Comparative compositional analysis of untreated and hydrotreated oil by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry

Zhigang Wu, Ryan P. Rodgers, Alan G. Marshall, James J. Strohm, Chunshan Song

Research output: Contribution to journalArticle

41 Citations (Scopus)

Abstract

The ultrahigh mass resolving power (> 350 000) and mass accuracy (< 1 ppm) of electrospray ionization (ESI) Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) enable resolution and identification of most of the thousands of polar heteroatomic species in petroleum distillates. Here, we compare elemental compositions of components of a 1:1 mixture of light cycle oil and refined chemical oil before and after each of three catalytic hydrotreatments over NiMo: single-pass at 690 °F, double-pass at 690 and 725 °F, and double-pass for a reactor partly clogged with coke. The effects of catalysis are reflected by changes in the relative abundances of various heteroatomic classes (NnOoSs), aromaticity (rings plus double bonds, or double bond equivalents, DBE) distributions for species of a given class, and carbon number (i.e., alkylation distributions for species of a given class and DBE. Apart from expected changes (e.g., selective removal of heteroatom-containing species, reduction of aromatic species), some surprising results (e.g., increase in relative abundance of the most highly aromatic species, increase in carbon number for a given class and DBE, etc.) can be explained by partial saturation of aromatic rings and preferential removal of saturated rings, but incomplete cleavage of carbon-nitrogen bonds, in accord with a theoretical catalytic model. Incomplete hydrotreatment is shown to introduce new heteroatomic compounds not found in the original sample. Detailed elemental composition comparisons of the type shown here provide a new and rational basis for optimizing parameters for hydrotreatment of hydrocarbon fuel streams and evaluation of catalyst performance. Identification of which species increase or decrease in abundance and especially which new species are produced should greatly improve understanding of differential catalytic efficiency for removal and/or conversion of potentially all of the chemical constituents of an oil feedstock.

Original languageEnglish (US)
Pages (from-to)1072-1077
Number of pages6
JournalEnergy and Fuels
Volume19
Issue number3
DOIs
StatePublished - May 1 2005

Fingerprint

Cyclotron resonance
Electrospray ionization
Mass spectrometry
Fourier transforms
Oils
Carbon
Ions
Petroleum distillates
Alkylation
Optical resolving power
Hydrocarbons
Chemical analysis
Coke
Feedstocks
Catalysis
Nitrogen
Catalysts

All Science Journal Classification (ASJC) codes

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

Cite this

@article{eb8542d6d45142d4acd1d820fe08040a,
title = "Comparative compositional analysis of untreated and hydrotreated oil by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry",
abstract = "The ultrahigh mass resolving power (> 350 000) and mass accuracy (< 1 ppm) of electrospray ionization (ESI) Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) enable resolution and identification of most of the thousands of polar heteroatomic species in petroleum distillates. Here, we compare elemental compositions of components of a 1:1 mixture of light cycle oil and refined chemical oil before and after each of three catalytic hydrotreatments over NiMo: single-pass at 690 °F, double-pass at 690 and 725 °F, and double-pass for a reactor partly clogged with coke. The effects of catalysis are reflected by changes in the relative abundances of various heteroatomic classes (NnOoSs), aromaticity (rings plus double bonds, or double bond equivalents, DBE) distributions for species of a given class, and carbon number (i.e., alkylation distributions for species of a given class and DBE. Apart from expected changes (e.g., selective removal of heteroatom-containing species, reduction of aromatic species), some surprising results (e.g., increase in relative abundance of the most highly aromatic species, increase in carbon number for a given class and DBE, etc.) can be explained by partial saturation of aromatic rings and preferential removal of saturated rings, but incomplete cleavage of carbon-nitrogen bonds, in accord with a theoretical catalytic model. Incomplete hydrotreatment is shown to introduce new heteroatomic compounds not found in the original sample. Detailed elemental composition comparisons of the type shown here provide a new and rational basis for optimizing parameters for hydrotreatment of hydrocarbon fuel streams and evaluation of catalyst performance. Identification of which species increase or decrease in abundance and especially which new species are produced should greatly improve understanding of differential catalytic efficiency for removal and/or conversion of potentially all of the chemical constituents of an oil feedstock.",
author = "Zhigang Wu and Rodgers, {Ryan P.} and Marshall, {Alan G.} and Strohm, {James J.} and Chunshan Song",
year = "2005",
month = "5",
day = "1",
doi = "10.1021/ef049828n",
language = "English (US)",
volume = "19",
pages = "1072--1077",
journal = "Energy & Fuels",
issn = "0887-0624",
publisher = "American Chemical Society",
number = "3",

}

Comparative compositional analysis of untreated and hydrotreated oil by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry. / Wu, Zhigang; Rodgers, Ryan P.; Marshall, Alan G.; Strohm, James J.; Song, Chunshan.

In: Energy and Fuels, Vol. 19, No. 3, 01.05.2005, p. 1072-1077.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Comparative compositional analysis of untreated and hydrotreated oil by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry

AU - Wu, Zhigang

AU - Rodgers, Ryan P.

AU - Marshall, Alan G.

AU - Strohm, James J.

AU - Song, Chunshan

PY - 2005/5/1

Y1 - 2005/5/1

N2 - The ultrahigh mass resolving power (> 350 000) and mass accuracy (< 1 ppm) of electrospray ionization (ESI) Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) enable resolution and identification of most of the thousands of polar heteroatomic species in petroleum distillates. Here, we compare elemental compositions of components of a 1:1 mixture of light cycle oil and refined chemical oil before and after each of three catalytic hydrotreatments over NiMo: single-pass at 690 °F, double-pass at 690 and 725 °F, and double-pass for a reactor partly clogged with coke. The effects of catalysis are reflected by changes in the relative abundances of various heteroatomic classes (NnOoSs), aromaticity (rings plus double bonds, or double bond equivalents, DBE) distributions for species of a given class, and carbon number (i.e., alkylation distributions for species of a given class and DBE. Apart from expected changes (e.g., selective removal of heteroatom-containing species, reduction of aromatic species), some surprising results (e.g., increase in relative abundance of the most highly aromatic species, increase in carbon number for a given class and DBE, etc.) can be explained by partial saturation of aromatic rings and preferential removal of saturated rings, but incomplete cleavage of carbon-nitrogen bonds, in accord with a theoretical catalytic model. Incomplete hydrotreatment is shown to introduce new heteroatomic compounds not found in the original sample. Detailed elemental composition comparisons of the type shown here provide a new and rational basis for optimizing parameters for hydrotreatment of hydrocarbon fuel streams and evaluation of catalyst performance. Identification of which species increase or decrease in abundance and especially which new species are produced should greatly improve understanding of differential catalytic efficiency for removal and/or conversion of potentially all of the chemical constituents of an oil feedstock.

AB - The ultrahigh mass resolving power (> 350 000) and mass accuracy (< 1 ppm) of electrospray ionization (ESI) Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) enable resolution and identification of most of the thousands of polar heteroatomic species in petroleum distillates. Here, we compare elemental compositions of components of a 1:1 mixture of light cycle oil and refined chemical oil before and after each of three catalytic hydrotreatments over NiMo: single-pass at 690 °F, double-pass at 690 and 725 °F, and double-pass for a reactor partly clogged with coke. The effects of catalysis are reflected by changes in the relative abundances of various heteroatomic classes (NnOoSs), aromaticity (rings plus double bonds, or double bond equivalents, DBE) distributions for species of a given class, and carbon number (i.e., alkylation distributions for species of a given class and DBE. Apart from expected changes (e.g., selective removal of heteroatom-containing species, reduction of aromatic species), some surprising results (e.g., increase in relative abundance of the most highly aromatic species, increase in carbon number for a given class and DBE, etc.) can be explained by partial saturation of aromatic rings and preferential removal of saturated rings, but incomplete cleavage of carbon-nitrogen bonds, in accord with a theoretical catalytic model. Incomplete hydrotreatment is shown to introduce new heteroatomic compounds not found in the original sample. Detailed elemental composition comparisons of the type shown here provide a new and rational basis for optimizing parameters for hydrotreatment of hydrocarbon fuel streams and evaluation of catalyst performance. Identification of which species increase or decrease in abundance and especially which new species are produced should greatly improve understanding of differential catalytic efficiency for removal and/or conversion of potentially all of the chemical constituents of an oil feedstock.

UR - http://www.scopus.com/inward/record.url?scp=20544453595&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=20544453595&partnerID=8YFLogxK

U2 - 10.1021/ef049828n

DO - 10.1021/ef049828n

M3 - Article

AN - SCOPUS:20544453595

VL - 19

SP - 1072

EP - 1077

JO - Energy & Fuels

JF - Energy & Fuels

SN - 0887-0624

IS - 3

ER -