SARA fractionation separates the oil into fractions of saturates (S), aromatics (A), resins (R), and asphaltenes (A) based on the differences in their polarizability and polarity.Defined as a solubility class, asphaltenes are normally considered as a menace in the petroleum industry mainly due to their problematic precipitation and adsorption at oil water and oil-solid interfaces. As a broad range of molecules fall within the group of asphaltenes with distinct sizes and structures, considering the asphaltenes as a whole was noted to limit the deep understanding of governing mechanisms in asphaltene-induced problems.Extended-SARA (E-SARA) is being proposed as a concept of asphaltene fractionation according to their interfacial activities and adsorption characteristics, providing critical information to correlate specific functional groups with certain characteristics of asphaltene aggregation, precipitation and adsorption. Such knowledge obtained is essential to addressing asphaltene-related problems by targeting specific subfractions of asphaltenes for selective removal.2
Whole asphaltenes (WA) were fractionated by the E-SARA method according to their adsorption characteristics at oil−water interfaces from either toluene or heptol solutions. Heptol, a mixture of n-heptane and toluene at a 1:1 volume ratio, is a less aromatic solvent than toluene. The effect of solvent aromaticity on the composition of resulting asphaltene subfractions at oil−water interfaces was studied to determine the key functional groups that are critical to the asphaltene-induced stabilization of water-in-oil (W/O) petroleum emulsions. The interfacially active asphaltenes (IAA) were extracted as materials irreversibly adsorbed onto emulsified water droplets, while the asphaltenes remaining in the oil phase were considered as remaining asphaltenes (RA). Although toluene-extracted interfacially active asphaltenes (T-IAA) accounted for only 1.1 ± 0.3 wt % of WA, this subfraction of asphaltenes exhibited a greater interfacial activity and formed more rigid films at the oil−water interface than IAA extracted using heptol, known as HT-IAA which accounted for 4.2 ± 0.3 wt % of WA. The increased potential of T-IAA to stabilize W/O emulsions was attributed to their higher content of oxygen, resulting in a higher content of sulfoxide groups, as verified by elemental analysis, Fourier transform infrared (FTIR) spectroscopy, and X-ray photoelectron spectroscopy (XPS). Although the toluene-extracted remaining asphaltenes (T-RA) and heptol-extracted remaining asphaltenes (HT-RA) were shown to contain similar H/C ratios and nitrogen contents to those of T-IAA and HT-IAA, the two RA subfractions contained a much less amount of sulfur and oxygen, leading to a much reduced interfacial activity as compared with that of IAA subfractions. In spite of the small proportions in asphaltenes, oxygen-containing functional groups, in particular sulfoxides, were believed to contribute significantly to the increased stability of asphaltene-stabilized W/O petroleum emulsions.
Using the extended-SARA method to fractionate asphaltenes based on their interfacial activity, the current study reports the first results on the estimated size and shape of interfacially active asphaltene (IAA) and remaining asphaltene (RA) nanoaggregates. These fractions have been reported to exhibit distinctly different chemical architectures that influence the size of asphaltene clusters in good and poor solvents. However, little is known about the building blocks, commonly referred to as nanoaggregates, which form these clusters and how those subtle differences in chemical architecture impact aggregation of asphaltenes. The nanoaggregate size and shape of IAA and RA was measured using small-angle neutron scattering (SANS). The characteristic length and asymptotic power-law exponent of whole asphaltenes (WAs) extracted from heavy crude oil and dispersed in deuterated toluene were 28.0 ± 0.2 Å and 2.86 ± 0.01, respectively, showing negligible variations with changing asphaltene concentration, source of asphaltenes (bitumen and heavy crude oil), and solvent aromaticity. For RA fractions, which account for 98.5 wt % of WA, the characteristic length and power-law exponent of 28.8 Å and 2.86 were comparable to that of WA but in contrast to 59.7 Å and 2.20 for IAA. A ∼100% increase in the characteristic length and reduced power-law exponent of the IAA fraction confirms that these two asphaltene subfractions form dissimilar nanoaggregate structures.
In part 1 of this series of papers, the results of electron spray ionization mass spectrometry (ESI-MS) and molecular dynamics (MD) simulation revealed a close relationhsip between nanoaggregation of polyaromatic (PA) compounds and their chemical structures. In this paper, we present the results of investigating the flocculation of fractionated asphaltenes and synthesized PA molecules by dynamic light scattering (DLS). Together, these two papers complement one another and draw a full picture of asphaltene aggregation. Three asphaltene fractions were obtained on the basis of their different adsorption characteristics onto calcium carbonate. The DLS results suggest that the irreversibly adsorbed (Irr-Ads) asphaltenes containing the highest number of polar groups are the fraction of asphaltenes responsible for the observed flocculation in whole asphaltenes. To better understand the aggregation behavior of asphaltenes, flocculation of three synthesized PA compounds, N-(1-hexylhepyl)-N′-(5-carboxypentyl)perylene-3,4,9,10-tetracarboxylic bisimide (C5Pe), N-(1-undecyldodecyl)-N′-(5-carboxypentyl)-perylene-3,4,9,10-tetracarboxylic bisimide (C5PeC11), and N,N′-bis(1-undecyldodecyl)perylene-3,4,9,10-tetracarboxylic bisimide (BisAC11), was further studied using DLS. The observed flocculation corresponds well with the results of studying nanoaggregation using ESI-MS. The flocculation of PA compounds was found enhanced with increasing heptane content in the solvent. Among the three synthesized PA compounds studied, C5PeC11 showed flocculation kinetics similar to that of the Irr-Ads asphaltenes. Experiments using mixed PA compounds showed reduced flocculation of C5PeC11 in the presence of C5Pe under otherwise identical solution conditions. The presence of polar groups in PA molecules was proven to be critical in accelerating the flocculation of PA compounds beyond the nanoscale. The results from MD simulations showed that π–π stacking between polyaromatic cores, hydrogen bonding between polar groups, and tail–tail interactions among aliphatic chains all contribute to the observed flocculation of PA compounds.
Asphaltenes are a complex mixture of molecular structures with a variety of functionalities, which in turn impacts their physical properties. Discriminating between asphaltenes that are strongly and weakly interfacially active is providing a new direction to mitigate asphaltene-related problems. Whole asphaltenes (WA) were extracted from a South American heavy crude oil, further fractionated into interfacially active asphaltenes (IAA) and remaining asphaltenes (RA), and molecularly characterized by positiveion (+) atmospheric pressure photoionization (APPI) using a 9.4 T Fourier transform ion cyclotron mass spectrometer (FT-ICR MS). The IAA fraction was found to contain a greater abundance of heteroatoms with >50% of IAA containing two or more heteroatoms as compared to ∼30% for RA. The IAA fraction was enriched in oxygen-containing species, more specifically higherorder O x and O x S y groups that were predominantly of low DBE. Gas-phase fragmentation of RA and IAA precursor ions (m/z 650) by infrared multiphoton dissociation (IRMPD) revealed an abundance of multi-core motifs in IAA, while RA was found to be a mixture of single-core and multi-core structures. Analysis of the fragmented ions showed a prevalence of nitrogen-containing species of high DBE (aromatic molecular structures), while oxygen-containing species were most likely associated with aliphatic side chains. Extrography fractionation of RA and IAA verified the abundance of multi-core motifs in IAA, which were highly polar and of low DBE and carbon number. These "atypical" structures of IAA are classified as asphaltenes as a result of their functionality and polarity rather than high aromaticity.
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