Coal-derived Asphaltenes Research Articles

Computational Workflows to Predict Ensemble Property Distributions from Structures Obtained by Single-Molecule Imaging: Application to Steam-Cracked Tar, Coal-Derived Asphaltene, and Petroleum Pitch

Computational Workflows to Predict Ensemble Property Distributions from Structures Obtained by Single-Molecule Imaging: Application to Steam-Cracked Tar, Coal-Derived Asphaltene, and Petroleum Pitch

Competitive adsorption of CO2, N2, and CH4 in coal-derived asphaltenes, a computational study

Greenhouse gases are major contributors to global warming, and their concentration is increasing due to the widespread use of fossil fuels. Coal bed methane (CBM) offers a potential solution to this issue. However, the gas adsorption mechanisms of CBM, particularly in the context of coal-derived asphaltenes, are not fully understood. This study provides a comprehensive theoretical investigation of the competitive adsorption of carbon dioxide (CO2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$_2$$\\end{document}), methane (CH4\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$_4$$\\end{document}), and nitrogen (N2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$_2$$\\end{document}) in the processes of CO2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$_2$$\\end{document}- and N2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$_2$$\\end{document}-enhanced coalbed methane recovery, with a focus on coal-derived asphaltenes functionalized with CH4\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$_4$$\\end{document}, NH, O, and S groups. Using the Grand Canonical Monte Carlo (GCMC) simulation method and performing Molecular Dynamics (MD) simulations, we studied the adsorption process. To investigate the electronic effects and nature of the interactions, we performed density functional theory (DFT) calculations. The adsorption energy values and non-covalent interactions (NCI) for the adsorption of gases signify the physical adsorption (van der Waals interaction), with CO2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$_2$$\\end{document} exhibiting the highest (absolute) adsorption energy. The Monte Carlo results indicated that elevated temperatures led to a reduction in adsorption capacity. Coal-derived asphaltenes demonstrated greater selectivity for CO2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$_2$$\\end{document} compared to CH4\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$_4$$\\end{document} and N2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$_2$$\\end{document} in competitive adsorption, especially at elevated temperatures. Our findings highlight the significant potential of our asphaltene model, not only in mitigating CO2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$_2$$\\end{document} greenhouse gas emissions but also in recovering CH4\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$_4$$\\end{document}, which is a valuable resource.

Multi-scale analysis on the aggregation mechanism of oxygen-rich coal-derived asphaltene molecules

Significant differences exist in the structural features between coal-derived asphaltene and petroleum asphaltene (e.g., the degree of alkylation, aromatic nuclei size, heteroatom content, as well as morphology characteristics). The self-aggregation behavior exhibited by coal tar asphaltene for coal tar processing should be investigated in accordance with the structural characteristics of coal tar asphaltene. In this study, the focus was placed on the effect exerted by oxygen structure format, location and content on the aggregation behavior of asphaltene. The electrostatic potential (ESP) maps, theoretical reactivity parameters, molecular orbitals, dimerization interaction energies, and weak interactions of coal tar asphaltene were determined based on quantum chemistry. The self-aggregation behavior exhibited by coal-derived asphaltene was explored through molecular dynamics simulations. As indicated by the results of this study, the π-π interactions among asphaltenes were enhanced by the heteroatoms embedded in polycyclic aromatic hydrocarbons (PAHs). In the identical oxygen content, the π-π stacking of asphaltenes with five-membered heterocyclic structures turned out to be more intense. The carboxyl and hydroxyl were more likely to form hydrogen bonds, such that the stability of asphaltene aggregates was increased. Furthermore, as indicated by the molecular dynamics simulation results, the oxygen-containing structures far from PAHs exhibited small steric resistance and a higher probability of the formation of hydrogen bonds.

Molecular representation of coal-derived asphaltene based on high resolution mass spectrometry

The asphaltene separated by solubility in small molecular alkanes and toluene is the most structurally diverse and complex components in heavy oil, such as vacuum residue and coal tar. The coal-derived asphaltene is always regard as a succession of maltene fraction from small molecules to large molecules, and also a continuum of island- and archipelago-type structures, which is difficult to be identified accurately through current characterization methods. This limits the further study of molecular dynamics and reaction dynamics simulation of asphaltenes. In this work, a representation model of molecular composition and structure for coal-derived asphaltene is developed mainly based on Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) coupled with collision induced dissociation (CID) and traditional methods of nuclear magnetic resonance spectroscopy (13C NMR), Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS). Island- and archipelago-type structures are considered qualitatively in the representation of asphaltene. The asphaltene molecules are systematic assembled using stochastic algorithms and optimized by simulated annealing algorithm according to the group contribution method. The bulk properties for simulating asphaltenes are in good agreement with the experimental results giving acceptable predictions for the composition and structure of the asphaltenes. Moreover, the representative average structure asphaltene molecules are obtained using the developed molecular similarity function, which could be applied in the further study of molecular aggregation simulation and reaction kinetics simulation.

Comparison of the composition and structure for coal-derived and petroleum heavy subfraction by an improved separation method

The property of coal-derived asphaltene and resin shows remarkable differences from petroleum one, such as the molecular aggregation and thermal cracking characteristics. It is significant to make deep-level analysis of their composition and structure to provide detailed molecule information for coal tar deep processing. In this paper, an improved separation method, which innovatively developed two-stage asphaltene extraction and two-stage silica gel separation coupling process, was built to obtain the purified asphaltene and resin components derived from coal tar (C-asp and C-res) and petroleum (P-asp and P-res). All samples were analyzed comparatively through Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), solid state cross polarization/magic angle spinning nuclear magnetic resonance spectroscopy (13C-CP/MAS-NMR), thermogravimetric analysis (TG) and scanning electron microscopy (SEM). It is found that C-asp and C-res contain more OH groups resulting in stronger aggregate effect and OH-OH and OH-ether O are the main hydrogen bond. C-asp and C-res have more C-O of phenols and C = O of COOH group. C-asp and C-res have fewer and shorter alkyl side chains. The aromatic ring substitutive degree (σ) of C-asp and C-res is higher while the alkyl branching degree of P-asp and P-res is higher. Besides, asphaltene has higher σ, alkyl substituents number (n), average stack height of aromatic sheet (Lc), average number of aromatic sheets associated in per stacked cluster (M) and shorter average substituted alkyl chain length (L) compared with resin. Finally, the average molecular structure models of C-asp, P-asp, C-res and P-res are obtained.

Theoretical and experimental examinations to substantiate the structure of coal derived asphaltene by formation of complex with o-chloranil

The structure of coal derived asphaltene (CDA) proposed by Mullins et al has been corroborated through theoretical and experimental examination by the virtue of its electron donor property. Here, o-chloranil has been used as an electron acceptor. Investigation of o-chloranil/CDA complex in gas phase has been performed by density functional theory (DFT) methods. The Charge transfer (CT) transition energy of the complex in gas phase was calculated by the time-dependent density function theory (TD-DFT) using the ground state optimized geometry at the respective levels of theory. For this, the three semi empirical methods AM1, PM3 and PM3MM were computed under the MPW1PW91, B3PW91, PBE1PBE, BPV86 and RCIS formalism. It is found that the two formalisms MPW1PW91 and PBEPBE under PM3 and PM3MM reproduced values close to the experimental one. However, all of them provide lower charge transfer (CT) transition energy values than that has been experimentally determined. Experimentally, FTIR spectra of the donor, acceptor and the complex further supported the understanding of complex formation and demonstrated close similarity with the theoretically determined CDA frequencies. These findings support the validity of the CDA structure to an extent.

Asphaltenes: Separations, structural analysis and applications

Abstract Asphaltenes, complex aromatic compounds from various carbonaceous sources, could be obtained by solvent dissolution, filtration and adsorption. It was difficult to clarify the molecular structures and chemical properties of asphaltene due to its structural similarity, composition complexity and source dependences. Many techniques, like Mass spectrometry, Chromatography, Nuclear magnetic resonance spectroscopy, Infrared spectroscopy, Roman spectroscopy, Fluorescence spectroscopy, X-ray diffraction analysis and Small-angle scattering techniques and so on, have revealed some valuable descriptions of asphaltenes chemical compositions and fundamental structures. Moreover, advanced Mass spectrometry, Atomic force microscopy and Scanning tunneling microscopy could provide more clear and essential molecular compounds and structures in asphaltenes. In addition, several asphaltenes models have succeeded to illustrate aggregation properties asphaltene. In this work, the progress on asphaltene separation, characterization and application was summarized, and the similarities and differences between coal-derived asphaltenes and petroleum asphaltenes were compared. Furthermore, the reactivity of asphaltenes has been discussed in the aspect of hydroprocessing, pyrolysis and gasification. Asphaltene was excellent carbon precursor for functional carbon material due to its high aromaticity and carbon yield; several porous carbon nanosheets from asphaltenes that would be prospective electrode materials after being graphitized were shown. Pitch-based carbon fiber derived from coal-derived asphaltenes displayed a tensile strength of 1.0 GPa and elastic modulus of 350 MPa, respectively. These powerful advances will provide asphaltenes promising developments.

Time of flight-secondary ion mass spectrometry (TOF-SIMS) study of diverse asphaltenes

Mass spectrometry has been used to elucidate a large variety of properties of asphaltenes. Here, time-of-flight secondary ion mass spectrometry (TOF-SIMS) is used to probe three diverse asphaltene types with wide ranging fractions of alkyl carbon to the sum of alkyl plus aromatic carbon (Rc), immature source rock asphaltenes (ISA with Rc ∼ 0.75); petroleum asphaltenes (PA with Rc ∼ 0.5); and coal-derived asphaltenes (CDA with Rc ∼ 0.25). In addition, the asphaltenes from a commercial bitumen are examined. Primary ion surface bombardment using the Bi3+ ion yields high energy density of deposition and significant molecular fragmentation with secondary ion formation. Formation of free radical cation fragments is generally suppressed especially for smaller fragments except for specific cases. Possible structures, especially cations of common aromatic compounds, are suggested for fragments with relatively large cross section of formation. Principal component analysis of the fragmentograms allows identification of key properties of the complex fragmentation patterns for the different samples. Comparisons of TOF-SIMS fragmentograms show a fundamental difference for small fragments between CDAs and all petroleum derived asphaltenes with CDAs being dominated by aromatic carbon fragments whereas all petroleum derived asphaltenes show a large fraction of fragments from alkyl carbon. However, the type of alkyl carbon fragments did not exhibit systematic trends with Rc, nor with the extent of chemical reaction or chemical processing of the materials. Consequently, it appears that having an appreciable alkane fraction is a basic property of petroleum derived asphaltenes, but the exact type of alkane carbon for differing samples of these asphaltenes is more idiosyncratic than systematic.

Nanoaggregates of Diverse Asphaltenes by Mass Spectrometry and Molecular Dynamics

Asphaltene nanoaggregates for three diverse source materials—coal-derived asphaltenes dominated by aromatic carbon, petroleum asphaltenes with comparable abundances of aromatic and aliphatic carbon, and immature source-rock asphaltenes dominated by aliphatic carbon—are examined by means of surface-assisted laser desorption ionization mass spectrometer (SALDI-MS) coupled with laser desorption laser ionization mass spectrometry (L2MS). All three types of asphaltenes form nanoaggregates with aggregation numbers close to 7. Molecular dynamics calculations for proposed island molecular structures show the important roles that π-stacking and alkane steric hindrance play in nanoaggregate formation. These results are discussed in terms of entropy and enthalpy changes. All results are consistent with the Yen-Mullins model, which bodes well for its expanded use in oilfield reservoir evaluations.

Identification of nitrogen-polyaromatic compounds in asphaltene from co-processing of coal and petroleum residue using chromatography with mass spectrometry

Asphaltene, from co-processing of coal and petroleum residues is one of the most precious and complex molecular mixtures existing, with tremendous economic relevance. Asphaltene was separated by Soxhlet extraction with methylbenzene and then divided into three parts by distillation. Gas chromatography (GC) and high-performance liquid chromatography (HPLC) were coupled with quadrupole time-of-flight mass spectrometry (Q-TOF MS) to separate and characterize organic nitrogen species in the distillates of asphaltene at molecular level. Molecular mass of compounds was mainly distributed from 150 to 600 μ. Number of rings plus double bonds (rdb) and synchronous fluorescence spectra indicated that most of the organonitrogen compounds (NPAC) contained heterocyclic aromatic rings, including pyridines, anilines, quinolins, pyrroles, carbazoles and indoles plus various alkyl groups. Constant-wavelength synchronous fluorescence spectrometry (CWSFS) indicated NPAC with 2–3 rings were the main structures of organonitrogen compounds and the corresponding structural information was proposed. Some organic nitrogen isomers were separated and identified by atmospheric pressure chemical ionization (APCI) GC-Q-TOF MS and electrospray ionization (ESI) HPLC-Q-TOF MS. The methodology applied here contained chromatographic injection of the diluted sample using conventional columns sets and Data Analysis 4.2 software. Identifying molecular structures provides a foundation to understand all aspects of coal-derived asphaltene, enabling a first-principles approach to optimize resource utilization.

Single-Core PAHs in Petroleum- and Coal-Derived Asphaltenes: Size and Distribution from Solid-State NMR Spectroscopy and Optical Absorption Measurements

Using solid-state 13C NMR spectroscopy of two different asphaltenes, one derived from petroleum and the other from coal liquids, it was shown that the asphaltene molecular architecture consists of a spectrum of sizes, ranging from smaller polyaromatic hydrocarbons (PAHs; 9 condensed rings), but their distribution varies between the two. It is shown that smaller PAHs are likely more abundant in the coal-derived asphaltenes, while the largest PAH cores of the two different asphaltenes are similar in size. These observations are reinforced by optical absorption. The coal-derived asphaltenes were found to contain a small fraction of archipelago-type structures, where a small PAH is tethered to the larger PAH core via an aryl linkage, which are less evident, and likely less abundant, in the petroleum asphaltenes. An important difference between the two asphaltenes lies in their alkyl fraction, with the petroleum asphaltenes possessing significantly longer and more mobi...

Steady state fluorescence spectroscopic studies on the aggregation of coal derived asphaltene at lower concentration

Steady state fluorescence spectroscopic technique has been used to investigate the aggregation of coal derived asphaltene (CDA) sourced from Lodna Coke Plant situated at Dhanbad, India. The emission spectra of CDA provide information regarding the various stages of onset of aggregation in carbon tetrachloride medium. Almost similar results have also been inferred from the analysis of corresponding excitation spectra. It has been observed that the onset of aggregation of CDA occurs at concentration beyond a concentration of 10mgL−1. Studies indicate the formation of a trimer at this concentration range. The association constant (K) for the trimer formation has also been evaluated from the spectroscopic data.

Spectroscopic Investigation of Asphaltene Aggregation in Carbon Tetrachloride Medium Containing Microquantities of Water

By fluorescence spectroscopy it has been established that coal derived asphaltene (CDA) forms aggregates in CCl4 medium. The new feature of this compound is that even before aggregate formation it can incorporate water molecules and the critical aggregation concentration (CAC) in nonaqueous medium increases with increase in ω (= water:CDA mole ratio). The fluorescence spectroscopic determination of the equilibrium constant (K) of the molecular complex of [60] fullerenes with CDA in carbon tetrachloride medium has revealed that K increases on addition of microquantities of water. This observation has been rationalized by assuming that the nitrogenatoms at one end of CDA molecules attach themselves to the water micropool and thus producing a different conformation with a wider distance at the other end. This pre-organization further facilitates inclusion. By utilizing fluorescence variation of [60]fullerene/CDA complex in CCl4 as continuous medium with change in ω a critical ω (=5) has been found. The formation of CDA/[60]fullerene complex has also been established by NMR spectroscopy.

Study of Molecular Complex Formation of Coal-Derived Asphaltene with TCNQ in Homogeneous and Heterogeneous Media by UV-Vis and Fluorescence Spectroscopic Studies

Coal-derived asphaltene (CDA) has been shown to form electron donor–acceptor-type molecular complexes with electron acceptor such as 2,5-cyclohexadiene-1,4-diylidene also known as tetracyanoquinodimethane (TCNQ) in homogeneous medium of carbon tetrachloride and heterogeneous medium of aqueous SDS. This has been investigated both by UV-Vis and fluorescence spectrophotometric method. The Charge transfer (CT) absorption peaks have been detected by difference spectral method and the wavelengths of the CT peaks are close in both the medium. The formation constants (K) have been determined using the Benesi–Hildebrand equation. The magnitudes of K are in the order of 103 L mol−1 that are comparable to some supramolecular or inclusion complexes. The study reveals the presence of π-donor (i.e., aromatic) type of compounds in CDA molecule. It also supports the view that CDA molecules exist in solution forming micellar aggregate, in the cavities of which the TCNQ molecules are included. The remarkable increase (three fold) in the formation constant in the SDS medium compared to CCl4 further indicates that the CDA aggregate in SDS undergoes some preorganization to further facilitate inclusion.

Absorbance spectrometric study of electron donor acceptor complexes of coal derived asphaltene with [60]- and [70]fullerenes

Coal derived asphaltene (CDA) has been observed to form molecular complexes with electron acceptors such as [60]- and [70]fullerenes in carbon tetrachloride medium. The UV–vis spectroscopic studies show that CDA forms an inclusion complex of 2(CDA):1(fullerene) stoichiometry with [60]fullerene. On the other hand, CDA forms similar complex of 3(CDA):1(fullerene) stoichiometry with [70]fullerene. This is established by determining the thermodynamic parameters such as formation constants, enthalpies and entropies of the complex formation. The results also indicate that the process of complex formation in both the cases is entropy driven one.

Laser-Based Mass Spectrometric Determination of Aggregation Numbers for Petroleum- and Coal-Derived Asphaltenes

Petroleum- and coal-derived asphaltenes have been studied with three laser-based mass spectrometric techniques: laser desorption ionization–mass spectrometry (LDI–MS), in which a single laser desorbs and ionizes solid analytes; surface-assisted laser desorption ionization–mass spectrometry (SALDI–MS), in which a single laser desorbs and ionizes solid analytes from an activated surface; and laser desorption laser ionization mass spectrometry (L2MS), in which desorption and ionization are separated spatially and temporally with independent pulsed laser sources. We find that asphaltene nanoaggregates can be detected in LDI–MS and SALDI–MS under mild conditions of relatively low laser power, whereas L2MS avoids aggregation and fragmentation, detecting asphaltenes as monomeric molecules. A comparison of the L2MS and SALDI–MS results yields an estimate of the distribution of aggregation numbers (number of molecules comprising the nanoaggregate). The most probable aggregation number observed for nanoaggregates of petroleum asphaltenes is approximately 6–8 molecules, consistent with the Yen–Mullins model of asphaltenes and predictions from the island geometry for asphaltene molecules. Additionally, the nanoaggregates are found to be relatively monodisperse, because most aggregates observed have aggregation numbers within one molecule of the most probable. In contrast, the nanoaggregates of coal asphaltenes are found to be smaller and more polydisperse, with aggregation numbers ranging from 3 to 6 molecules. Under higher powers, SALDI–MS measurements show that nanoaggregates decompose to form small multimers and monomers, suggesting that the aggregates are bound noncovalently. Coal asphaltene nanoaggregates decompose at lower laser powers than petroleum asphaltene nanoaggregates, indicating that the coal asphaltene nanoaggregates are bound less strongly than petroleum asphaltene nanoaggregates.

Molecular Size Determination of Coal-Derived Asphaltene by Fluorescence Correlation Spectroscopy

The molecular properties of asphaltenes have been the subject of uncertainty in the literature; in particular the molecular architecture is still a matter of debate. Some literature reports provide evidence that the contrast of petroleum asphaltenes versus coal-derived asphaltenes is useful for understanding the governing principles of asphaltene identity. Here, we employ fluorescence correlation spectroscopy to measure the diffusion constants of asphaltenes obtained from the distillation resid from coal liquefaction fluids. Concentrations employed herein are ∼10−8 molar, precluding asphaltene aggregation. These are compared with the same measurements on petroleum asphaltenes. These results confirm that the molecular sizes of these coal-derived asphaltenes are much smaller than virgin petroleum asphaltenes. Coal-derived asphaltenes are simpler than petroleum asphaltenes and provide correspondingly tighter constraints for understanding asphaltene molecular architecture. The small size, small alkane fraction, and large PAH of coal-derived asphaltenes are consistent with an “island” molecular architecture.

Comparison of Coal-Derived and Petroleum Asphaltenes by 13C Nuclear Magnetic Resonance, DEPT, and XRS

The molecular architecture of asphaltenes is still a matter of debate. Some literature reports provide evidence that the contrast of petroleum asphaltenes versus coal-derived asphaltenes is useful for understanding the governing principles of asphaltene identity. Coal-derived asphaltenes provide an excellent test for understanding the relationship of asphaltene molecular architecture with asphaltene properties. Diffusion measurements have shown that coal-derived asphaltenes are half the size of many crude oil asphaltenes, but there are relatively few studies comparing coal-derived and petroleum asphaltenes using liquid state 13C NMR. 13C NMR confirms that the molecular sizes of these coal-derived asphaltenes are smaller than virgin petroleum asphaltenes. DEPT-45 experiments were performed in order to determine the relative amount of nonprotonated and protonated carbon in the aromatic region of the spectrum. In contrast to previous NMR work on asphaltenes that ignored interior bridgehead carbon, we show th...

The Role of Water in the Aggregation of Coal-Derived Asphaltene: Dominance of π-π Interaction

The effect of water to the self-aggregational phenomenon of coal-derived asphaltene (sourced from coal liquefaction plant at CIMFR, Dhanbad, India) has been studied tensiometrically and fluorimetrically in CCl4 medium. Although asphaltene molecule contains small number of hydrophilic groups such as –NH, –SH, and sometimes –OH, the main force behind the aggregation of asphaltene is π-π stacking interaction between the asphaltene molecules. This has been established by showing that critical micelle concentration (CMC) of asphaltene/CCl4 system increases with addition of microquantity of water and also by studying the variation of surface tension (ST) with addition of water to asphaltene solution above its CMC.

Absorption Spectrophotometric Study of Molecular Complexation of Asphaltene with Bromanil

It has been shown by UV−vis spectrophotometric method that p-bromanil forms inclusion complex of 1:2 stoichiometry with coal-derived asphaltenes. The absorption peak for the complex has been detected by difference spectral method and has been compared with those for complexes involving chloranils. The wavelengths of the maximum absorption are in the expected order of electron affinities of the chloranils and bromanil. The formation constants (K) have been determined using the Benesi−Hildebrand equation. The magnitudes of K are large compared to those of weak charge transfer complexes (for which K ≈ 101 to 103 dm3 mol−1) but are comparable to those of some recently reported supramolecular or inclusion complexes. The study reveals the presence of π-donor (i.e., aromatic) type of groups in asphaltene molecule. It also supports the view that bromanil molecules get included into structures provided by asphaltene molecules. Thermodynamic parameters ΔH0 sand ΔS0 for the complexation process have also been determined.