Understanding Asphaltene Fraction Behavior through Combined Quartz Crystal Resonator Sensor, FT-ICR MS, GPC ICP HR-MS, and AFM Characterization. Part I: Extrography Fractionations

Acevedo, Nelson; Moulian, Rémi; Chacón-Patiño, Martha L.; Mejı́a, Aurora; Radji, Sadia; Daridon, Jean-Luc; Barrère-Mangote, Caroline; Giusti, Pierre; Rodgers, Ryan P.; Piscitelli, Vincent; Castillo, Jimmy; Carrier, Hervé; Bouyssière, Brice

doi:10.1021/acs.energyfuels.0c02687

Cited by 29 publications

(44 citation statements)

References 69 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…For whole asphaltenes, ∼59, 27, and 10% of the total area correspond to HMW, MMW, and LMW species, plus a ∼3% for the tailing region. Thus, the size GPC profiles for the extrography fractions indicate that the separation reported by Chacón-Patiño yields asphaltene cuts with distinctive aggregation behavior . The acetone fraction, previously shown to contain abundant single-core (island) motifs with a high production efficiency of non-aggregated ions in APPI, or high MIY, mostly reveals MMW (∼61%) and LMW (∼25%) vanadium-containing species, whereas Hep/Tol and Tol/THF/MeOH fractions, shown to be enriched in multicore (archipelago) structures with a much lower MIY, mostly elute in the HMW region (73/66%).…”

Section: Resultsmentioning

confidence: 62%

“…In previous work, we accessed the precipitation behavior by titration and the molecular composition via direct-infusion (+) APPI FT-ICR MS, of whole PetroPhase 2017 asphaltenes and its extrography fractions. The results suggested a stronger precipitation tendency in heptane/toluene mixtures for Hep/Tol and Tol/THF/MeOH, whereas acetone featured up to ∼20-fold higher stability. , Thus, ionization efficiency in APPI was linked to asphaltene precipitation, and strong aggregation (low concentration of monomeric species) was suggested as the reason for poor ionization efficiency. Furthermore, 51 V-containing compounds, or vanadyl porphyrins (N 4 O 1 51 V 1 ) as revealed by (+) APPI FT-ICR MS, were only detected in the acetone fraction.…”

Section: Resultsmentioning

confidence: 97%

See 1 more Smart Citation

Compositional Trends for Total Vanadium Content and Vanadyl Porphyrins in Gel Permeation Chromatography Fractions Reveal Correlations between Asphaltene Aggregation and Ion Production Efficiency in Atmospheric Pressure Photoionization

et al. 2020

Self Cite

View full text Add to dashboard Cite

Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) has exposed the ultracomplexity of fossil fuels, thereby validating the compositional trends that rule petroleum distillation, known as the Boduszynski Continuum. Routine FT-ICR MS analysis of a single crude oil sample can reveal tens-of-thousands of unique molecular formulas; however, currently available ionization methods suffer from limitations for such complex mixtures that are not yet completely understood. Simply put, MS detects ions, and thus, it depends heavily on the ability of ion sources to indiscriminately volatilize and subsequently ionize samples of interest. Despite advances in soft ionization methods, the characterization of complex matrices remains a challenge due to the lack of an ion source, commercial or custom-built, that can vaporize and ionize all compounds without bias, save analyte concentration. However, atmospheric pressure photoionization (APPI) has been shown to provide the most uniform ion production for mixtures of petroleum model compounds and real samples, with little to no fragmentation. In this work, we investigated the molecular composition of PetroPhase 2017 asphaltenes and its extrography fractions, with a focus on the total vanadium content and molecular composition of vanadyl porphyrins as a function of aggregate size distribution, accessed through separate experiments: online gel permeation chromatography (GPC) inductively coupled plasma−MS (ICP−MS) and online GPC APPI FT-ICR MS (at 21 T). The results reveal that the extrography separation provides asphaltene fractions (i.e., acetone, Hep/Tol, and Tol/THF/MeOH) enriched in 51 V-containing compounds with distinctive aggregate size distributions. The acetone fraction features smaller aggregate sizes, as it elutes later in the GPC chromatogram than Hep/Tol and Tol/THF/MeOH fractions, and overall, presents up to ∼14-fold higher ionization efficiency in APPI. Such behavior suggests a correlation between aggregate size and production efficiency of monomeric ions in APPI. Bulk compositional trends accessed by GPC separation and highlighted by ICP−MS detection indicate that despite multiple separation steps (i.e. extrography followed by GPC), APPI FT-ICR MS can only access ∼37% of the total V-containing compounds. Although the more stable/larger aggregates dominate the size distributions of all asphaltene samples studied, it is the weakly aggregated/monomeric species that are preferentially observed by APPI-MS. Tendencies in the molecular composition of vanadyl porphyrins and S/O-containing compounds strongly suggest that London forces might be central in the self-assembly process of asphaltene nanoaggregates to produce more massive clusters. The results demonstrate that the observed compositional trends (albeit limited) can be accessed when coupling advanced chromatographic separations with online high-field FT-ICR MS detection.

show abstract

Section: Resultsmentioning

confidence: 62%

Section: Resultsmentioning

confidence: 97%

Compositional Trends for Total Vanadium Content and Vanadyl Porphyrins in Gel Permeation Chromatography Fractions Reveal Correlations between Asphaltene Aggregation and Ion Production Efficiency in Atmospheric Pressure Photoionization

et al. 2020

Self Cite

View full text Add to dashboard Cite

show abstract

“…All measurements were carried out with use of the peak force quantitative nanomechanical mapping mode. 53 Images were analyzed by using NanoScope Analysis v1.40 software from Bruker. The height of the asphaltene deposit h D (AFM) was determined as the vertical distance between the average height of the asphaltene-covered surface and the maximal depth of the area over 500 × 500 nm.…”

Section: Methodsmentioning

confidence: 99%

“…AFM imaging of coupons was performed with a MultiMode 8 (BrukerNano) instrument by operating triangular silicon nitride cantilevers, with a spring constant of 0.47 ± 0.03 N/m, and a tip with a diameter of around 10 nm. All measurements were carried out with use of the peak force quantitative nanomechanical mapping mode . Images were analyzed by using NanoScope Analysis v1.40 software from Bruker.…”

Section: Experimental Sectionmentioning

confidence: 99%

Evaluation of the Influence of a Chemical Inhibitor on Asphaltene Destabilization and Deposition Mechanisms under Atmospheric and Oil Production Conditions Using QCM and AFM Techniques

et al. 2021

Self Cite

View full text Add to dashboard Cite

An immersed quartz crystal resonator (QCR) was employed to assess the effectiveness of a modified alkylphenol resin in reducing asphaltene deposition on metal surfaces under various temperature and pressure conditions. The QCR response to asphaltene flocculation was first monitored during isothermal n-heptane titration experiments of dead crude oils with different contents of the asphaltene inhibitor (AI). In addition, the effect of the AI presence on the morphology of asphaltene deposits was analyzed by atomic force microscopy (AFM). Then, constant mass expansion experiments were carried out to determine whether the presence of the AI influenced the asphaltene instability pressure and the deposition rate of asphaltenes in a dead oil + CH4 system with various CH4 contents. The results of all these investigations in the nanometer range shed new light on the AI technology and clearly demonstrate that the presence of the AI can reduce the asphaltene deposition rate and modify the viscoelastic properties of the asphaltene solution in oil production conditions.

show abstract

“…This lack of information is due to the challenge of isolating specific asphaltenes from crude oil mixtures and the general difficulty of probing the molecular structure within molecular monolayers. Acevedo et al have used many techniques, such as Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS), to study the structure of unfractionated asphaltene samples and its relation to precipitation of the process . They found that smaller asphaltenes form more organized structures and suffer less deposition than the larger “archipelago” constituents, which form less-organized structures with a greater amount of deposition.…”

Section: Introductionmentioning

confidence: 99%

Model Asphaltenes Adsorbed onto Methyl- and COOH-Terminated SAMs on Gold

et al. 2021

View full text Add to dashboard Cite

Petroleum asphaltenes are surface-active compounds found in crude oils, and their interactions with surfaces and interfaces have huge implications for many facets of reservoir exploitation, including production, transportation, and oil−water separation. The asphaltene fraction in oil, found in the highest boiling-point range, is composed of many different molecules that vary in size, functionality, and polarity. Studies done on asphaltene fractions have suggested that they interact via polyaromatic and heteroaromatic ring structures and functional groups containing nitrogen, sulfur, and oxygen. However, isolating a single pure chemical structure of asphaltene in abundance is challenging and often not possible, which impairs the molecular-level study of asphaltenes of various architectures on surfaces. Thus, to further the molecular fundamental understanding, we chose to use functionalized model asphaltenes (AcChol-Th, AcChol-Ph, and 1,6-DiEtPy[Bu-Carb]) and model self-assembled monolayer (SAM) surfaces with precisely known chemical structures, whereby the hydrophobicity of the model surface is controlled. We applied solutions of asphaltenes to these SAM surfaces and then analyzed them with surface-sensitive techniques of near-edge X-ray absorption fine structure (NEXAFS) and X-ray photoelectron spectroscopy (XPS). We observe no adsorption of asphaltenes to the hydrophobic surface. On the hydrophilic surface, AcChol-Ph penetrates into the SAM with a preferential orientation parallel to the surface; AcChol-Th adsorbs in a similar manner, and 1,6-DiEtPy[Bu-Carb] binds the surface with a bent binding geometry. Overall, this study demonstrates the need for studying pure and fractionated asphaltenes at the molecular level, as even within a family of asphaltene congeners, very different surface interactions can occur.

show abstract

Understanding Asphaltene Fraction Behavior through Combined Quartz Crystal Resonator Sensor, FT-ICR MS, GPC ICP HR-MS, and AFM Characterization. Part I: Extrography Fractionations

Cited by 29 publications

References 69 publications

Compositional Trends for Total Vanadium Content and Vanadyl Porphyrins in Gel Permeation Chromatography Fractions Reveal Correlations between Asphaltene Aggregation and Ion Production Efficiency in Atmospheric Pressure Photoionization

Compositional Trends for Total Vanadium Content and Vanadyl Porphyrins in Gel Permeation Chromatography Fractions Reveal Correlations between Asphaltene Aggregation and Ion Production Efficiency in Atmospheric Pressure Photoionization

Evaluation of the Influence of a Chemical Inhibitor on Asphaltene Destabilization and Deposition Mechanisms under Atmospheric and Oil Production Conditions Using QCM and AFM Techniques

Model Asphaltenes Adsorbed onto Methyl- and COOH-Terminated SAMs on Gold

Contact Info

Product

Resources

About