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Article
UNDERSTANDING THE EFFECT OF CHEMICAL STRUCTURE
OF ASPHALTENES ON WAX CRYSTALLIZATION
OF CRUDE OILS FROM COLORADO OIL FIELD
Daniel R. Molina V., Emiliano Ariza Leon, and Arlex Chaves-Guerrero
Energy Fuels, Just Accepted Manuscript • DOI: 10.1021/acs.energyfuels.7b01149 • Publication Date (Web): 03 Aug 2017
Downloaded from http://pubs.acs.org on August 4, 2017

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Page 1 of 24 Energy & Fuels

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UNDERSTANDING THE EFFECT OF CHEMICAL STRUCTURE OF ASPHALTENES ON
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5 WAX CRYSTALLIZATION OF CRUDE OILS FROM COLORADO OIL FIELD
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7 Daniel Molina V.a, Emiliano Ariza Leóna, Arlex Chaves-Guerrerob
8
a
9 Laboratorio de Resonancia Magnética Nuclear, Universidad Industrial de Santander, Bucaramanga, Colombia.
b
10 Escuela de Ingeniería Química, Universidad Industrial de Santander, Bucaramanga, Colombia
11
12
13 ABSTRACT: In a previous article (Molina et al.)1 the structural differences of asphaltenes in
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15 Colombian light crude oils from the same field, i.e., the Colorado oilfield, were presented. Colorado
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crude oil is a light crude with very low content of asphaltenes (<0.3 % wt / wt) and presents paraffin
17
18 crystallization problems during its production. In the parafinic deposits, asphaltenes have also been
19
20 found. In this work, a new methodology is proposed to determine the effects of chemical structure and
21
22 concentration of asphaltenes on the wax crystallization of the crude oils from the Colorado oilfield. Six
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crude oils (from different sands) were fractionated in their respective asphaltenes and maltenes. The
25 crystallization properties of crudes oils and maltenes were obtained: wax appearance temperature
26
27 (WAT), pour point and crystallization enthalpy. Asphaltenes were characterized by Nuclear Magnetic
28
29 Resonance (NMR), Mass Spectrometry (MS), X-Ray diffraction (DRX) and Raman, and their main
30
31 average molecular parameters (AMP's) were calculated. Partial least squares regression (PLS) analysis
32
was used to understand the influence of asphaltenes chemical structure on the crystallization processes.
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34
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36 The proposed characterization-statistical analysis methodology allowed for the understanding of the
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38 effect of the average molecular structure of asphaltenes on the crystallization properties of paraffins
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40
from the crude oils of the Colorado Field. The effect of asphaltenes was analyzed through correlation
41 between the differences in WAT, the differences in pour point and the relative crystallization (Cr) with
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43 the AMP´s of asphaltenes.
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45
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47 The AMPs of the asphaltenes causing the greatest impact on the increase of the crystallization
48 temperature are the pericondensed carbons (Caaa), ratio of peripheral carbons / aromatic carbons (Cp/Car)
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50 and aromaticity factor (fa), and decreases in these properties are attributed to the length of the aliphatic
51
52 chains (n) and the naphthenic rings (Cn); the concentration of asphaltenes (Coasf) has little effect. The
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54 degree of crystallization is increased by fa and decreased with Caaa, Cp/Car, paraffinic carbons (Cs) and
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56
Coasf. The pour point is only increased by fa and decreased with Caaa and Cn; and the concentration of
57 asphaltenes (Coasf) is negligible.
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1. INTRODUCTION
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7 Petroleum is a complex mixture of hydrocarbons and molecules and other elements (Speight)2 such as
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9 nitrogen, oxygen, sulfur, and metals, as well as water and fines of solid rocks (fines). The simplified
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11
model of petroleum suggested by Pfeiffer and Saal3 is based on four fractions (Hammami and
12 Ratulowski,)4: Saturate, Aromatic, Resins and Asphaltenes (SARA), which are defined based on
13
14 solubility and polarity (Aske).5 The maltenes are defined as crude deasphalted, namely, it is composed
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16 of the fractions of saturates, resins and aromatics. However, the saturates (waxes with heavy
17
18 hydrocarbons, C16 +) and the asphaltenes can cause problems during the extraction and transportation
19 of crude oils as changes in pressure, temperature and composition can precipitate them and become
20
21 organic deposits (OD).
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23
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25 Paraffins are apolar molecules that tend to precipitate from the crude below their crystallization points,
26
27
and Van der Waals forces prevail among their interactions. The crystallization of paraffins is governed
28 by three successive phenomenons, which are nucleation, growth, and agglomeration.
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30
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32 Denis et al.6 proposed basic equations for nucleation studies, such as the enthalpy of nucleation to the
33
34 critical size of crystal appearance and the nucleation frequency per unit volume, which experimentally
35 depend on supersaturation.
36
37
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39 Crystal growth occurs at sites where the cohesive surface energy between crystal and paraffin in solution
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41 is the most favorable. Growth is faster on the side faces, at a growth rate which increases with
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43
supersaturation and in structural orders such as mono and multimolecular layers in which the chains are
44 arranged in a zig-zag form. These layers are planar and parallel to one another, with their terminal
45
46 methyls parallel or perpendicular to the plane or oblique axis of the chain. Agrawal et al.7 determined
47
48 the angle C-C-C be approximately 112°, and in measured cases, it is 113.9° for C28 and C36 (Nyburg et
49
50 al.).8
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53 The crystallization process has been followed by microscopy, differential scanning calorimetry (DSC),
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55 X-ray diffraction (XRD), and nuclear magnetic resonance (NMR).9, 10, 11 Studies with XRD have shown
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57 that the n-alkanes CnH2n+2 (n > 6) crystallize into four isostructural assemblies according to the
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magnitude and parity of n. The alkanes crystallize into one of three systems: triclinic (n (even) < 26),
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5 monoclinic, orthorhombic for single compounds (26 < n (even) < 36), and orthorhombic (11 < n (odd) <
6
7 39). The crystallization depends on the parity of the number of carbons and the conditions of
8
9 crystallization; therefore, paraffin can crystallize into different polymorphic structures.6, 8
Scanning
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11
electron microscopy (SEM) analyses have shown that the morphologies adopted by the crystals are
12 mainly disks or tablets (when cooling is slow), needles (for quick cooling and if there are impurities) and
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14 irregularly packed dendrites, long crystals, parallelepipeds and pyramidal blocks.
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16
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18 Agglomeration occurs when the product is cooled below the crystallization point. The crystal size is
19 dramatically increased, and the rheological properties of the solution are modified. Finally, they become
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21 agglomerated, deposited or organized in rigid crystalline networks.
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25 The crystallization of paraffins during the production of petroleum is mainly caused by cooling of the
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crude oil; the temperature at which nucleation is evidenced, that is, the formation of solid paraffin less
28 than 0.1% in the crude at a given pressure is called the crystallization point (Ball et al.)12 or wax
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30 appearance temperature (WAT) or cloud point.
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32
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34 If the temperature continues falling below the WAT value, then the paraffin crystals start to grow and
35 depending on the hydrodynamic conditions of the flow, solid material accumulation may occur. The oil
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37 becomes even colder and can reach a temperature where the mobility is lost (pour point).
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41 Investigations on the influences of asphaltenes on the nucleation, growth, and agglomeration of paraffins
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43
have been made in crude oils, in synthetic hydrocarbon fluids and mixtures with inconclusive and
44 sometimes contradictory results.
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46
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48 Yang and Kilpatrick13 evaluated the chemical composition and molecular properties of five crude oils
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50 and their corresponding organic deposits using techniques such as Fourier Transform Infrared
51 Spectroscopy (FTIR), NMR and elemental analysis. The properties of asphaltenes from deposits were
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53 compared with the properties from their parent crude oils. They concluded that the asphaltenes are likely
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55 a component of the occluded oil in the deposit and there is no evidence for intermolecular interaction
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57 between asphaltenes and waxes, in other words, does not affect wax precipitation. Also, Chacon et al.14
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using High-Resolution Mass Spectrometry analyzed asphaltenes isolated from Colombian heavy crude
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5 oil and proposed that it would be possible that during the agglomeration of asphaltenes several
6
7 compounds such as saturated and biomarkers are occluded.
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9
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Other investigations have demonstrated that asphaltenes do interact with paraffins and affect the waxy
12 oil properties. For example, it has been reported that the presence of flocculated asphaltenes in the oil
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14 generates crystallization sites of waxes, increasing the crystallization temperature because of paraffins
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16 grow around the aggregated asphaltenes, forming a paraffin-asphaltenes mixture (Garcia, M.).15 The
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18 presence of asphaltenes dispersed in the crude can connect the smaller paraffin crystals, forming crystal
19 networks and accelerating the gelation processes (Lei et al.).16 In calorimetric studies by DSC on
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21 mixtures of asphaltenes and waxes, exothermic effects were noted in all the mixtures. This was
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23 explained by the partial dissolution of n-alkanes upon interacting with the lateral aliphatic chains of the
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25 asphaltenes, the almost solid nature of the partially immobilized alkanes caused the effect of wax
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nucleation and induced asphaltenes flocculation (Mahamoud et al.).17 Similar results were found by
27
28 other researchers.18, 19
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32 Orea et al.20 studied asphaltenes from Furrial and Ayacucho crude oils to test retention of alkane
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34 compounds on asphaltenes. The retention takes place on the alkyl chains of asphaltenes, and the n-
35 alkane compounds are the strongest retained. It was found that asphaltenes from the unstable Furrial
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37 crude (higher length alkyl chains) showed a higher capacity to retain alkanes than asphaltenes from the
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39 stable Ayacucho crude oil. These results open a new way to the interpretation of the interactions of
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41 asphaltenes and alkanes at a molecular level and to understand the role of both compound classes in the
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mechanisms of asphaltenes precipitation and wax crystallization.
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46 Carbognani and Rogel21 realized a study of dissolution kinetics for wax in toluene at 25°C using pure
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48 asphaltenes and complex mixtures formed for these fractions, to observe the interaction among each
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50
other. The authors found that the unstable asphaltenes have proved to be highly aromatic and devoid of
51 alkyl appendages. Consequently, their aromatic cores have extended possibilities for interaction.
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53 However, when waxes were mixed with these asphaltenes, alkanes deposit around the aromatic cores,
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55 forming an artificial alkyl layer that facilitates the steric repulsion of the aggregates favoring the elution
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57 by the carrier solvent used in the dissolution experiment. On the other hand, stable asphaltenes are less
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aromatic and enriched in alkyl moieties. It is presumed that alkyl chains already surround the particles
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5 forming a peripheral alkyl layer. In this way, steric repulsion is already existing among the particles
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7 thanks to the existing alkyl layer. When additional alkanes were added by mixing waxes with this type
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9 of asphaltenes, no significant steric repulsion was exerted, and consequently, no significant effect was
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11
noticed during the dissolution experiments. It is believed that the discussed results support the existence
12 of peripheral alkyl layers on stable low-aromatic asphaltenes. Also, support the creation of such a layer
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14 by the artificial mixing of unstable highly-aromatic asphaltenes with foreign alkane sources.
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16
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18 Carbognani et al.22 also found that asphaltenes affect the precipitation of paraffins. In their work they
19 took asphaltic cuts from two Venezuelan crude oils, one paraffinic and one naphthenoaromatic; also
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21 tested a 28.9 °API Venezuelan crude oil that had been stored for four years at ambient conditions
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23 (25°C, 0.9 atm), and slowly precipitated a solid sediment. Large molecular mass aromatic waxy
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25 compounds were characterized by chromatography and NMR. These authors determined that the alkyl
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chains are attached to the aromatic or naphthenic rings, or both. They also found that the asphaltenes
28 that interacted with alkanes to form the solid sediment were the more aromatic ones and with the longest
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30 average chain length on their alkane substituents. They concluded that the asphaltenes within the crude
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32 serve as nucleation centers for the precipitation of paraffins, driven by interactions with the alkyl
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34 substituents of these asphaltenes as the temperature of the crude oil drops.
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37 On the contrary, others researchers such as Venkatesan et al.23 found that asphaltenes in a network of
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39 paraffins turn weak the paraffins crystals, retarding the gelation processes of crude. In a study realized
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41 by Oh and Deo24 using seven oil models synthesized from two different waxes, asphaltenes taken from
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deposits of production, two different white mineral oil, kerosene, and toluene; it was found that 0.1%
44 wt/wt of asphaltenes caused a reduction in the pour point up to 4°C.
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48 Kriz and Andersen25 found that the concentration and the grade of dispersion of asphaltenes affect the
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50 paraffin crystallization in crude oil more than type or origin of the asphaltenes. They report that to very
51 low concentration, the asphaltenes are either dispersed or dissolved in the crude oil matrix and can
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53 interact with the waxes; when the crude oil is over-cooled, wax crystals form and grow, in which the
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55 asphaltenes can be incorporated until a critical concentration is reached where the crystal structure is the
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57 strongest and WAT is the highest. At concentrations slightly higher than the critical concentration,
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where complete dispersion cannot be maintained for the rest of the oil, the fragile balance is broken, and
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5 the asphaltenes molecules tend to flocculate with each other and adhere weakly to the wax crystal
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7 networks. Therefore, when there is a shear stress, the structure is broken at the weak points, and WAT
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9 drops.
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12 Other investigations have been carried out with commercial pure paraffins or mixtures dissolved in
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14 aromatic or aliphatic solvents or mixtures thereof, to which the authors have added crude asphaltenes to
15
16 study the phenomenon of crystallization. This helps the understanding of the phenomenon of
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18 crystallization, but does not represent the behavior of crude oils; therefore, it is necessary to continue to
19 research the subject deeply. Despite the wide spectrum of publications and scientific articles on this
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21 subject, there is still no consensus or agreement on the results regarding the effect of asphaltenes on the
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23 precipitation of paraffins.26
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25
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27
In this paper, we propose to determine the effects of chemical structure and concentration of asphaltenes
28 on the precipitation of paraffins in crude oils from the Colorado oilfield, Colombia. Asphaltenes were
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30 characterized by NMR, MS and Elemental Analysis to determine their main structural parameters, and
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32 PLS analysis was used to correlate the structural parameters of the asphaltenes with the change in the
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34 properties between maltenes and crude to evaluate the effect of chemical structure of the asphaltenes on
35 the crystallization of paraffins.
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37
38
39 2. EXPERIMENTAL
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43
2.1 Materials
44 Samples of six crude oils produced from B and C Colorado field sands, also from the blends B with C
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46 and C with E were used, and the characteristics are presented in Table 1. The Colorado Oilfield has
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48 proven reserves of 128 million barrels of oil with °API between 34 and 42°.1
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50
51 2.2 Extraction and characterization of asphaltenes and maltenes
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53
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55 Asphaltenes were obtained according to ASTM D6560-12 standard, using n-heptane (J.T. Baker,
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57 99.3%)/crude ratio of 20:1. The mixture was refluxed 1 hour at a temperature of 98 °C, allowed to stand
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for 24 hours and then filtered. Subsequently, the asphaltenes were extracted with n-heptane in a Soxhlet
4
5 until the solvent was clear. Toluene (J.T. Baker, 99,90%) was then added to the Soxhlet flask to dissolve
6
7 the asphaltenes until the solution in the Soxhlet was colorless. Finally, the toluene was removed by roto-
8
9 evaporation.
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11
12 2.2.1 Characterization of asphaltenes and maltenes
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14
15
16 The methodology used to calculate the AMPs of the asphaltenes was based on a combination of
17
18 Elemental Analysis, Matrix Assisted Laser Desorption and Ionization – Time of Flight (MALDI-TOF)
19 Mass Spectrometry, and 1H and 13C – Nuclear Magnetic Resonance. Elemental analysis was conducted
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21 using a Thermo Scientific Flash 2000 elemental analyzer. The MALDI-TOF spectra were acquired using
22
23 a Bruker Reflex II MALDI-TOF Mass Spectrometer equipped with a Nd:YAG laser emitting at the third
24
25 harmonic, 355 nm, with a repetition rate of 500 Hz and a pulse width of 3.5 ns. The TOF-MS analyzer
26
27
was operated in the reflector mode and was equipped with a microchannel plate detector. The reflection
28 plates were polarized at 25 kV to obtain a potential gradient according to the kinetic energy of the ions,
29
30 allowing the best reflection properties and refocusing the ions close to the detector. The asphaltenes
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32 were dissolved in a saturated solution of anthracene in toluene at approximately 3 wt%. An aliquot of 4
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34 µL of this solution was deposited in the MS holder, and the solvent was removed with a current of air.
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36
This procedure was repeated three times to concentrate the sample. Subsequently, the holder with the
37 asphaltenes was introduced into the spectrometer for measurement.
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39
40
41 The 1H and 13
C NMR measurements of the asphaltenes and the maltenes were obtained with a Bruker
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43 Avance III spectrometer operating at 400.16 and 100.63 MHz, respectively. The 1H NMR samples were
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45 4 wt% solutions in CDCl3 (Merck, 99.8% D, 0.03 %vol TMS), and the measurements were performed
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47
with 30° pulses (Bruker zg30 pulse sequence), a sweep width of 49000 Hz, 32K data points and a delay
48 time between scans of 10 s. Tetramethylsilane (TMS) was used as the reference, and 16 scans were
49
50 13
averaged for each spectrum. The C NMR samples were 10 wt% solutions in CDCl3 using Cr(acac)3
51
52 (Merck) as the paramagnetic relaxation reagent at 0.05 M concentration. The measurements were
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54 performed with 30° pulses (Bruker zgig30 pulse sequence), a sweep width of 22400 Hz, 32K data points
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56 and a delay time between scans of 20 s. The zgig30 pulse sequence suppresses the Overhauser effect and
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58
C to H coupling with an inverse gated decoupling sequence and composite pulse decoupling (CPD).
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Tetramethylsilane (TMS) was used as the reference, and 2000 scans were averaged for each spectrum.
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5 For both 1H and 13C NMR, the phase and baseline values of the resulting spectra were manually adjusted
6
7 and corrected using a very large expansion of the frequency axis.
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9
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11 For the processing of the NMR spectra, MestreNova 19.2.5 was used. For each spectra the phase,
12
baseline and scale were adjusted. The integration areas chosen of the spectra for both the 13C (Figure 1)
13
14 and 1H (Figure 2) those areas were standardized. . The ppm ranges over the NMR spectra were based on
15
16 the methodology proposed by Ferfoug et al.[30 (Tables 6 and 7). For each sample (crude oils or
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18 maltenes) the spectra processing was repeated for five times to finally obtain an average of the areas.
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20 The standard deviation of the areas was less than 0.1 for 1H and 1.0 in percentage points for 13C. With
21
22
the information obtained from elemental analysis, average weight molecular of MS and NMR spectra
23 finally AMP´s were calculated.
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25
26
27 2.3 Thermodynamic properties of maltenes and crude oils
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29
30 2.3.1 Crystallization temperature (Tc)
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32
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34 The crystallization temperature (Tc) or the wax appearance temperature (WAT) was determined for
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36 maltenes and crude oils using differential scanning calorimetry (DSC) following the ASTM D4419-90
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38
(2010) standard (TA Instruments Inc.). The samples were added to the sample holder (approximately 10
39 mg) and heated from room temperature to 120°C to melt the paraffins present. The cooling ramp was set
40
41 between 120° and -40°C at a rate of 3°C / min. The crystallization temperature (TC) was determined in
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43 the thermograms as the onset of the exothermal peak during the cooling process corresponding to the
44
45 liquid–solid transition. Experimental error was ± 1 °C.
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47
48 2.3.2 Relative crystallization (Cr)
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50
51
52 Relative crystallization (Cr) is defined in equation 1.
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55 ∆H Crystallization Enthalpy of Crude Oil
56 Cr = (1)
57 ∆H Crystallization Enthalpy of maltenes
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The crystallization enthalpy (∆H) was determined as the area under the curve of the thermograms and
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5 represented the amount of precipitated wax. According to Eq. (1), a Cr value of 1.0 means that there is
6
7 no effect of the asphaltenes on paraffin precipitation; less than 1.0 means that the asphaltenes decrease
8
9 the crystallization and greater than 1.0 means that they cause an increase. The relative error for the
10
11
change in enthalpy of crystallization was calculated at 4%.
12
13
14 2.3.3 Pour point
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16
17
18 The pour point of the maltenes and their respective crudes was determined according to ASTM D97-12
19 Standard using a circulating thermal bath with cooling to -20°C at a cooling rate of 1°C / min and a test
20
21 kit with a -30 to 150°C thermometer with ± 1°C accuracy. For each sample, the test was done in
22
23 duplicate, and the experimental error was ± 3°C.
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25
26
27
3. RESULTS AND DISCUSSION
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29
30 3.1 Characterization of asphaltenes
31
32
33
34 Table 2 shows the AMPs of the Colorado asphaltenes,1 which were characterized by elemental analysis
35 following spectroscopic techniques described before: MS28 NMR27, 29, 30, 31
, Raman32 and XRD.33
36
37 Studied asphaltenes show changes in the amount and distribution of carbon and hydrogen atoms. From
38
39 the aliphatic carbons (Cal), paraffinic carbons (Cs) are in greater proportion than naphthenic (Cn), and the
40
41 average length of the chains (n) varies between 3 and 7. The aromaticity factor (fa), defined as the ratio
42
43
of aromatic carbons (Car) to total carbons (Car + Cal), ranges from 0.46 to 0.61. When analyzing the
44 asphaltenes of the crude produced from different sands, the produced asphaltenes from sand B were
45
46 determined relatively more aromatic (0.56) than those of sand C (0.53) which is deeper. On the other
47
48 hand, those extracted from crudes that are mixtures of sands C and E are relatively more aromatic than
49
50 those of sand B-C and the asphaltenes of the crude Col CE-2 are the most aromatic (the deepest sand of
51 the oil field).
52
53
54
55 The number of aromatic rings (Ra) varies between 4 and 5. The ratio of peripheral to aromatic carbons
56
57 (Cp/Car) is between 0.74 and 0.66, and it is observed that higher the value, the smaller the number of
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rings of the asphaltenes average molecule, i.e., it is less condensed. The above agrees with the
4
5 condensation index Φ (0.26 to 0.34), that is, greater Φ indicates a greater abundance of internal carbons
6
7 and therefore higher number of rings (Figure 3).
8
9
10
11
The average molecular weight ranges from 547.5 to 589.3 g / mol.
12
13
14 Asphaltenes from the Col-CE2 crude oil have the largest size out of the asphaltene molecules (La) and
15
16 the highest aggregate height (Lc), confirming it as the most aromatic asphaltene of the Colorado crude
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18 oils. Also, it was observed by comparison between values of fa versus values La and Lc (BC-1, CE-1, B1
19 and CE-2) that a direct relationship exists (Table 2), indicating that the asphaltenes with greater fa have
20
21 large aromatic core (La) and this produces larger stacking.
22
23
24 3.2 Characterization of maltenes
25
26
27 13
28 The results of C and 1H-NMR analysis show variation in both the aromatic (Car) and aliphatic (Cal)
29
carbons and the Har and Hal protons among the crudes and their maltenes. The average content of the
30
31 aromatic carbons of the maltenes is 18.8% wt/wt, while that of the aliphatic carbons is 81.8% wt/wt
32
33 (Table 3, Figure 4). The maltenes from sand C have a higher aliphatic content than those of sand B, and
34
35 the maltenes from Col-CE2 (mixture of crude oils from C and E sands) have the highest content of
36
37 aromatic carbons.
38
39
40 The methodology applied to obtain 1H-NMR of the maltenes was based on Speight.29 The average
41
42 content of aliphatic protons (Hal) - Hγ, Hβ and Hα - is 96.6% wt/wt, while for aromatics, the average is
43
44 3.4% (Table 4, Figure 4); the highest aromatic proton content occurred for Col-CE2 at 8.77% wt/wt.
45
46
47 To know the relationship between the independent variables shown in Table 2, including the
48
49 concentration of asphaltenes (Table 1), a correlation matrix was used to discard variables that are
50
51 colinear, allowing the selection of eight independent variables to evaluate the effect of asphaltenes on
52
53
the precipitation of paraffins through the change in properties (difference between the value of the
54 property in the crude oil and the value of the property in the maltenes). The change in the properties
55
56 (response variables) was determined by the crystallization temperature (∆Tc) and pour point (∆Tpp),
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while the changes in crystallization were determined by the relative crystallization (Cr) presented in Eq.
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5 (1).
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7
8
9 Twenty-four parameters were evaluated for the asphaltenes (Table 2) in addition to the concentration of
10
11
asphaltenes in the crude (Coasf, Table 1). Using a multivariate analysis it was determined between which
12 pairs of variables there are exists collinearity (P-value lower than 0.05), thus these were discarded.
13
14 Finally, eight independent variables were selected: pericondensed carbons (Caaa), average length of
15
16 aliphatic chains in asphaltene (n) molecules, ratio of peripheral carbons to aromatics (Cp/Car),
17
18 aromaticity factor (fa), molecular weight (Mw), crude asphaltenes concentration (Coasf), paraffinic
19 carbons (Cs) and naphthenic carbons (Cn). The response variables, which represent the effect of
20
21 asphaltenes present in crude oil are shown in Table 5.
22
23
24
25 Subsequently, a multivariate PLS (partial least squares regression) analysis was performed to determine
26
27
a correlation between the predictor or independent variables and the response or dependent variables,
28 that is, between the structural parameters of the asphaltenes and the crystallization properties of the
29
30 paraffins. Several models with different numbers of components were obtained. To select the best
31
32 model, a cross-validation was performed, leaving one component out (leave one out) until the model
33
34 complied with a define P-value <0.05 and R2 close to 1.0 (100%). The p-value is the probability for a
35 given statistical model that, when the null hypothesis is true, the statistical summary would be the same
36
37 as or more extreme than the actual observed results. The standardized regression coefficients of the
38
39 parameters were used, with their sign and magnitude, to explain the effect and importance of each
40
41 parameter (predictor variable). The greater the magnitude, the greater the impact on the dependent
42
43
variable. A negative sign means that if the value of the factor increases, the value of the change of
44 property decreases, and the opposite is true for a positive sign.
45
46
47
48
49
50 3.3 Effect of asphaltenes on the crystallization onset
51
52
53 From the results presented in Table 5, it is possible to establish that the asphaltenes of the crude oils Col-
54
55 BC2, Col-CE1 and Col-B1 depress the crystallization temperature (greater value in the maltenes), while,
56
57 in Col- BC1, Col-CE2, and Col-C1 are promoters of this property (positive ∆Tc). Figure 5 presents the
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standardized regression coefficients of the predictive variables of asphaltenes that cause changes in the
4
5 crystallization temperature between maltenes and crude oils.
6
7
8
9 The crystallization temperature (Tc) increases if the following properties are increased in the molecules:
10
11
aromaticity factor (fa), peri-condensed aromatic carbons (Caaa), Cp/Car ratio and paraffinic carbons (Cs).
12 Tc decreases with increasing naphthenic carbons (Cn), asphaltene concentration (Coasf), molecular
13
14 weight (Mw) and aliphatic chain length (n) of asphaltenes. This may be because asphaltene molecules
15
16 with aromatic carbons with high proportion of condensed carbons (Caaa), high Cp/Car ratio and a high
17
18 number of paraffinic carbons (Cs) behave like nucleation centers so that the more soluble solutes
19 (paraffins) initiate crystallization at a higher temperature than that of the paraffins alone. The opposite
20
21 case occurs with molecules of asphaltenes having high values of naphthenic carbons, long chains of
22
23 aliphatic carbons and greater concentration because they create disorder in the system, delaying the
24
25 beginning of nucleation.
26
27
28 The results of the present investigation show that by increasing the aromaticity factor of asphaltenes,
29
30 there is an increase in the WAT (wax appearance temperature) or the crystallization temperature. This is
31
32 contrary to the results obtained by Alcazar et al34, who prepared two samples by varying the aromaticity
33
34 of asphaltenes: a mixture of C24 (15% wt/wt) and C28 (10% wt/wt) paraffins in solvent (37.5% decane
35 and 37% xylene) with 0.5% of asphaltenes with fa of 0.53 and the other with fa of 0.67. In their work,
36
37 they found that the presence of asphaltenes caused a slight increase in WAT from fa of 0.53 and a
38
39 decrease in WAT from fa of 0.67 on waxes without asphaltenes.
40
41
42
43
3.4 Effect of asphaltenes on the degree of crystallization
44
45
46 For relative crystallization (Cr), the major depressant effect is caused by Col-BC2 asphaltenes with a Cr
47
48 value of 0.66 and a concentration of 90 ppm (Table 5), whereas Col-CE1 causes the major promoter
49
50 effect with Cr = 1.11 and 850 ppm. The asphaltenes of Col-C1 (Cr = 0.99) at 1500 ppm show no
51 significant changes in the crystallization ∆H when the crude asphaltenes are removed. This result shows
52
53 that the concentration of asphaltenes, in this case, does not cause any effect on the degree of
54
55 crystallization.
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The multivariate analysis (Figure 6) shows that Cr is affected by the chemical structure of asphaltenes.
4
5 The value of Cr increases if the aromaticity factor of asphaltenes (fa) increases. In contrast, this property
6
7 decreases if the condensed aromatic rings (Caaa), long aliphatic chains (n), protonated aromatic carbons
8
9 and aliphatic carbons are increased in the molecules of the asphaltenes. Our results agree with
10
11
Carbognani et al.21 2003 and Carbognani et a. 200022 which reported that the asphaltenes with higher
12 aromaticity favored wax precipitation.
13
14
15
16 An explanation of this result can be given by taking into account that the molecules of asphaltenes with
17
18 greater aromaticity (fa) present in the crude favor the formation of a more ordered crystalline structure,
19 which is necessary to release more energy compared to when asphaltenes are not present. However, if
20
21 the asphaltenes are in a higher concentration and have in their structure polycondensed rings (high Caaa
22
23 value), long aliphatic chains and naphthenic rings, it is difficult to incorporate them into the crystals,
24
25 causing disorder and delaying the crystallization and therefore favoring the conditions to decrease the
26
27
crystallization.
28
29
30 Alcazar and Buenrostro35 prepared two samples of asphaltenes with different fa. A mixture of paraffins
31
32 C24 (15% wt/wt) and C28 (10% wt/wt) was dissolved in a solvent composed of 37.5% decane and 37%
33
34 xylene. To a part of the mixture, they added asphaltenes at a concentration of 0.5% wt/wt with fa 0.53
35 and the other at the same concentration but with fa of 0.67. The crystallization temperature (WAT) and
36
37 enthalpy of crystallization (by DSC) showed that asphaltenes with lower aromaticity and longer
38
39 aliphatic chains increased the heat of crystallization with a slight increase in WAT. In contrast, the more
40
41 aromatic asphaltenes with short aliphatic chains inhibited the crystallization due to the formation of a
42
43
disordered phase, decreasing the heat of crystallization and the WAT. The results of the present
44 investigation are the opposite, probably because Alcazar and Buenrostro used a binary mixture of
45
46 paraffins dissolved in solvents (paraffinic and aromatic mixture) without the presence of resins and
47
48 aromatics, which does not represent the complex mixture of the maltenes of crude oil and asphaltenes.
49
50
51 3.5 Effect of asphaltenes on pour point
52
53
54
55 The change in the pour point between crude oils and maltenes for the samples studied is positive and is
56
57 between 3 and 18°C (Table 5), indicating that the asphaltenes of the Colorado field have an effect on
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promoting the pour point probably due to the facilitation of bonding between already formed crystals
4
5 which favors agglomeration. This is in agreement with the results of Fang et al. 36 and contrary to those
6
7 obtained by Venkatesan et al.23 and Alcazar et al.34, who concluded that the asphaltenes act as natural
8
9 depressants of the point of fluidity, with the most aromatic asphaltenes having the greatest effect.
10
11
12 The aromaticity factor (fa) is one of the most important parameters affecting wax crystallization
13
14 properties, which has been showed in previous sections in this paper and is according with the results
15
16 found by Carbognani et al. 2000. The effect of molecular parameters on the increase of pour point
17
18 between maltenes and crude oil (Figure 7) shows fa increases this property, while the asphaltenes
19 concentration (Coasf) practically does not affect this property in comparison with other structural
20
21 characteristics of asphaltenes. On the other hand, the peri-condensed aromatic carbons and the
22
23 naphthenic carbons, as well as the long aliphatic chains present in the asphaltenes have a tendency to
24
25 decrease the pour point; the aliphatics at this temperature already have crystallized. The outcome is an
26
27
increase in this property, and the magnitude is lower in crudes that have asphaltenes with a relatively
28 lower factor of aromaticity.
29
30
31
32 In general, the presence of aromatic carbons in the asphaltenes tends to accelerate the crystallization
33
34 process and form networks of crystals to stop the mobility of the oil at a higher temperature. However, if
35 Caaa carbons predominate, that is, there are more polycondensed aromatic rings, as well as naphthenic
36
37 (Cn) and aliphatic (n) chains, the agglomeration of the crystals is disturbed, which creates favorable
38
39 conditions for reaching the cessation of movement of crudes at a lower temperature.
40
41
42
43
There is no correlation between the pour point and the WAT; although the fa increases these properties,
44 the Caaa parameter contributes to increasing the WAT and on the contrary, strongly impacts to decrease
45
46 the pour point of crude oil. The preceding probably happens because higher asphaltenes Caaa increases
47
48 WAT since polycondensed rings act as nucleation centers for waxes; on the other hand at lower
49
50 temperatures when the solid phase is more abundant than liquid (strong gel) the presence of
51 polycondensed rings creates interference between paraffin crystals weakening their interaction, thus
52
53 decreasing the temperature to reach non-fluidity.
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Conclusions
4
5
6
7 A proposed characterization-statistical analysis methodology allowed for the understanding of the effect
8
9 of the average molecular structure of asphaltenes on the crystallization properties of paraffins from the
10
11
crude oils of the Colorado Field. The aromaticity factor of asphaltenes (fa) provided an important
12 contribution to an increase in the properties of crude oils: WAT, Cr and pour point. Other structural
13
14 parameters and characteristics of asphaltenes, such as Caaa, n, Cp/Car, Mw, Cs and Cn, were also found
15
16 having effects.
17
18
19 The changes in the crystallization temperature were minor in absolute terms. The asphaltenes affected
20
21 the relative crystallization differently depending on their chemical structure. Those that were depressants
22
23 of this property (Cr <1) were the most aliphatic ones (Col-BC1 and Col-BC2). The promoters of
24
25 crystallization (Cr> 1) were those having larger aromaticity (fa). Finally, all the asphaltenes were found
26
27
to increase the pour point of the crude oils from the Colorado Field.
28
29
30 The multivariate analysis showed that an increase in the concentration of asphaltenes in the crude oils
31
32 (Coasf), tended to decrease the properties of crystallization temperature and the degree of crystallization
33
34 while contributing to a slight increase in the temperature of pour point; in this last property, the great
35 effect is due to fa.
36
37
38
39 ACKNOWLEDGMENTS
40
41
42
43
The authors express their gratitude to the Universidad Industrial de Santander and the Colorado School
44 Field for their support on the development of research in the area of organic precipitation and
45
46 hydrocarbon flow assurance.
47
48
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Table 1. Characteristics of the Colorado oil field wells and their crude oils.
4
5 Bottom hole Production Asphaltenes
6 Oil Depth API
Well Temperature by Sand Concentration
7 Sand (ft) Gravity
(°C) (% vol.) (ppm)
8 Col-B1 B 2112 40 100 36.0 2270
9
Col-C1 C 5540 60 100 39.0 1500
10
11 Col-BC1 B-C 4802 59 21 and 79 36.5 440
12 Col-BC2 B-C 5600 62 53 and 47 39.0 90
13 850
Col-CE1 C-E 5900 65 68 and 32 39.0
14
15 Col-CE2 C-E 6178 66 71 and 29 38.2 750
16
17 Table 2. Average Molecular Parameters of Colorado asphaltenes.
18
19 Parameter Method Col-B1 Col-BC1 Col-BC2 Col-CE1 Col-CE2 Col-C1
b
20 H EA and MS 48.4 46.1 47.5 45.3 41.4 45.1
21 C EA and MS b 41.1 39.9 40.1 38.4 37.2 39.0
22 Cal NMR a 18.1 18.9 21.6 18.6 14.6 19.1
23 a
Car NMR 23 21 18.5 19.8 22.5 19.9
24 a
25 Har NMR 6.5 3.9 2.7 5.2 5.4 5.4
26 n NMR a 3.9 3.9 6.7 3.8 4 3.2
27 Car-alk NMR a 5.3 8.5 8.1 5.6 6.1 5.6
28 NMR a 1 0.7 0.7 0.6 0.8 0.8
Car-CH3
29 a
30 Car-n NMR 3.1 2.3 2 2.5 2.7 2.3
31 Car-H NMR a 6.5 3.9 2.7 5.2 5.4 5.4
32 Cp NMR a 15.8 15.4 13.4 13.9 15 14
33 a
Ci NMR 7.1 5.5 5.1 5.9 7.6 5.9
34
Caa NMR a 5.5 3.7 3.3 4.3 5.5 4.1
35
36 Caaa NMR a 1.6 1.9 1.8 1.6 2.1 1.8
37 Cs NMR a
9.6 13.3 16.1 14.2 11.7 15.5
38 NMR a
Cn 8.5 5.6 5.5 4.4 2.9 3.6
39 a
Ra NMR 5 4 4 4 5 4
40
a
41 fa NMR 0.56 0.53 0.46 0.52 0.61 0.51
42 Φ NMR a 0.31 0.26 0.28 0.30 0.34 0.30
43 Cp / Car NMR a 0.69 0.74 0.72 0.7 0.66 0.7
44 NMR a
Tar 0.27 0.44 0.47 0.31 0.31 0.32
45 b
46 MW (g / mol) MS 589.3 573.2 584.1 547.5 561.3 585.6
47 La (Å) RAMAN c 16.5 14.7 - 13.6 19.4 -
48 Lc (Å) XRD d 26.1 8.5 - 8.5 28.3 -
49 Reference of Methodology: a [27, 29, 30, 31]; b [28]; c [32]; d [33]
50
51 H: total number of hydrogens. C: total numbers of carbons. Cal: number of aliphatic carbons. Car: number of aromatic carbons. Har: number
52 of aromatic hydrogens. n: average length of aliphatic chains. Caralk: number of aromatic carbons attached to alkyls. CarCH3: number of
aromatic carbons with attached methyl groups. Carn: number of aromatic carbons attached to naphthenic groups. CarH: number of protonated
53
aromatic carbons. Caa: number of kata-condensed aromatic carbons or a bridge of two aromatic rings. Caaa: number of pericondensed
54 aromatic carbons or a bridge of three aromatic rings. Cs: number of saturated carbons. Cn: number of naphthenic carbons. Ra: aromatic ring
55 number. fa: aromaticity factor. Φ: aromatic condensation index. Cp/Car: the ratio of peripheral aromatic carbons to aromatics. Tar: Aromatic
56 Substitution Ratio (Car-talk + Car-CH3) / Car. MW: average molecular weight. La: average size of the asphaltene molecule. Lc: average height
57 of the asphaltene cluster.
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5 Table 3. Relative percentage of Carbon atoms by 13C-NMR of the Colorado maltenes
6
7 Relative content (% )
8 Carbons
Col-B1 Col-BC1 Col-BC2 Col-CE1 Col-CE2 Col-C1
9
10 Car-CH3 4.7 4.8 4.3 4.4 2.9 4.5
11 1.2 2.7 2.8 2.7 8.8 2.1
Car-H
12
13 Caaa 4.7 2.1 1.7 2.6 7.7 2.5
14 Caa 3.7 3.1 2.8 2.8 3.4 3.0
15
16 Car-n 2.0 1.7 1.5 1.4 2.2 1.5
17 Car-alk 3.0 2.5 1.6 1.1 4.0 0.9
18
19 Car 19.2 16.7 14.7 15.1 28.9 14.6
20 Cs 69.9 75.4 78.0 76.6 54.3 76.9
21
22 Cn 10.9 7.8 7.2 8.3 16.7 8.5
23 Cal 80.9 83.3 85.3 84.9 71.1 85.4
24
25
26
27 Table 4. Relative percentage of Hydrogen atoms by 1H-NMR of the Colorado maltenes
28 Relative content (% )
29 Protons
30 Col-B1 Col-BC1 Col-BC2 Col-CE1 Col-CE2 Col-C1
31 Har 1.2 2.7 2.8 2.7 8.8 2.1
32
33 Hγ 42.4 29.7 31.9 36.1 22.6 39.1
34 Hβ 54.8 62.9 62.0 58.2 61.8 56.5
35
36 Hα 1.7 4.7 3.3 3.1 6.8 2.4
37 Hal 98.8 97.3 97.2 97.3 91.2 97.9
38
39 Hβ/ Hγ 1.3 2.1 1.9 1.6 2.7 1.5
40
41
42 Table 5. Change in properties of the Colorado Field oils due to effects from asphaltenes
43
44 Well Asphaltenes (ppm) *∆Tc (°C) **(Cr) *∆Tpp(°C)
45
46 Col-BC2 90 -2.36 0.66 6.00
47
48 Col -BC1 440 0.65 0.90 3.00
49 Col -CE2 750 1.87 1.06 12.00
50
51 Col -CE1 850 -1.50 1.11 18.00
52 Col -C1 1500 0.78 0.99 9.00
53
54 Col -B1 2270 -4.70 1.08 9.00
55 *Properties were determined over oils and maltenes and the differential properties can be attributed to asphaltenes present in crude oils.
56 ** From equation 1.
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Figure 1. 13C NMR spectrum of asphaltenes and the spectral partition according to the different
4
5 chemical shifts.
6
7
8
9
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12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34 Figure 2. 1H NMR spectrum of asphaltenes and the spectral partition according to the different
35 chemical shifts.
36
37
38
39
40
41
42
43
44
45
46
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49
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Table 6. Carbon chemical shift correlation chart for hydrocarbons
4
5
6 Domain in ppm Area Type of Assignment
7 carbon
8
9 137.0 – 160.0 A1 Car-alk Alkyl-substituted aromatic carbón except CH3
10
132.0 – 137.0 A2 Car-n Carbon at junction of an aromatic and naphtenic
11
rings
12
128.0 – 136.0 A3 Caa Carbon at juction of two aromatic rings
13
14 A4 Car-H + Caaa Aromatic protonated carbons plus carbon at
118.0 – 130.0
15 junction of three aromtic rings
16
17 18.00 – 20.00 A5 Car-CH3 Methyl-substituted aromatic carbon
18
19 5.00 – 75.00 A6 Cal Saturated carbons
20
21
22
23
Table 7. Proton chemical shift correlation chart for hydrocarbons
24
25 Domain in ppm Area Type of proton Assignment
26
27
28 6.30 -9.30 a1 Har Aromatic protons
29
30 1.85 – 4.50 a2 Hα Protons attached to α a
31
32 1.00 – 1.85 a3 Hβ Protons attached to β a
33
0.50 – 1.00 a4 Hγ Protons attached to γ a
34
35 a
36 with respect to an aromatic ring.
37
38
39
40
41
42
43
44
45
46
47
48
49
50
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Figure 3. Correlation between Φ and Ra and Cp/Car of asphaltenes from Colorado field oils.
4
5
6
7 0.75 6
8 0.74
9 5
0.73
10
0.72 4
11
12 0.71
Cp/Car

Ra
13 0.7 3
14 0.69
15 2
0.68
16 0.67
17 1
0.66
18
19 0.65 0
20 0.24 0.26 0.28 0.3 0.32 0.34 0.36
21 Φ
22
23 Cp/Car Ra
24
25
26
27
28
29
30
31
Figure 4. Relative percentage of chemically different Carbon and Hydrogen atoms of the
32 maltenes.
33 100
Relative content of carbons and protons (% )

34
90
35
36 80
37 70
38
39 60
40 50
41
42 40
43 30
44
20
45
46 10
47 0
48
49
50
51
Carbons and protons of the maltenes in crude oils
52
53 Col-B1 Col-BC1 Col-BC2 Col-CE1 Col-CE2 Col-C1
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Figure 5. Multifactorial analysis of the effect of asphaltenes on the change in crystallization
5 temperature.
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31
32 Figure 6. Multifactorial analysis of the effect asphaltenes on the crystallization ratio between
33
34 crude and maltenes
35
36
37
38
39 nada
40
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Figure 7. Multifactorial analysis of the effect asphaltenes on the pour point of oils Colorado field.
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