Reactivity of asphalt supercritical fractions

Liu, M M; Chaffin, J M; Davison, R R; Glover, C J; Bullin, J A

doi:10.1021/ie9605645

Title: Reactivity of asphalt supercritical fractions

Full Record
Other Related Research

Abstract

The reactivities of six supercritical fractions of asphalt SHRP AAF-1 were investigated in the context of their chemical composition. The supercritical fractions were obtained using pentane as the solvent. Each fraction was aged in a pressure oxygen vessel (POV) under seven conditions of temperature and pressure. As with whole asphalts, there is an initial rapid oxidation that slows to a constant rate. The oxidation rates for the constant rate region were measured at each of the conditions to determine the kinetic parameters of the fractions. Arrhenius plots were then constructed for the fractions to compare their reactivities. Variations in activation energy and reaction order were within experimental error. Results show that reactivity increases with fraction number for the supercritical fractions. The heavier fractions are more reactive not only because they contain more polar aromatics in terms of Corbett analysis fractions but also because the polar aromatics of the heavier fractions are larger in molecular size and are more reactive. Additionally, heavier fractions contain more asphaltenes that are larger in molecular size. Because for light fractions the reaction rates, and as previously shown the hardening rates, are very low and remain constant with oxidation, air blowing of some light fractions wouldmore »« less

Authors:

Liu, M M; Chaffin, J M; Davison, R R; Glover, C J; Bullin, J A ^[1]

Texas A and M Univ., College Station, TX (United States)

Publication Date:: Sun Jun 01 00:00:00 EDT 1997

Sponsoring Org.:: USDOE Assistant Secretary for Energy Efficiency and Renewable Energy, Washington, DC (United States)

OSTI Identifier:: 514629

DOE Contract Number:: FC04-93AL94460

Resource Type:: Journal Article

Journal Name:: Industrial and Engineering Chemistry Research

Additional Journal Information:: Journal Volume: 36; Journal Issue: 6; Other Information: PBD: Jun 1997

Country of Publication:: United States

Language:: English

Subject:: 02 PETROLEUM; PETROLEUM FRACTIONS; ACTIVATION ENERGY; STRUCTURAL CHEMICAL ANALYSIS; MOLECULAR WEIGHT; SUPERCRITICAL GAS EXTRACTION; FRACTIONATION

Citation Formats


                    Liu, M M, Chaffin, J M, Davison, R R, Glover, C J, and Bullin, J A. Reactivity of asphalt supercritical fractions.  United States: N. p., 1997. 
        Web.  doi:10.1021/ie9605645.

Copy to clipboard


                    Liu, M M, Chaffin, J M, Davison, R R, Glover, C J, & Bullin, J A. Reactivity of asphalt supercritical fractions.  United States.  https://doi.org/10.1021/ie9605645

Copy to clipboard


                    Liu, M M, Chaffin, J M, Davison, R R, Glover, C J, and Bullin, J A. 1997.  
        "Reactivity of asphalt supercritical fractions".  United States.  https://doi.org/10.1021/ie9605645.

Copy to clipboard


                    
@article{osti_514629,

  title        = {Reactivity of asphalt supercritical fractions},

  author       = {Liu, M M and Chaffin, J M and Davison, R R and Glover, C J and Bullin, J A},

  abstractNote = {The reactivities of six supercritical fractions of asphalt SHRP AAF-1 were investigated in the context of their chemical composition. The supercritical fractions were obtained using pentane as the solvent. Each fraction was aged in a pressure oxygen vessel (POV) under seven conditions of temperature and pressure. As with whole asphalts, there is an initial rapid oxidation that slows to a constant rate. The oxidation rates for the constant rate region were measured at each of the conditions to determine the kinetic parameters of the fractions. Arrhenius plots were then constructed for the fractions to compare their reactivities. Variations in activation energy and reaction order were within experimental error. Results show that reactivity increases with fraction number for the supercritical fractions. The heavier fractions are more reactive not only because they contain more polar aromatics in terms of Corbett analysis fractions but also because the polar aromatics of the heavier fractions are larger in molecular size and are more reactive. Additionally, heavier fractions contain more asphaltenes that are larger in molecular size. Because for light fractions the reaction rates, and as previously shown the hardening rates, are very low and remain constant with oxidation, air blowing of some light fractions would be expected to produce an asphalt with a very low hardening rate. Data explicitly show that for petroleum fractions from the same crude source molecular size distribution is a good indicator of reactivity. This is not necessarily true for petroleum fractions from different crude sources, however.},

  doi          = {10.1021/ie9605645},

  url          = {https://www.osti.gov/biblio/514629},
  journal      = {Industrial and Engineering Chemistry Research},
number       = 6,

  volume       = 36,

  place        = {United States},

  year         = {Sun Jun 01 00:00:00 EDT 1997},

  month        = {Sun Jun 01 00:00:00 EDT 1997}

}

Copy to clipboard

Journal Article:

https://doi.org/10.1021/ie9605645

Other availability

Find in Google Scholar

Search WorldCat to find libraries that may hold this journal

Save / Share:

Export Metadata

Save to My Library

Similar records in OSTI.GOV collections:

Oxygen uptake as correlated to carbonyl growth in aged asphalts and asphalt Corbett fractions

Journal Article Liu, M; Ferry, M; Davison, R; ... - Industrial and Engineering Chemistry Research

Ten asphalts, including seven Strategic Highway Research Program (SHRP) asphalts and three Texas asphalts, plus naphthene and polar aromatic Corbett fractions for five of the seven SHRP asphalts were aged at laboratory conditions. The oxygen content by direct measurement and the FTIR carbonyl content were obtained for samples which were aged to varying degrees. It was found that, for each material, the oxygen content correlates linearly with the carbonyl content. The correlation is independent of aging temperature and aging pressure over the ranges studied. Furthermore, each material has a unique correlation coefficient, and the correlation slope for a whole asphaltmore »« less
https://doi.org/10.1021/ie980450o
Characterization of Corbett fractions of asphalt by FT-IR and NMR spectrometry

Conference Philip, C; Bullin, J; Glover, C; ... - American Chemical Society, Division of Petroleum Chemistry, Preprints; (USA)

The Corbett separation technique utilizes the difference in the solubility of chemical species in solvents with varying polarity. Asphalt samples are separated into four fractions-asphaltenes, saturates, naphthene aromatics and polar aromatics. Some of the drawbacks of the Corbett separation technique which is very labor intensive, includes lack of reproducibility and overlapping of fractions. Proton and {sup 13}C NMR spectrometry can identify the chemical nature of hydrogens and carbons even in complex organic mixtures such as petroleum crude and its refinery products. The wide use of Fourier Transform infrared spectrometry (FT-IR) for the analysis of fossil fuels has been reported. NMRmore »« less
Supercritical fractions as asphalt recycling agents and preliminary aging studies on recycled asphalts

Journal Article Chaffin, J; Liu, M; Davison, R; ... - Industrial and Engineering Chemistry Research

Several asphalts were fractionated using supercritical pentane. These fractions were analyzed by gel permeation chromatography and high-performance liquid chromatography, and their viscosities were measured. The properties of these fractions vary not only among the fractions of a given asphalt but also for the same fraction produced from different asphalts. These widely varied fractions previously have been shown to have potential for reblending to produce superior asphalts. This study investigates the potential for using some of the fractions as asphalt recycling agents. A modified strategic highway research program (SHRP) pressure aging vessel (PAV) test and kinetics studies were conducted on ninemore »« less
https://doi.org/10.1021/ie9604435
Viscosity, relaxation time, and dynamics within a model asphalt of larger molecules

Journal Article Li, Derek - Journal of Chemical Physics

The dynamics properties of a new “next generation” model asphalt system that represents SHRP AAA-1 asphalt using larger molecules than past models is studied using molecular simulation. The system contains 72 molecules distributed over 12 molecule types that range from nonpolar branched alkanes to polar resins and asphaltenes. Molecular weights range from 290 to 890 g/mol. All-atom molecular dynamics simulations conducted at six temperatures from 298.15 to 533.15 K provide a wealth of correlation data. The modified Kohlrausch-Williams-Watts equation was regressed to reorientation time correlation functions and extrapolated to calculate average rotational relaxation times for individual molecules. The rotational relaxationmore »« less
https://doi.org/10.1063/1.4848736
Investigation of structural inhomogeneity and physical aging in asphalts by solid state NMR

Conference VanderHart, D; Manders, W; Campbell, G - American Chemical Society, Division of Petroleum Chemistry, Preprints; (United States)

This work is part of the Strategic Highways Research Program (SHRP) and involves the characterization of certain asphalt cements which have been identified as core asphalts in this program. One motivation was to see if solid state NMR could shed any light on the physical aging (or hardening) of asphaltic materials from the point of view of average changes in molecular mobilities. For this work the authors assumed that there would be gradients of molecular mobility and composition on some spatial scale and they sought to determine this scale. Proton spin diffusion was used to obtain a measure of themore »« less

Similar Records