and form
40
41
42 wax crystals. This wax precipitation can cause a variety of issues for the safe
43
44
45 transportation of waxy oils [2-7].
46
47
48 Asphaltenes are heavy fractions of crude oils, which are insoluble in n-pentane or n-
49
50
heptane but soluble in benzene or methylbenzene [8]. Asphaltenes are complex
51
52
53
54
molecules that contain condensed aromatic rings, naphthenic rings, alkyl chains and
55
56 heteroatoms [9]. It has been shown that the aromatic core of an asphaltene molecule is
57
58
59 surrounded by a number of naphthenic rings, and both of aromatic cores and naphthenic
60

1
2
3
4 rings contain alkyl chains [10]. Asphaltene molecules can associate into aggregates, or
5
6
7 even clusters if conditions are favorable [11]. Resins are another type of heavy fraction
8
9
10 of crude oils, which are soluble in n-pentane or n-heptane. Resins are chemically similar
11
12 to asphaltenes and contain condensed aromatic rings, naphthenic rings, alkyl chains and
13
14
15 heteroatoms as well. N1, N2, N1O1, N1O2, N2O1, N1S1, S1, S2, S3, O1S1, O1S2, O2S1, O1
16
17
18 and O2 class species have been identified by Fourier Transform Ion Cyclotron
19
20 [12-14],
Resonance Mass Spectrometry (FT-ICR MS) which consist of fused benzenes
21
22
23 rings or naphthalene rings. The π−π interactions between the resin molecules can drive
24
25
26 resin molecules aggregate into particles, whose sizes enlarge when resin concentrations
27
28
29 are increased [15]. The interactions between resin molecules result in the crystal structure
30
31 of resins. Results from XRD showed that three peaks centered at 2θ =20°~60° can be
32
33
34 observed for resins [16].
35
36
37
38 Both asphaltenes and resins have been shown to affect the rheological properties of
39
40 waxy oil [15, 17-22]. The effects of asphaltenes on gelation temperature, yield stress, WAT,
41
42
43 and structure of wax crystals of waxy oil have been studied for many years, but the
44
45
46 literature still contains conflicting views [17-20]. Many studies have reported that adding
47
48
asphaltenes can decrease the gelation temperature, yield stress and WAT of waxy oil
49
50
51 [17-19]. Nevertheless, higher asphaltenes concentration can also increase the WAT [19].
52
53
54 Moreover, an unexpected “high peak” of gelation temperature, yield stress and WAT
55
56 [20].
57 were observed around asphaltene concentrations of 0.01% In addition to
58
59 concentration, asphaltene aggregation state is also a factor that can affect the gelation
60

1
2
3
4 and crystallization of waxy oil [19]. Dispersed asphaltenes could inhibit wax crystal
5
6
growth, and aggregated asphaltenes could bridge wax crystals [21], which is in good
7
8
9
10 agreement with the low concentration asphaltenes decreasing WAT and high
11
12 concentration asphaltenes increasing WAT [19]. Asphaltenes also could make wax
13
14
15 crystals become globular from rod-like and smaller in shape and lead to the formation
16
17
18 of a weaker gel [22].
19
20
21 The effects of resins on viscosity of waxy oils have been studied. The viscosity of
22
23
24 waxy oils has been found to increase with the increasing resin content [15, 23-25]. Besides,
25
26
the resins can affect the performances of the magnetic treatment [26] [27] and chemical
27
28
29
30
treatment [28] [29] of waxy oil. Almost all previous studies focused on the effects of
31
32 resins on viscosity, whereas the impacts on the gelation and crystallization of
33
34
35 waxy oils have received just limited prior attention. Our current work is intended
36
37
38 to fill these gaps. We examined the influence of resins upon the gelation and
39
40 crystallization of waxy oils. Two types of model oil systems were employed. The
41
42
43 effects of resins on the gelation temperature and yield stress of model oils were
44
45
46 first presented. Then the influences of resins on WAT, precipitated wax
47
48
49
concentration, structure of wax crystals were studied to reveal how resins affect
50
51 the gelation temperature and yield stress of model oils.
52
53
54
55 2. Materials and methods
56
57
58 2.1. Materials
59
60

1
2
3
4 The resins were extracted from a deoiled asphalt from Venezuelan residue
5
6
7 by SARA fractionation method. The procedure is outlined in Figure 1 [30]. The
8
9
10 asphaltenes of a deoiled asphalt from Venezuelan residue was n-heptane
11
12 insoluble. The SARA mass fractions are listed in Table 1.
13
14
15
16
17
18
19
20
21
22
23
24
25
26 Figure 1. Separation procedure of saturates, aromatics, resins and
27
28
29 asphaltenes.
30
31
32
33
Table 1. Quantitative assays of saturates, aromatics, resins and asphaltenes in
34
35 Venezuelan deoiled asphalt
36
37
38
39 fractions yields (wt%)
40
41
42
Saturates 1.51
43
44
45
46 Aromatics 8.01
47
48
49
50
Resins 30.18
51
52
53 Asphaltenes 56.36
54
55
56
57 In order to independently control the resin concentration, two types of model
58
59 oil systems were employed, and the synthetic procedure has been reported [31].
60

1
2
3
4 Both two types of model oil systems were composed of waxes, resins, 97%
5
6
7 pure n-decane, and 97% pure o-xylene, which provided solubility for the resins.
8
9
10 The concentrations of waxes in the mode oils were maintained at 15 wt %, the
11
12 concentrations of o-xylene in the mode oils were maintained at 30 wt % and
13
14
15 resins concentrations in the model oils were varied from 0 wt % to 7 wt %,
16
17
18 respectively. The n-decane and o-xylene were obtained from Aladdin Group
19
20
21
Company, Limited. Two types of waxes were explored, namely Wax A (the
22
23 analytically pure n-tetracosane) obtained from Aladdin Group Company,
24
25
26 Limited and Wax B (a commercial wax with a melting temperature of 52-54 °C)
27
28
29 obtained from Sinopharm Chemical Reagent Company, Limited. Wax A only
30
31 has the n-C24 and Wax B has a continuous carbon-number distribution ranging
32
33
34 from C14 to C37, which contains 84% n-alkanes and 16% branched- and cyclo-
35
36
37 alkanes as shown in Figure 2.
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60

1
2
3
4 Figure 2. Composition of Wax B as determined by high temperature gas
5
6
7 chromatography (HTGC).
8
9
10
2.2. Resin fractionation and characterization
11
12
13
14 Resins were firstly fractioned into subfractions of different polarity, namely
15
16
17 Resins 1 (R1), Resins 2 (R2) and Resins 3 (R3), and then each subfraction was
18
19
further fractioned into acidic, alkaline and neutral subfractions. FT-ICR was
20
21
22 employed to analyze the resins molecules [12-14]: Acidic resins molecules can
23
24
25 be analyzed by Negative-Ion Electrospray Ionization Fourier Transform Ion
26
27
28 Cyclotron Resonance-Mass Spectrometry (Negative-Ion ESI FT-ICR), alkaline
29
30 resins molecules can be analyzed by Positive-Ion Electrospray Ionization
31
32
33 Fourier Transform Ion Cyclotron Resonance-Mass Spectrometry (Positive-Ion
34
35
36 ESI FT-ICR), and neutral resins molecules can be analysis by both negative-
37
38
ion ESI FT-ICR and positive-ion ESI FT-ICR.
39
40
41
42 1g resins were firstly fractioned into Resins 1 (R1), Resins 2 (R2) and Resins
43
44
45 3 (R3) using the solvent systems in sequence: (1) n-heptane/benzene (85:15,
46
47
v/v, 100 mL), (2) n-heptane/benzene (1:1, v/v, 100 mL), (3) benzene/ethanol
48
49
50 (1:1, v/v, 40 mL), benzene (40 mL), ethanol(40 mL). The procedure is outlined
51
52
53 in Figure 3 [32]. The mass fractions of Resins 1, Resins 2 and Resins 3 are listed
54
55
56 in Table 2.
57
58
59
60

1
2
3
4
5
6
7
8
9
10
Figure 3. Separation procedure of Resins1, Resins2, Resins3.
11
12
13
14 Table 2. Quantitative assays of Resins1, Resins2 and Resins3 in parent resins.
15
16
17
18 subfractions yields (wt%)
19
20
21 Resins1 37.36
22
23
24
25 Resins2 27.57
26
27
28 Resins3 33.53
29
30
31
32 Residue amount 1.54
33
34
35
1g Resins X (X was 1, 2 and 3) were fractioned into Acidic Resins X, Neutral
36
37
38 Resins X and Alkaline Resins X. Resins X (X was 1, 2 and 3) were fractionated
39
40
41 into Acidic Resins X and non - Acidic Resins X though an alkaline alumina
42
43
44 (about 40g, 100-200 mesh, with 9 wt% H2O) using the solvent systems in
45
46 sequence: (1) benzene (100 mL), (2) benzene/ethanol (1:1, v/v, 40 mL),
47
48
49 benzene (40 mL), ethanol (40 mL). Non - Acidic Resins X were fractionated into
50
51
52 Neutral Resins X and Alkaline Resins X though an acidic alumina (about 40g,
53
54
100-200 mesh, with 4 wt% H2O) column using the solvent systems in sequence:
55
56
57 (1) cyclohexane/ethyl acetate (4:1, v/v, 100 mL), (2) benzene/ethanol (1:1, v/v,
58
59
60 40 mL), benzene (40 mL), ethanol (40 mL). The procedure is outlined in Figure

1
2
3
4 4 [12]. The Acidic Resins X, Neutral Resins X and Alkaline Resins X mass
5
6
7 fractions are listed in Table 3.
8
9
10
11
12
13
14
15
16
17
18
19
20
21 Figure 4. Separation procedure of Acidic Resins X, Neutral Resins X and
22
23
24
Alkaline Resins X, X is 1, 2 and 3.
25
26
27 Table 3. Quantitative assays of Acidic Resins X, Neutral Resins X and Alkaline
28
29
30 Resins X in Resins X.
31
32
33 subfractions yields (wt%)
34
35
36
37 Acidic Resins 1 4.02
38
39
40
41
Neutral Resins 1 94.11
42
43
44 Alkaline Resins 1 0
45
46
47
49
50
51 Neutral Resins 2 87.58
52
53
54
56
57
59
60

1
2
3
4 Neutral Resins 3 58.63
5
6
7
9
10
11 Acidic Resins X and Neutral Resins X (X was 1, 2 and 3) were recovered,
12
13
14 both of which can be analyze by negative-ion ESI FT-ICR. Bruker Apex Ultra
15
16
17 FT-ICR MS equipped with a 9.4 T superconducting magnet and ESI in negative-
18
19
20
ion model [12] was employed to analyze the molecular composition of R1, R2
21
22 and R3. The sample preparation for negative-ion ESI FT-ICR analysis and the
23
24
25 equipment operating conditions and data processing have been reported [12, 33-
26
27 35].
28
29
30
31 2.3. Differential Scanning Calorimetry
32
33
34
35 Both the WAT and the precipitation curve of the model oils were determined
36
37
via a TA Q20 differential scanning calorimeter. The sample was placed into
38
39
40 sealed aluminum crucible to prevent the evaporation of solvent. A sample was
41
42
43 initially heated to 80 °C fast, held at 80 °C for 1 min, and cooled to −20 °C with
44
45
46 a rate of 5 °C/min to induce wax precipitation [36] [37].
47
48
49 2.4. Rheological Measurements.
50
51
52
53 2.4.1. Gelation Temperature.
54
55
56 The gelation temperature of the model oils was determined via a stress-controlled
57
58
59 HAAKE RS150HIII rheometer, which was equipped with concentric cylinder
60

1
2
3
4 geometry [31]. A sample was heated to the 50 °C, held at 50 °C for 10 min, and
5
6
7 cooled with a rate of 0.5 °C/min while subjecting to oscillatory shear stress of
8
9
10 0.02 Pa and 0.5 Hz at rheometer. The magnitude and frequency of the imposed
11
12 stress have been pre-determined to ensure that the sample behaves in the
13
14
15 linear viscoelasticity region. The gelation temperature was defined as the
16
17
18 temperature at which the crossover of G′ and G″ takes place.
19
20
21 2.4.2. Yield Stress.
22
23
24
25 The yield stress of the model oils was determined via an Anton PaarRheolab
26
27
28 QC rheometer, which was equipped with concentric vane geometry [31]. A
29
30 sample was heated to the 50 °C, held at 50 °C for 10 min, and cooled to the
31
32
33 desired testing temperature with a rate of 0.5 °C/min and held for 30 min at
34
35
36 rheometer. The shear stress was increased with a rate of 50 Pa/min, and the
37
38
shear strain of the sample was recorded simultaneously. The yield stress was
39
40
41 defined as the stress at which a sudden increase in the shear strain was
42
43
44 observed.
45
46
47
2.5. Microscopy
48
49
50
51 The morphology of resins and wax crystals was determined via a Nikon
52
53
54 OPTIPHOT2-POL polarizing microscope, which was equipped with a Linkam
55
56
PE60 cooling station, and were captured via a CCD digital camera [31]. A sample
57
58
59 was heated to the 50 °C, held at 50 °C for 10 min, and cooled to the desired
60

1
2
3
4 testing temperature with a rate of 0.5 °C/min. The particle size distribution of
5
6
7 resins particles and the fractal dimension of wax crystals were determined via
8
9
10 Image J software. The 12 images were analyzed to ensure the reliability of
11
12 results at each condition.
13
14
15
16 2.6. X-ray diffraction
17
18
19
The crystal structure of resins and wax crystals were determined via X-ray
20
21
22 diffraction at the temperature of 20 °C. The high-speed centrifuge was used to
23
24
25 separate wax crystals from the model oils. The separation procedure is as follows [36]:
26
27
28
(1) The model oil was heated to the 50 °C, and then placed in a centrifuge tube. (2) The
29
30 centrifuge tube was loaded into the centrifuge cell and held at 50 °C for 10 min. (3) The
31
32
33 model oil was then cooled to 8 °C at a rate of 0.5 °C/min and held at 8 °C for 30 min.
34
35
36 (4) At 8 °C, the model oil was centrifuged for 45 min at a speed of 12,000 rpm. (5) The
37
38
wax crystals were collected and used for the subsequent X-ray diffraction experiments.
39
40
41 The wavelength of the X-rays was 0.154 nm. A sample was placed in the
42
43
44 sample holder and scanned in the Bragg angle ranging from 1.0 to 35° with a
45
46
47 rate of 8°/min. The diffraction intensities were recorded at a step size of 0.02°
48
49 in 2θ [36].
50
51
52
53 3. Results and discussion
54
55
56
The results of resins characterization including molecular structure and
57
58
59 aggregation state have been firstly reported. Then the effects of resins on the
60

1
2
3
4 gelation temperature and yield stress are presented. The influence of resins on
5
6
7 crystallization containing WAT, precipitated wax concentration, morphology
8
9
10 and crystal structure of wax crystals are discussed in the end.
11
12
13 3.1. Resins Characterization
14
15
16
17 In this section, the molecular structure of resins is firstly discussed. Then the
18
19
aggregation state is presented.
20
21
22
23 3.1.1. Molecular structure
24
25
26
27
The broad-band negative-ion ESI FT-ICR MS spectra of subfractions R1−R3
28
29 is displayed in Figure 5. The data shows that the molecular weight of resins
30
31
32 ranges from 200 to 600Da. The relative abundance of the dominant class
33
34
35 species in resins is displayed on Figure 6. N1, N1O1, N1S1, N1O2, N1O1S1, O1,
36
37
O1S1, and O2 species are observed in the resins.
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
6. 吸收峰
58
59
60

1
2
3
4 Figure 5. Broad-band negative-ion ESI FT-ICRMS spectrum of the subfractions
5
6
7 R1−R3.
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28 Figure 6. Relative abundances of the dominant class species in subfractions
29
30 R1−R3.
31
32
33
34 The isoabundance maps of DBE as a function of the carbon number for N1,
35
36
37 N1O1, and N1S1 class species can be seen in Figure 7 and those for O1, O1S1,
38
39 O2 and N1O2 class species can be seen in Figure 8. The DBE distribution center
40
41
42 for N1O1 and N1S1 species is at 14, and the DBE distribution center for N1
43
44
45 species is at 12 in Resins 1. An enhancement of 2 shows that oxygen could be
46
47
in furanic and sulfur atoms could be in thiophenic rings [12]. N1, N1O1 and N1S1
48
49
50 species have a higher DBE and higher carbon number distribution center in
51
52
53 Resins 2 and Resins 3, which show that molecular structures of Resins 2 and
54
55
56 Resins 3 may contain more condensed aromatic rings. The O1 and O1S1
57
58 species could be phenolic compounds and sulfur - containing phenolic
59
60

1
2
3
4 compounds [12]. The O2 class species could be carboxylic acids, whose DBE
5
6
7 carbon number distribution center is at 2 (no rings), naphthenic acids, whose
8
9
10 DBE carbon number distribution center is ranging from 3 to 6 (2−5 naphthenic
11
12 rings) and aromatic acids whose DBE carbon number distribution center is
13
14
15 more than 5 [12]. The N1O2 class species could be nitrogen-containing carboxylic
16
17
18 acids, whose DBE carbon number distribution center is ranging from 11 to 14
19
20 [12].
21
The molecular structures of N1, N1O1, N1S1, O1, O1S1, O2 and N1O2 species
22
23 [12] can be seen in the insets of Figure 7 and Figure 8, which consist of 1-4 fused
24
25
26 benzenes rings or 1-2 fused naphthalene rings.
27
28
29
30
Almost all resins molecules are amphoteric compounds containing two basic
31
32 moieties: a polar moiety and a nonpolar moiety, which is similar to polymeric
33
34
35 wax inhibitors and pour point depressants [22]. Polar moieties could be pyrrole
36
37
38 rings, phenol rings, furanic rings, thiophenic rings, sulfur-containing phenol
39
40 rings, whose benzenes rings varying from 1 to 4 or naphthalene rings varying
41
42
43 from 1 to 2. Nonpolar moieties could be long alkyl chains. Resins may interact
44
45
46 with wax crystals via nucleation, adsorption or co-crystallization or solubilization
47
48 [22].
49
50
51
52
53
54
55
56
57
58
59
60

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33 Figure 7. Isoabundance maps of DBE as a function of the carbon number for
34
35 N1, N1O1 and N1S1 class species.
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60

1
2
3
4 Figure 8. Isoabundance maps of DBE as a function of the carbon number for
5
6
7 O1, O1S1, O2 and N1O2 class species.
8
9
10
3.1.2. Aggregation state
11
12
13
14 The aggregation state of asphaltenes has been reported to significantly affect
15
16
17 their interactions with wax [19] [21]. Thus, it is necessary to examine the
18
19
aggregation state of resins [15] under the conditions examined. The
20
21
22 concentrations of waxes and o-xylene in the mode oils were maintained at 15
23
24
25 wt % and 30 wt %, respectively. The particle size distribution of resins at
26
27
28 concentrations of 1 wt%, 3 wt% and 7 wt% is shown in Figure 9. These
29
30 measurements were conducted at 40 °C which is higher than the WAT to avoid
31
32
33 the presence of wax crystals. Figure 9 demonstrates the particle size
34
35
36 distribution of resins at different concentrations. When the resin content is
37
38
below 3 wt%, the resin particles are smaller in size and have a narrower size
39
40
41 distribution compared to those observed at 7 wt%. As resin concentration
42
43
44 reaches 7 wt%, the fraction of resins ranging from 1 to 2 μm dramatically
45
46
47 decreases and those above 10 μm dramatically increases. These results
48
49 suggest that high concentration resins could promote the self-aggregation of
50
51
52 resin particles, which is in good agreement with the findings from previous
53
54
55 research [15], and this trend may be attributed to the fact that increasing resin
56
57
58
59
60

1
2
3
4 concentration diminishes the distances between resin molecules thus
5
6
7 facilitating resin assembling.
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28 Figure 9. Particle size distribution of resins. The concentrations of waxes and
29
30 o-xylene in the mode oils were maintained at 15 wt % and 30 wt %, respectively.
31
32
33
34 3.2. Effect of resins on rheological properties of waxy oils
35
36
37
In this section, the effects of resins on gelation temperature and yield stress
38
39
40 of waxy oils are discussed, which are crucial for safety of waxy oil
41
42
43 transportations and successful restart operations.
44
45
46
3.2.1. Gelation temperature
47
48
49
50 The effect of the resins on the gelation temperature is displayed on Figure
51
52
53 10. For both waxy oil systems, an increase in resin concentration results in a
54
55 decrease in the gelation temperature. Up to 7 °C of reduction in the gelation
56
57
58 temperature is achieved when the waxy oil contains 7 wt% resins. The
59
60

1
2
3
4 decreasing trend of gelation temperature is in good agreement with the effects
5
6
7 of some asphaltenes [17-19] and pour point depressants [38]. The molecular
8
9
10 structures of resins, as one of heavy fractions of crude oil, are similar to
11
12 asphaltenes, indicating that interaction between resins and wax is similar to
13
14
15 asphaltenes. It may also be caused by the fact that the molecular structures of
16
17
18 resins are similar to pour point depressants, co-crystallizing with wax.
19
20
21
Regardless, the result suggests that the resins can act as a natural gelation
22
23 temperature depressant.
24
25
26
27 The efficiency of the resins on decreasing the gelation temperature depends
28
29
30
on the polydispersity of the wax. For the Wax A model oil, the gelation
31
32 temperature gradually decreases from 17.1 °C to 12.5 °C with increasing resin
33
34
35 content, and for the Wax B model oil, the resins effect is pronounced only at the
36
37
38 resin concentration below 0.2 wt%, and the gelation temperature remarkably
39
40 decreases from 24.5 °C to 18.5 °C at the concentration of 0.2 wt%. The stronger
41
42
43 effect of resins at low concentration for Wax B waxy oil may be caused by the
44
45
46 compositional variations between Wax A and Wax B. Wax A only has n-C24 and
47
48
49
Wax B has n-alkanes, branched- alkanes and cyclo-alkanes ranging from C14
50
51 to C37. The performance may be caused by wax polydispersity or may be
52
53
54 caused by branched- alkanes and cyclo- alkanes. The presence of the resin
55
56
57 may have a percolation threshold for the Wax B model oil, which is similar to
58
59 the percolation effect of micro-crystalline wax in altering the aspect ratio [39].
60

1
2
3
4 The resins are active as gelation suppressers at concentrations of 0.2 wt%,
5
6
7 while the micro-crystalline wax is active at concentrations above 1 wt%. The
8
9
10 resins may have higher interfacial activity than micro-crystalline wax.
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30 Figure 10. Effect of resins on gelation temperature of model oils.
31
32
33
34 3.2.2. Yield stress
35
36
37
The effect of the resins on the yield stress at 8 °C is displayed on Figure 11.
38
39
40 For both waxy oil systems, an increase in the resin concentration results in a
41
42
43 decrease in the yield stress. Up to 60% of reduction in the yield stress is
44
45
46 achieved when the waxy oil contains 7 wt% resins. The decreasing trend in the
47
48 yield stress is also in good agreement with the effects of some asphaltenes [17-
49
50
51 19] and pour point depressants [38]. The aggregation state of resins is similar to
52
53
54 asphaltenes, indicating that interaction between resins and wax crystals may
55
56
cause waxy oils to form softer gels. It may also be caused by the fact that the
57
58
59
60

1
2
3
4 molecular structures of resins are similar to those of pour point depressants,
5
6
7 thus interrupting wax crystal growth [22].
8
9
10
The efficiency of the resins on decreasing the yield stress depends on the
11
12
13 polydispersity of the wax. The reduction in yield stress caused by adding resins
14
15
16 is greater for the waxy oil containing Wax A than Wax B. For the Wax A model
17
18
19 oil, the resin effect is pronounced at the resin concentration of 1 wt%, where
20
21 the yield stress remarkably decreases from 4200 Pa to 2400 Pa. For the Wax
22
23
24 B model oil, the yield stress gradually decreases from 1900 Pa to 600 Pa with
25
26
27 increasing resin concentration. Stronger effect of resins at low concentration for
28
29
30
Wax A model oil may be caused by the compositional variations between Wax
31
32 A and Wax B. Wax A only has n-C24, which can crystalize into triclinic crystals
33
34
35 [36] and Wax B has n-alkanes, branched-alkanes and cyclo-alkanes ranging
36
37
38 from C14 to C37, which can crystalize into orthorhombic crystals [36]. The triclinic
39
40 crystals may be affected by resins easier than orthorhombic crystals. The
41
42
43 effects of resin on the behaviors of Wax A model oil is similar to the influences
44
45
46 of micro-crystalline wax upon the behaviors of waxy oils containing macro-
47
48
49
crystalline wax [39].
50
51
52
53
54
55
56
57
58
59
60

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21 Figure 11. Effect of resins on yield stress of model oils.
22
23
24
25 3.3. Effect of resins on wax crystallization
26
27
28
Wax crystallization causes the formation of waxy gels. In this section, the
29
30
31 effects of resins on wax crystallization are first discussed, which include WAT,
32
33
34 precipitated wax concentration at both gelation temperature and 8°C,
35
36
37 morphology and crystal structure of wax crystals. Then the results are used to
38
39 analyze the effects of resins on gelation temperature and yield stress.
40
41
42
43 3.3.1. WAT
44
45
46
The effect of the resins on the WAT is displayed on Figure 12. For both waxy
47
48
49 oil systems, an increase in resin concentration results in a decrease in WAT.
50
51
52 Up to 6 °C of reduction in WAT is achieved when the waxy oil contains 7 wt%
53
54
55
resins. The decrease in WAT demonstrate that resins suppress wax
56
57 precipitation and model oil needs to be decreased ΔT1 further to precipitate
58
59
60 wax (ΔT1 is defined as the difference between the WAT of virgin model oil and

1
2
3
4 the WAT of resins-contained model oil, ΔT1A for Wax A model oil and ΔT1B for
5
6
7 Wax B model oil). Adding resins decreases the thermodynamic phase transition
8
9
10 temperature of waxy oils, and increases the solubility of waxes in waxy oils.
11
12 Contradictory trends are observed regarding the influence of asphaltenes [40]
13
14
15 and pour point depressants [41] on the wax appearance temperature. Hence the
16
17
18 decrease in WAT is in good agreement with the effects of some asphaltenes
19
20
21
[18] and is contrary to with the effects of other asphaltenes [20].The decrease in
22
23 WAT is in good agreement with the effects of the comb-type pour point
24
25
26 depressants [41] and is contrary to the effects of co-polymerized ethylene pour
27
28
29 point depressants [41].
30
31
32 The efficiency of resins on decreasing the WAT depends on the polydispersity
33
34
35 of the wax. While for the Wax A model oil, the WAT gradually decreases from
36
37
38 18.4 °C to 14.3 °C with increasing resin content, and for the Wax B model oil,
39
40 the resins effect is pronounced only at the resin concentration below 0.2 wt%,
41
42
43 with the WAT remarkably decreasing from 25.4 °C to 21.1 °C when the resin
44
45
46 content increases from 0 to 0.2 wt%. At low resin concentrations, the effect of
47
48
49
resins on Wax B model oil is higher than Wax A model oil, which could be
50
51 caused by enhancement activity of the high concentration of cyclo+branched
52
53
54 alkanes [22] of Wax B.
55
56
57
58
59
60

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21 Figure 12. Effect of resins on WAT of model oils, ΔT1A for Wax A model oil and
22
23
24 ΔT1B for Wax B model oil.
25
26
27
28 3.3.2. Precipitated wax concentration at gelation temperature
29
30
31 The effect of resins on the precipitated wax concentration at gelation
32
33
34 temperature is displayed on Figure 13. For both waxy oil systems, adding resins
35
36
37 results in an increase in precipitated wax concentration at gelation temperature,
38
39 which shows that more precipitated wax is needed to cause the formation of
40
41
42 waxy gels for resins-contained waxy oils and shows that adding resins may lead
43
44
45 the formation of weak gels. In addition, adding resins results in precipitated wax
46
47
concentrations having the variation tendency of M type, indicating a variety of
48
49
50 interactions between resins and wax at different resin contents.
51
52
53
54 The increase in precipitated wax concentration at gelation temperature shows
55
56
that resins–contained model oils need to be decreased ΔT2 further to
57
58
59 precipitate enough wax concentration to cause the formation of waxy gels (ΔT2
60

1
2
3
4 is the gelation temperature of resins-contained model oil subtracted the
5
6
7 temperature when the precipitated wax concentration of resins-contained
8
9
10 model oil is equal to the precipitated wax concentration of virgin model oil at
11
12 gelation temperature, ΔT2A for Wax A model oil and ΔT2B for Wax B model oil).
13
14
15 The effect of resins on precipitated wax concentration at gelation temperature
16
17
18 depends on the polydispersity of the wax, which may be caused by fact that the
19
20
21
compositional variations between Wax A and Wax B. According to percolation
22
23 theory, resins may reduce the aspect ratio of both Wax A crystals and Wax B
24
25
26 crystals, which leads to more precipitated wax at the gelation temperature [42].
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45 Figure 13. Effect of resins on precipitated wax concentration of Wax A model
46
47
48 oil (Left) and Wax B model oil (Right) at gelation temperature, ΔT2A for Wax A
49
50
51 model oil and ΔT2B for Wax B model oil.
52
53
54 Both the suppressed wax precipitation (increasing the solubility of waxes in
55
56
57 waxy oil) and modified wax crystals (increasing the precipitated wax
58
59
60 concentration at gelation temperature) contribute to the decrease in the gelation

1
2
3
4 temperature of waxy oils to some extent. At temperatures below the WAT,
5
6
7 adding resins cause waxy oils to be decreased ΔT2 further to precipitate
8
9
10 enough wax concentration to format waxy gels. The ΔT2 is displayed on Figure
11
12 14. ΔT2A is less than 1 °C, which is less than the decrease in gelation
13
14
15 temperature of Wax A model oils. ΔT2B is less than 3 °C, which is less than the
16
17
18 decrease in gelation temperature of Wax B model oils. Besides changing wax
19
20
21
crystals, there could be others factors leading to the decrease in the gelation
22
23 temperature of model oils. At temperatures above the WAT, adding resins leads
24
25
26 model oils to be decreased ΔT1 further to precipitate wax. The ΔT1 is also
27
28
29 displayed on Figure 14. ΔT1A is up to 4 °C and ΔT1B is up to 6 °C, which could
30
31 be another factor leading to the decrease in the gelation temperature of model
32
33
34 oils. In addition, the noticeable decrease in gelation temperature of Wax B
35
36
37 model oils at low resin concentrations is in good agreement with the noticeable
38
39
40
decrease in WAT caused by cyclo+branched alkanes at the low resin
41
42 concentration.
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60

1
2
3
4 Figure 14. ΔT1 and ΔT2 of Wax A model oil (Left) and Wax B model oil (Right),
5
6
7 A is resin concentration of Wax A model oil, B is resin concentration of Wax B
8
9
10 model oil.
11
12
13 3.3.3. Precipitated wax concentration at 8 °C
14
15
16
17 The effect of resins on the precipitated wax concentration at 8 °C is displayed
18
19
on Figure 15. For both waxy oil systems, an increase in resin concentration
20
21
22 results in a decrease in precipitated wax concentration at 8 °C, which shows
23
24
25 that resins suppress wax precipitation. The effect of resins suppressing wax
26
27
28 precipitation is in good agreement with the effect of resins decreasing the wax
29
30 appearance temperature. The efficiency of the resins on decreasing the
31
32
33 precipitated wax concentration at 8 °C depends on the polydispersity of the
34
35
36 wax. The decrease in precipitated wax concentration at 8 °C caused by adding
37
38
resins is higher for Wax A model oils than Wax B model oils.
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60

1
2
3
4 Figure 15. Effect of resins on precipitated wax concentration of model oils at 8
5
6
7 °C.
8
9
10
3.3.4. Microscopic analysis of wax crystals
11
12
13
14 The microscopic analysis of wax crystals at 8 °C is displayed on Figure 16
15
16
17 and Figure 17. Wax A crystals are branch–like, which is in good agreement with
18
19
the effects of pour point depressants on the dotriacontane model oil [43]. In order
20
21
22 to confirm these crystals are indeed wax crystals, the system was heated to 40
23
24
25 °C (above WAT) and held for 10 min. The disappearance of crystals at higher
26
27
28 temperatures confirmed our speculation. The process can be seen in Figure
29
30 18. Bright spots have been observed in Figure 18 (D). Note that there is no wax in
31
32
33 this model oil, and hence the bright spots are not wax crystals. Due to the crystal
34
35
36 structure of resins [16], those bright spots could be the resins particles caused
37
38
by the stacking aromatic rings[15] of N1, N1O1, N1S1, O1, O1S1, O2 and N1O2
39
40
41 species.
42
43
44
45 For both waxy oil systems, resins observably changed the structure of wax
46
47
crystals at 8 °C, especially the Wax A crystals. Moreover, the influence of the
48
49
50 resins on structure depends on the polydispersity of the wax. The Wax A
51
52
53 crystals are slice-like in the virgin model oil, and branch-like in the resins-
54
55
56 contained model oil. Resin particles may provide 1-D restricted geometry to
57
58 wax crystal, which may cause the 1-D confined crystallization [44]. Resins may
59
60

1
2
3
4 also act as natural pour point depressants, whose nonpolar groups may co-
5
6
7 crystalize with wax and incorporate into wax crystals. The Wax B crystals are
8
9
10 rod- like in the virgin model oil, and smaller, needle-like in the resins-contained
11
12 model oil. The fractal dimension [31] of Wax A crystals and Wax B crystals is
13
14
15 displayed in Figure 19. The increase in resin concentration results in the
16
17
18 decrease in fractal dimension.
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48 Figure 16. Microscope images of Wax A model oil at 8 °C, A: 0% resins, B: 1%
49
50
51 resins, C: 3% resins, D: 7% resins.
52
53
54
55
56
57
58
59
60

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31 Figure 17. Microscope images of Wax B model oil at 8 °C, A: 0% resins, B: 1%
32
33
34 resins, C: 3% resins, D: 7% resins.
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60

1
2
3
4 Figure 18. Microscope images of branch-like crystals is heated, A : 8 °C, B : 18
5
6
7 °C, C : 20 °C, D : 40 °C and held for 10min.
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28 Figure 19. Area box fractal dimension of Wax A crystals and Wax B crystals at
29
30 8 °C.
31
32
33
34 3.3.5 Crystal structure of wax crystals
35
36
37 We first performed X-ray diffraction of resins, and the result is shown in Figure 20.
38
39
40 One peak is observed at 2θ ≈ 20°, indicating that resin particles contain crystal structure.
41
42
43 This observation is also confirmed by previous research [16].
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60

1
2
3
4 Figure 20. Powder diffraction patterns (λ = 0.154 nm) of resins, 2θ =5°~30°.
5
6
7
8 The X-ray diffraction of wax crystals at 8 °C is displayed on Figure 21. For
9
10
both model oil systems, adding resins considerably affect the structure of wax
11
12
13 crystals, especially those in Wax A model oil. Moreover, the influence of resins
14
15
16 depends on the polydispersity of the wax. The disappearance of (001) series in
17
18
19 Wax A crystals and (002) series in Wax B crystals demonstrates that resin
20
21 particles may provide 2-D restricted geometry to wax crystals, which may cause
22
23
24 the 2-D confined crystallization and a randomization of the z-coordinates for
25
26
27 both Wax A and Wax B crystals [45]. For Wax A crystals, the change of the peaks
28
29
30
at 2θ≈20°~25°may be caused by the co-crystallization between resins and wax
31
32 [22]. For Wax B crystals, adding resins do not change the peaks at 2θ≈20°~25°,
33
34
35 suggesting that wax crystals may not be modified by resins, which may be
36
37
38 caused by the co-crystallization of alkanes molecules of Wax B.
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60

1
2
3
4 Figure 21. Powder diffraction patterns (λ = 0.154 nm) of Wax A crystals and
5
6
7 Wax B crystals at 8 °C, A : Wax A crystals, 2θ=1°~10°, B: Wax A crystals,
8
9
10 2θ=10°~35°, C: Wax B crystals, 2θ=1°~10°, D : Wax B crystals, 2θ=10°~35°.
11
12
13 Resins suppressing wax precipitation lead to the decrease in precipitated wax
14
15
16 concentration at 8 °C. Resins changing wax crystals lead to the change of both
17
18
19 morphology and crystal structure of wax crystals. For both model oil systems,
20
21 there is little decrease in precipitated wax concentration at the resin
22
23
24 concentration of 1 wt%, but noticeable decrease in yield stress. Hence the
25
26
27 resins changing wax crystals could be the major factor leading to the decrease
28
29
30
in yield stress at the resin concentration of 1 wt%, which could be morphology
31
32 or crystal structure or both. There is almost nothing changed in both of
33
34
35 morphology and crystal structure at the resin concentration varied from 1 wt%
36
37
38 to 7 wt%, and the resins suppressing wax precipitation could be the major factor
39
40 leading to the decrease in yield stress.
41
42
43 4. Conclusion
44
45
46
Resins consist of 1-4 fused benzenes rings or 1-2 fused naphthalene rings
47
48
49 constructed by N1, N1O1, N1S1, N1O1S1, N1O2, O1, O1S1 and O2 class species.
50
51
52 The interaction of resin molecules results in larger resin particles at higher resin
53
54
55 contents and cause resin particles to have crystal structure.
56
57
58
59
60

1
2
3
4 The effects of resins upon the gelation and crystallization of waxy model oils
5
6
7 were studied. Both monodisperse n-tetracosane (Wax A) and polydisperse
8
9
10 commercial wax (Wax B) were examined. For both types of waxes, adding
11
12 resins to the waxy oils suppresses wax precipitation and leads to the formation
13
14
15 of weaker gels. Wax appearance temperature has been found to decrease with
16
17
18 increasing resin content. More precipitated wax is required to induce the
19
20
21
gelation of resins-contained waxy oils. The precipitated wax concentration at
22
23 the gelation temperature varies with the resin contents in an irregular “M”
24
25
26 manner, indicating a variety of interactions between resins and wax at different
27
28
29 conditions. Up to 7 °C of reduction in gelation temperature and 6 °C of reduction
30
31 in wax appearance temperature were achieved when the waxy oils contain 7
32
33
34 wt% resins.
35
36
37
38 The effects of resins on gelation temperature, yield stress, crystallization
39
40 depend on wax composition. While for the Wax A model oil, the gelation
41
42
43 temperature decreases gradually with increasing resin content, for the Wax B
44
45
46 model oil the resin effect is pronounced only at the resin concentration below
47
48
49
0.2 wt%. The reduction in yield stress caused by adding resins is also greater
50
51 for the Wax A model oil than Wax B model oil, especially at low resin
52
53
54 concentration. The resins cause the formation of branch-like crystals for the
55
56
57 Wax A model oil, and smaller, needle-like crystals for Wax B model oil.
58
59
60

1
2
3
4 AUTHOR INFORMATION
5
6
7
8 Corresponding Authors
9
10
11 *Telephone: 86-10-8973-4627. E-mail: [email protected].
12
13
14
15 ACKNOWLEDGMENT
16
17
18
The authors greatly acknowledge the financial support from the National
19
20
21 Natural Science Foundation of China (51534007). The authors thank Yingda
22
23
24 Lu at the China University of Petroleum (Beijing) for his intensive editions.
25
26
27 References
28
29
30 (1) Huang, Z.Y.; Zheng, S.; Fogler, H. S. Wax Deposition: Experimental
31
32
33 Characterizations, Theoretical Modeling, and Field Practices; CRC Press: Boca
34
35 Raton, FL, 2015.
36
37
38
39 (2) Ma, C. B.; Lu, Y. D.; Chen, C. H.; Feng, K.; Li, Z. X.; Wang, X. Y.; Zhang,
40
41
42 J. J. Electrical treatment of waxy crude oil to improve its cold flowability.
43
44 Industrial & Engineering Chemistry Research 2017, 56, 10920−10928.
45
46
47
48 (3) Lu, Y. D.; Huang, Z. Y.; Hoffmann, R.; Amundsen, L.; Fogler, H. S.
49
50
51 Counterintuitive effects of the oil flow rate on wax deposition. Energy Fuels
52
53 2012, 26 (7), 4091−4097.
54
55
56
57
58
59
60

1
2
3
4 (4) Huang, Z. Y.; Lu, Y. D.; Hoffmann, R.; Amundsen, L.; Fogler, H. S. The
5
6
7 effect of operating temperatures on wax deposition. Energy Fuels 2011, 25
8
9
10 (11), 5180−5188.
11
12
13 (5) Liu, H. F.; Lu, Y. D.; Zhang, J. J. A comprehensive investigation of the
14
15
16 viscoelasticity and time-dependent yielding transition of waxy crude oils.
17
18
19 Journal of Rheology 2018, 62 (2), 527-541.
20
21
22 (6) Liu, H. F.; Zhang, J. J.; Lu, Y. D. Yielding characterization of waxy gels by
23
24
25 energy dissipation. Rheologica Acta 2018, 57 (6), 473-480.
26
27
28
(7) Li, M.; Sun, M. R.; Lu, Y. D.; Zhang, J. J. Experimental study on the
29
30
31 strength of original samples of wax deposits from pipelines in the field. Energy
32
33
34 Fuels 2017, 31 (11), 11977-11986.
35
36
37
(8) Speight, J. G. The Chemistry and Technology of Petroleum, 3th ed.;
38
39
40 Marcel Dekker: New York, 1999.
41
42
43
44 (9) Sjoblom, J.; Aske, N.; Auflem, I. H.; Brandal, O.; Havre, T. E.; Saether, O.;
45
46
Westvik, A.; Johnsen, E. E.; Kallevik, H. Our current understanding of water-in-
47
48
49 crude oil emulsions.: Recent characterization techniques and high pressure
50
51
52 performance. Advances in Colloid and Interface Science 2003, 100−102,
53
54
55
399−473.
56
57
58
59
60

1
2
3
4 (10) Mullins, O. C.; Sabbah, H.; Eyssautier, J.; Pomerantz, A. E.; Barre,́ L.;
5
6
7 Andrews, A. B.; Ruiz-Morales, Y.; Mostowfi, F.; McFarlane, R.; Goual, L.;
8
9
10 Lepkowicz, R.; Cooper, T.; Orbulescu, J.; Leblanc, R. M.; Edwards, J.; Zare, R.
11
12 N. Advances in asphaltene science and the yen-mullins model. Energy Fuels
13
14
15 2012, 26 (7), 3986−4003.
16
17
18
19 (11) Hoepfner, M. P.; Fogler, H. S. Multiscale scattering investigations of
20
21 asphaltene cluster breakup, nanoaggregate dissociation, and molecular
22
23
24 ordering. Langmuir 2013, 29 (49), 15423− 15432.
25
26
27
28 (12) Wang, L. T.; He, C.; Zhang, Y. H.; Zhao, S. Q.; Chung, K. H.; Xu, C. M.;
29
30 Hsu, C. S.; Shi, Q. Characterization of acidic compounds in heavy petroleum
31
32
33 resid by fractionation and negative-ion electrospray ionization fourier transform
34
35
36 ion cyclotron resonance mass spectrometry analysis. Energy Fuels 2013, 27
37
38
(8), 4555−4563.
39
40
41
42 (13) Zhu, X. C.; Shi, Q.; Zhang, Y. H.; Pan, N.; Xu, C. M.; Chung, K. H.; Zhao,
43
44
45 S. Q. Characterization of nitrogen compounds in coker heavy gas oil and its
46
47
subfractions by liquid chromatographic separation followed by fourier transform
48
49
50 ion cyclotron resonance mass spectrometry. Energy Fuels 2011, 25 (1), 281–
51
52
53 287.
54
55
56
(14) Shi, Q.; Pan, N.; Liu, P.; Chung, K. H.; Zhao, S. Q.; Zhang, Y. H.; Xu, C.
57
58
59 M. Characterization of sulfur compounds in oilsands bitumen by methylation
60

1
2
3
4 followed by positive-ion electrospray ionization and fourier transform ion
5
6
7 cyclotron resonance mass spectrometry. Energy Fuels 2010, 24 (5), 3014–
8
9
10 3019.
11
12
13 (15) Li, T.; Xu, J.; Zou, R.; Feng, H.; Li, L.; Wang, J. Y.; Stuart, M. A. C; Guo,
14
15
16 X. H. Resin from Liaohe heavy oil: molecular structure, aggregation behavior,
17
18
19 and effect on oil viscosity. Energy Fuels 2017, 32(1), 306-313.
20
21
22 (16) Sun, Q. X. The research of nature about Liaohe heavy oil and its heavy
23
24
25 components after thermal reaction. Master Dissertation, College of Chemical
26
27
28 Engineering, Beijing University of Chemical Technology, Beijing, 2014.
29
30
31 (17) Venkatesan, R.; Ostlund, J. A.; Chawla, H.; Wattana, P.; Nyden, M.;
32
33
34 Fogler, H. S. The effect of asphaltenes on the gelation of waxy oils. Energy
35
36
37 Fuels 2003, 17 (6), 1630−1640.
38
39
40 (18) Alcazar-Vara, L. A.; Garcia-Martinez, J. A.; Buenrostro-Gonzalez, E.
41
42
43 Effect of asphaltenes on equilibrium and rheological properties of waxy model
44
45
46 systems. Fuel 2012, 93 (1), 200− 212.
47
48
49 (19) Tinsley, J. F.; Jahnke, J. P.; Dettman, H. D.; Prud’home, R. K. Waxy gels
50
51
52 with asphaltenes 1: Characterization of precipitation, gelation, yield stress, and
53
54
55
morphology. Energy Fuels 2009, 23 (4), 2056−2064.
56
57
58
59
60

1
2
3
4 (20) Kriz, P.; Andersen, S. I. Effect of asphaltenes on crude oil wax
5
6
7 crystallization. Energy Fuels 2005, 19 (3), 948−953.
8
9
10
(21) Lei, Y.; Han, S. P.; Zhang, J. J.; Bao, Y. Q.; Yao, Z. W.; Xu, Y. N. Study
11
12
13 on the effect of dispersed and aggregated asphaltene on wax crystallization,
14
15
16 gelation, and flow behavior of crude oil. Energy Fuels 2014, 28 (4), 2314−2321.
17
18
19
(22) Yang, F.; Zhao, Y. S.; Sjoblom, J.; Li, C. X.; Paso, K. G. Polymeric wax
20
21
22 inhibitors and pour point depressants for waxy crude oils: a critical review.
23
24
25 Journal of Dispersion Science and Technology 2015, 36 (2), 213–225.
26
27
28
(23) Ilyin, S. O.; Pakhmanova, O. A.; Kostyuk, A. V.; Antonov, S. V. Effect of
29
30
31 the asphaltene, resin, and wax contents on the physicochemical properties and
32
33
34 quality parameters of crude oils. Petroleum Chemistry 2017, 57 (12), 1141-
35
36
37 1143.
38
39
40 (24) Ilyin, S. O.; Arinina, M. P.; Polyakova, M. Y.; Kulichikhin, V. G.; Malkin,
41
42
43 A. Y. Rheological comparison of light and heavy crude oils. Fuel 2016, 186,
44
45
46 157-167.
47
48
49 (25) Malkin, A. Y.; Rodionova, G.; Simon, S.; Ilyin, S. O.; Arinina, M. P.;
50
51
52 Kulichikhin, V. G.; Sjoblom, J. Some compositional viscosity correlations for
53
54
55
crude oils from Russia and Norway. Energy Fuels 2016, 30 (11), 9322-9328.
56
57
58
59
60

1
2
3
4 (26) Loskutova, Y. V.; Yudina, N. V. Effect of constant magnetic field on the
5
6
7 rheological properties of high-paraffinicity oils. Colloid Journal 2003, 65 (4),
8
9
10 469–473.
11
12
13 (27) Loskutova, Y. V.; Yudina, N. V. Effect of constant magnetic field on the
14
15
16 structural and mechanical properties of paraffin-base crude oils. Petroleum
17
18
19 Chemistry 2004, 44 (1), 58-62.
20
21
22 (28) Song, X.; Yin, H. Y.; Feng, Y. J.; Zhang, S.; Wang, Y. Effect of SiO2
23
24
25 nanoparticles on wax crystallization and flow behavior of model crude oil.
26
27
28 Industrial & Engineering Chemistry Research 2016, 55 (23), 6563-6568.
29
30
31 (29) Jin, W. B.; Jing, J. Q.; Wu, H. F.; Yang, L.; Li, Y.; Shu, X. B.; Wang, Y. L.
32
33
34 Study on the inherent factors affecting the modification effect of EVA on waxy
35
36
37 crude oils and the mechanism of pour point depression. Journal of Dispersion
38
39 Science and Technology 2014, 35 (10), 1434-1441.
40
41
42
43 (30) Wang, Y. F.; Cheng, J. A.; Jian, S. S.; Shen, B. X. Investigation on the
44
45
46 compatibility and incompatibility of vacuum residua with catalytic cracking
47
48 bottom oil. Energy Fuels 2003, 17 (2), 344-347.
49
50
51
52 (31) Li, Y. Z.; Han, S. P.; Lu, Y. D.; Zhang, J. J. Influence of asphaltene
53
54
55
polarity on crystallization and gelation of waxy oils. Energy Fuels 2018, 32 (2),
56
57 1491−1497.
58
59
60

1
2
3
4 (32) Ren W. P.; Chen H. G.; Yang C. H.; Shan H. H. Molecular size
5
6
7 characterization of heavy oil fractions in vacuum and solution by molecular
8
9
10 dynamic simulation. Frontiers of Chemical Engineering in China 2010, 4 (3),
11
12 250–256.
13
14
15
16 (33) Shi, Q.; Hou, D. J.; Chung, K. H.; Xu, C. M.; Zhao, S. Q.; Zhang, Y. H.
17
18
19 Characterization of heteroatom compounds in a crude oil and its saturates,
20
21 aromatics, resins, and asphaltenes (SARA) and non-basic nitrogen fractions
22
23
24 analyzed by negative-ion electrospray ionization fourier transform ion cyclotron
25
26
27 resonance mass spectrometry. Energy Fuels 2010, 24 (4), 2545−2553.
28
29
30 (34) Shi, Q.; Xu, C. M.; Zhao, S. Q.; Chung, K. H. Characterization of
31
32
33 heteroatoms in residue fluid catalytic cracking (RFCC) diesel by gas
34
35
36 chromatography and mass spectrometry. Energy Fuels 2013, 23 (12), 6062-
37
38
6069.
39
40
41
42 (35) Shi, Q.; Pan, N.; Long, H. Y.; Cui, D. C.; Guo, X. F.; Long, Y. H.; Chung,
43
44
45 K. H.; Zhao, S. Q.; Xu, C. M.; Hsu, C.S. Characterization of middle-temperature
46
47
gasification coal tar. Part 3: Molecular composition of acidic compounds.
48
49
50 Energy Fuels 2013, 27 (1), 108−117.
51
52
53
54 (36) Zhu, L. L. Role of n-alkane polydispersity on the gelation of crude oil.
55
56
Master Dissertation, Beijing Key Laboratory of Urban Oil & Gas Distribution
57
58
59 Technology, China University of Petroleum (Beijing), Beijing, 2013.
60

1
2
3
4 (37) Chen, J.; Zhang, J. J.; Li, H. Y. Determining the wax content of crude oils
5
6
7 by using differential scanning calorimetry. Thermochimica Acta 2004, 410 (1-
8
9
10 2), 23-26.
11
12
13 (38) Yao, B.; Li, C. X.; Yang, F.; Sjoblom, J.; Zhang, Y.; Norrman, J.; Paso,
14
15
16 K.; Xiao, Z. Q. Organically modified nano-clay facilitates pour point depressing
17
18
19 activity of polyoctadecylacrylate. Fuel 2016, 166, 96-105.
20
21
22 (39) Kurniawan, M.; Subramanian, S.; Norrman, J.; Paso, K. Influence of
23
24
25 microcrystalline wax on the properties of model wax-oil gels. Energy Fuels
26
27
28 2018, 32 (5), 5857-5867.
29
30
31 (40) Paso, K. G. Comprehensive treatise on shut-in and restart of waxy oil
32
33
34 pipelines. Journal of Dispersion Science and Technology 2014, 35 (8), 1060-
35
36
37 1085.
38
39
40 (41) Paso, K. G.; Kruckert, K. K.; Oschmann, H. J.; Ali, H.; Sjoblom, J. PPD
41
42
43 architecture development via polymer-crystal interaction assessment. Journal
44
45
46 of Petroleum Science and Engineering 2014, 115, 38-49.
47
48
49 (42) Paso, K.; Senra, M.; Yi, Y.; Sastry, A. M.; Fogler, H. S. Paraffin
50
51
52 polydispersity facilitates mechanical gelation. Industrial & Engineering
53
54
55
Chemistry Research 2005, 44 (18), 7242-7254.
56
57
58
59
60

1
2
3
4 (43) Mao, R. The research of waxy crude oil crystal microscopic parameters
5
6
7 changing under different conditions. Master Dissertation, Beijing Key
8
9
10 Laboratory of Urban Oil & Gas Distribution Technology, China University of
11
12 Petroleum (Beijing), Beijing, 2013.
13
14
15
16 (44) Haubruge, H. G.; Daussin, R.; Jonas, A. M.; Legras, R. Morphological
17
18
19 study of melt-crystallized poly(ethylene terephthalate): B. Thin films. Polymer
20
21 2003, 44 (26), 8053-8059.
22
23
24
25 (45) Huber, P.; Wallacher, D.; Albers, J.; Knorr, K. Quenching of lamellar
26
27
28 ordering in an n-alkane embedded in nanopores. Europhysics Letters 2004, 65
29
30 (3), 351-357.
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60

Dai 2018

Uploaded by

Copyright:

Available Formats

Dai 2018

Uploaded by

Document Information

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Dai 2018

Uploaded by

Copyright:

Available Formats

Subscriber access provided by Columbia University Libraries

is published by the American Chemical Society. 1155 Sixteenth Street N.W.,

ACS Paragon Plus Environment

ACS Paragon Plus Environment

ACS Paragon Plus Environment

ACS Paragon Plus Environment

ACS Paragon Plus Environment

ACS Paragon Plus Environment

ACS Paragon Plus Environment

ACS Paragon Plus Environment

ACS Paragon Plus Environment

ACS Paragon Plus Environment

ACS Paragon Plus Environment

ACS Paragon Plus Environment

ACS Paragon Plus Environment

ACS Paragon Plus Environment

ACS Paragon Plus Environment

ACS Paragon Plus Environment

ACS Paragon Plus Environment

ACS Paragon Plus Environment

ACS Paragon Plus Environment

ACS Paragon Plus Environment

ACS Paragon Plus Environment

ACS Paragon Plus Environment

ACS Paragon Plus Environment

ACS Paragon Plus Environment

ACS Paragon Plus Environment

ACS Paragon Plus Environment

ACS Paragon Plus Environment

ACS Paragon Plus Environment

ACS Paragon Plus Environment

ACS Paragon Plus Environment

ACS Paragon Plus Environment

ACS Paragon Plus Environment

ACS Paragon Plus Environment

ACS Paragon Plus Environment

ACS Paragon Plus Environment

ACS Paragon Plus Environment

ACS Paragon Plus Environment

ACS Paragon Plus Environment

ACS Paragon Plus Environment

ACS Paragon Plus Environment

ACS Paragon Plus Environment

ACS Paragon Plus Environment

ACS Paragon Plus Environment

You might also like