Asphaltene self-association: Modeling and effect of fractionation with a polar solvent

Daniel Merino Garcia, J Murgich, Simon Ivar Andersen

Research output: Contribution to journalJournal articleResearchpeer-review

Abstract

The self-association of asphaltenes in toluene is believed to occur step-wise, rather than by the formation of micelles. A number of step-wise models have been used to fit the calorimetric titration of asphaltenes in dried toluene solutions, with excellent results. All the models are based on chemical reactions equivalent to the ones found in polymerization. The study shows that the choice of the average properties of asphaltenes, such as the molecular weight, is critical in the final value of the parameter of interest, namely the average heat of self-association DeltaH(a). The low values of DeltaH(a) obtained suggest that a fraction of asphaltenes is not active in the calorimetric experiments. Asphaltenes from Venezuela (LM1) and Mexico (KU) have been fractionated by precipitation with a mixture of acetone and toluene. It is considered that the most polar compounds are collected in the soluble fraction. A calorimetry study was performed on the two fractions, and the results show that the soluble fraction (SOL) has a much higher heat developed than the insoluble fraction (INS). This suggests again that a fraction of asphaltenes is not active in the calorimetric experiments, either because it does not self-associate or because the dilution effect is not strong enough to break the aggregates. Fluorescence and IR spectroscopy experiments confirm there is self-association in INS fraction, leading to the conclusion that asphaltene aggregates are formed by bonds of different strengths. The stronger aggregates would be predominantly in INS fraction and would be inactive in the calorimetric experiments.
Original languageEnglish
JournalPetroleum Science and Technology
Volume22
Issue number7-8
Pages (from-to)735-758
ISSN1091-6466
DOIs
Publication statusPublished - 2004

Cite this

@article{59d75424b2114e6fbfd028dc018a6a4c,
title = "Asphaltene self-association: Modeling and effect of fractionation with a polar solvent",
abstract = "The self-association of asphaltenes in toluene is believed to occur step-wise, rather than by the formation of micelles. A number of step-wise models have been used to fit the calorimetric titration of asphaltenes in dried toluene solutions, with excellent results. All the models are based on chemical reactions equivalent to the ones found in polymerization. The study shows that the choice of the average properties of asphaltenes, such as the molecular weight, is critical in the final value of the parameter of interest, namely the average heat of self-association DeltaH(a). The low values of DeltaH(a) obtained suggest that a fraction of asphaltenes is not active in the calorimetric experiments. Asphaltenes from Venezuela (LM1) and Mexico (KU) have been fractionated by precipitation with a mixture of acetone and toluene. It is considered that the most polar compounds are collected in the soluble fraction. A calorimetry study was performed on the two fractions, and the results show that the soluble fraction (SOL) has a much higher heat developed than the insoluble fraction (INS). This suggests again that a fraction of asphaltenes is not active in the calorimetric experiments, either because it does not self-associate or because the dilution effect is not strong enough to break the aggregates. Fluorescence and IR spectroscopy experiments confirm there is self-association in INS fraction, leading to the conclusion that asphaltene aggregates are formed by bonds of different strengths. The stronger aggregates would be predominantly in INS fraction and would be inactive in the calorimetric experiments.",
author = "Garcia, {Daniel Merino} and J Murgich and Andersen, {Simon Ivar}",
year = "2004",
doi = "10.1081/LFT-120038710",
language = "English",
volume = "22",
pages = "735--758",
journal = "Petroleum Science and Technology",
issn = "1091-6466",
publisher = "Taylor & Francis Inc.",
number = "7-8",

}

Asphaltene self-association: Modeling and effect of fractionation with a polar solvent. / Garcia, Daniel Merino; Murgich, J; Andersen, Simon Ivar.

In: Petroleum Science and Technology, Vol. 22, No. 7-8, 2004, p. 735-758.

Research output: Contribution to journalJournal articleResearchpeer-review

TY - JOUR

T1 - Asphaltene self-association: Modeling and effect of fractionation with a polar solvent

AU - Garcia, Daniel Merino

AU - Murgich, J

AU - Andersen, Simon Ivar

PY - 2004

Y1 - 2004

N2 - The self-association of asphaltenes in toluene is believed to occur step-wise, rather than by the formation of micelles. A number of step-wise models have been used to fit the calorimetric titration of asphaltenes in dried toluene solutions, with excellent results. All the models are based on chemical reactions equivalent to the ones found in polymerization. The study shows that the choice of the average properties of asphaltenes, such as the molecular weight, is critical in the final value of the parameter of interest, namely the average heat of self-association DeltaH(a). The low values of DeltaH(a) obtained suggest that a fraction of asphaltenes is not active in the calorimetric experiments. Asphaltenes from Venezuela (LM1) and Mexico (KU) have been fractionated by precipitation with a mixture of acetone and toluene. It is considered that the most polar compounds are collected in the soluble fraction. A calorimetry study was performed on the two fractions, and the results show that the soluble fraction (SOL) has a much higher heat developed than the insoluble fraction (INS). This suggests again that a fraction of asphaltenes is not active in the calorimetric experiments, either because it does not self-associate or because the dilution effect is not strong enough to break the aggregates. Fluorescence and IR spectroscopy experiments confirm there is self-association in INS fraction, leading to the conclusion that asphaltene aggregates are formed by bonds of different strengths. The stronger aggregates would be predominantly in INS fraction and would be inactive in the calorimetric experiments.

AB - The self-association of asphaltenes in toluene is believed to occur step-wise, rather than by the formation of micelles. A number of step-wise models have been used to fit the calorimetric titration of asphaltenes in dried toluene solutions, with excellent results. All the models are based on chemical reactions equivalent to the ones found in polymerization. The study shows that the choice of the average properties of asphaltenes, such as the molecular weight, is critical in the final value of the parameter of interest, namely the average heat of self-association DeltaH(a). The low values of DeltaH(a) obtained suggest that a fraction of asphaltenes is not active in the calorimetric experiments. Asphaltenes from Venezuela (LM1) and Mexico (KU) have been fractionated by precipitation with a mixture of acetone and toluene. It is considered that the most polar compounds are collected in the soluble fraction. A calorimetry study was performed on the two fractions, and the results show that the soluble fraction (SOL) has a much higher heat developed than the insoluble fraction (INS). This suggests again that a fraction of asphaltenes is not active in the calorimetric experiments, either because it does not self-associate or because the dilution effect is not strong enough to break the aggregates. Fluorescence and IR spectroscopy experiments confirm there is self-association in INS fraction, leading to the conclusion that asphaltene aggregates are formed by bonds of different strengths. The stronger aggregates would be predominantly in INS fraction and would be inactive in the calorimetric experiments.

U2 - 10.1081/LFT-120038710

DO - 10.1081/LFT-120038710

M3 - Journal article

VL - 22

SP - 735

EP - 758

JO - Petroleum Science and Technology

JF - Petroleum Science and Technology

SN - 1091-6466

IS - 7-8

ER -