Preferential adsorption of nickel porphyrin to resin to increase asphaltene precipitation

Masoumeh Mousavi, Shahrzad Hosseinnezhad, Albert M. Hung, Ellie H. Fini

Research output: Contribution to journalArticle

Abstract

This paper incorporates a multi-scale approach to evaluate the contribution of nickel porphyrin to the aggregation and precipitation of asphaltenes in a medium of solvent/precipitator. This study provides an in-depth understanding of the role of metalloporphyrins in the complex matrix of petroleum/bitumen. Density functional theory (DFT) calculations and laboratory experiments were performed to examine the changes in physicochemical and rheological properties of a selected bituminous structure when doped with Ni octaethylporphyrin (NiOEP). Based on the DFT results, light and small assemblies of asphaltene-resin (in the limit of a single asphaltene molecule) are easily attracted to NiOEP. This in turn may help establish the role of a metal center as a nucleating agent promoting formation of small nanoaggregates in solution. Our experiment results using size-exclusion chromatography and rheological analysis of bitumen doped with NiOEP indicate an increased number of small-size nanoaggregates, as evidenced by a reduction in large molecular size (LMS) and a reduction in the polydispersity index. The latter is indicative of the formation of uniform particle size within the matrix after being doped with NiOEP. The modeling results further show that in larger nanoaggregates, asphaltene-asphaltene intermolecular interactions are too strong to allow an asphaltene core to be affected by NiOEP. In such cases, small resin molecules surrounding asphaltenes show preferential adsorption to NiOEP and take distance from the original nanoaggregates, reducing nanoaggregates’ overall size. This was in line with UV–Vis absorption spectroscopy of a NiOEP-doped solution of bitumen showing that at least 95% of the added NiOEP remained in the maltenes portion containing resin, while only a trace amount of NiOEP was found in the asphaltenes. Considering the role of resins in stabilizing asphaltene aggregates, their departure can promote precipitation of asphaltene nanoaggregates. The latter was also evidenced by TLC-FID chromatography measurement, showing a substantial increase in asphaltene extracts in NiOEP-doped specimens compared to a control sample.

Original languageEnglish (US)
Pages (from-to)468-479
Number of pages12
JournalFuel
Volume236
DOIs
StatePublished - Jan 15 2019
Externally publishedYes

Fingerprint

Porphyrins
Nickel
Asphaltenes
Resins
asphalt
Adsorption
Density functional theory
Molecules
Size exclusion chromatography
Polydispersity
Chromatography
Absorption spectroscopy
Agglomeration
Crude oil
Experiments
Particle size
Metalloporphyrins
octaethylporphyrin
asphaltene
Metals

Keywords

  • Asphaltene
  • Metalloporphyrin
  • Nanoaggregates
  • Peptizing
  • Polydispersity
  • Precipitation

ASJC Scopus subject areas

  • Chemical Engineering(all)
  • Fuel Technology
  • Energy Engineering and Power Technology
  • Organic Chemistry

Cite this

Preferential adsorption of nickel porphyrin to resin to increase asphaltene precipitation. / Mousavi, Masoumeh; Hosseinnezhad, Shahrzad; Hung, Albert M.; Fini, Ellie H.

In: Fuel, Vol. 236, 15.01.2019, p. 468-479.

Research output: Contribution to journalArticle

Mousavi, Masoumeh ; Hosseinnezhad, Shahrzad ; Hung, Albert M. ; Fini, Ellie H. / Preferential adsorption of nickel porphyrin to resin to increase asphaltene precipitation. In: Fuel. 2019 ; Vol. 236. pp. 468-479.
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N2 - This paper incorporates a multi-scale approach to evaluate the contribution of nickel porphyrin to the aggregation and precipitation of asphaltenes in a medium of solvent/precipitator. This study provides an in-depth understanding of the role of metalloporphyrins in the complex matrix of petroleum/bitumen. Density functional theory (DFT) calculations and laboratory experiments were performed to examine the changes in physicochemical and rheological properties of a selected bituminous structure when doped with Ni octaethylporphyrin (NiOEP). Based on the DFT results, light and small assemblies of asphaltene-resin (in the limit of a single asphaltene molecule) are easily attracted to NiOEP. This in turn may help establish the role of a metal center as a nucleating agent promoting formation of small nanoaggregates in solution. Our experiment results using size-exclusion chromatography and rheological analysis of bitumen doped with NiOEP indicate an increased number of small-size nanoaggregates, as evidenced by a reduction in large molecular size (LMS) and a reduction in the polydispersity index. The latter is indicative of the formation of uniform particle size within the matrix after being doped with NiOEP. The modeling results further show that in larger nanoaggregates, asphaltene-asphaltene intermolecular interactions are too strong to allow an asphaltene core to be affected by NiOEP. In such cases, small resin molecules surrounding asphaltenes show preferential adsorption to NiOEP and take distance from the original nanoaggregates, reducing nanoaggregates’ overall size. This was in line with UV–Vis absorption spectroscopy of a NiOEP-doped solution of bitumen showing that at least 95% of the added NiOEP remained in the maltenes portion containing resin, while only a trace amount of NiOEP was found in the asphaltenes. Considering the role of resins in stabilizing asphaltene aggregates, their departure can promote precipitation of asphaltene nanoaggregates. The latter was also evidenced by TLC-FID chromatography measurement, showing a substantial increase in asphaltene extracts in NiOEP-doped specimens compared to a control sample.

AB - This paper incorporates a multi-scale approach to evaluate the contribution of nickel porphyrin to the aggregation and precipitation of asphaltenes in a medium of solvent/precipitator. This study provides an in-depth understanding of the role of metalloporphyrins in the complex matrix of petroleum/bitumen. Density functional theory (DFT) calculations and laboratory experiments were performed to examine the changes in physicochemical and rheological properties of a selected bituminous structure when doped with Ni octaethylporphyrin (NiOEP). Based on the DFT results, light and small assemblies of asphaltene-resin (in the limit of a single asphaltene molecule) are easily attracted to NiOEP. This in turn may help establish the role of a metal center as a nucleating agent promoting formation of small nanoaggregates in solution. Our experiment results using size-exclusion chromatography and rheological analysis of bitumen doped with NiOEP indicate an increased number of small-size nanoaggregates, as evidenced by a reduction in large molecular size (LMS) and a reduction in the polydispersity index. The latter is indicative of the formation of uniform particle size within the matrix after being doped with NiOEP. The modeling results further show that in larger nanoaggregates, asphaltene-asphaltene intermolecular interactions are too strong to allow an asphaltene core to be affected by NiOEP. In such cases, small resin molecules surrounding asphaltenes show preferential adsorption to NiOEP and take distance from the original nanoaggregates, reducing nanoaggregates’ overall size. This was in line with UV–Vis absorption spectroscopy of a NiOEP-doped solution of bitumen showing that at least 95% of the added NiOEP remained in the maltenes portion containing resin, while only a trace amount of NiOEP was found in the asphaltenes. Considering the role of resins in stabilizing asphaltene aggregates, their departure can promote precipitation of asphaltene nanoaggregates. The latter was also evidenced by TLC-FID chromatography measurement, showing a substantial increase in asphaltene extracts in NiOEP-doped specimens compared to a control sample.

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