Characterization of bio-crude components derived from pyrolysis of soft wood and its esterified product by ultrahigh resolution mass spectrometry and spectroscopic techniques

Lozano, Diana Catalina Palacio; Ramírez, Carlos Alberto García; Chaparro, José Aristóbulo Sarmiento; Thomas, Mary J.; Gavard, Remy; Jones, Hugh E.; Hernández, Rafael Cabanzo; Mejía-Ospino, Enrique; Barrow, Mark P.

doi:10.1016/j.fuel.2019.116085

Cited by 24 publications

(34 citation statements)

References 46 publications

(58 reference statements)

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“…A detailed information of the pyrolytic and esterification conditions can be found elsewhere. 23 The crude bio-oil was subjected to esterification/acetalization with n -butanol in the presence of H 2 SO 4 /dehydration to produce an upgraded product. Hereafter referred to as the “esterified bio-oil,” this upgraded product results from the combined esterification of carboxylic acids to esters and acetalization of aldehydes and ketones into acetals.…”

Section: Methodsmentioning

confidence: 99%

Revealing the Reactivity of Individual Chemical Entities in Complex Mixtures: the Chemistry Behind Bio-Oil Upgrading

et al. 2022

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Bio-oils are precursors for biofuels but are highly corrosive necessitating further upgrading. Furthermore, bio-oil samples are highly complex and represent a broad range of chemistries. They are complex mixtures not simply because of the large number of poly-oxygenated compounds but because each composition can comprise many isomers with multiple functional groups. The use of hyphenated ultrahigh-resolution mass spectrometry affords the ability to separate isomeric species of complex mixtures. Here, we present for the first time, the use of this powerful analytical technique combined with chemical reactivity to gain greater insights into the reactivity of the individual isomeric species of bio-oils. A pyrolysis bio-oils and its esterified bio-oil were analyzed using gas chromatography coupled to Fourier transform ion cyclotron resonance mass spectrometry, and in-house software (KairosMS) was used for fast comparison of the hyphenated data sets. The data revealed a total of 10,368 isomers in the pyrolysis bio-oil and an increase to 18,827 isomers after esterification conditions. Furthermore, the comparison of the isomeric distribution before and after esterification provide new light on the reactivities within these complex mixtures; these reactivities would be expected to correspond with carboxylic acid, aldehyde, and ketone functional groups. Using this approach, it was possible to reveal the increased chemical complexity of bio-oils after upgrading and target detection of valuable compounds within the bio-oils. The combination of chemical reactions alongside with in-depth molecular characterization opens a new window for the understanding of the chemistry and reactivity of complex mixtures.

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Section: Methodsmentioning

confidence: 99%

Revealing the Reactivity of Individual Chemical Entities in Complex Mixtures: the Chemistry Behind Bio-Oil Upgrading

et al. 2022

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“…A crude pyrolysis bio-oil sample with humidity less than 10 wt % was produced using a mixture of softwoods as original material . The samples were dissolved in acetone at a final concentration of 3 ppm, and 1 μL was injected into a 30 m DB-5 column (0.25 mmID, 0.25 μm).…”

Section: Methodsmentioning

confidence: 99%

KairosMS: A New Solution for the Processing of Hyphenated Ultrahigh Resolution Mass Spectrometry Data

et al. 2020

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The use of hyphenated Fourier transform mass spectrometry (FTMS) methods affords additional information about complex chemical mixtures. Coeluted components can be resolved thanks to the ultrahigh resolving power, which also allows extracted ion chromatograms (EICs) to be used for the observation of isomers. As such data sets can be large and data analyses laborious, improved tools are needed for data analyses and extraction of key information. The typical workflow for this type of data is based upon manually dividing the total ion chromatogram (TIC) into several windows of usually equal retention time, averaging the signal of each window to create a single mass spectrum, extracting a peak list, performing the compositional assignments, visualizing the results, and repeating the process for each window. Through removal of the need to manually divide a data set into many time windows and analyze each one, a time-consuming workflow has been significantly simplified. An environmental sample from the oil sands region of Alberta, Canada, and dissolved organic matter samples from the Suwannee River Fulvic Acid (SRFA) and marine waters (Marine DOM) were used as a test bed for the new method. A complete solution named KairosMS was developed in the R language utilizing the Tidyverse packages and Shiny for the user interface. KairosMS imports raw data from common file types, processes it, and exports a mass list for compositional assignments. KairosMS then incorporates those assignments for analysis and visualization. The present method increases the computational speed while reducing the manual work of the analysis when compared to other current methods. The algorithm subsequently incorporates the assignments into the processed data set, generating a series of interactive plots, EICs for individual components or entire compound classes, and can export raw data or graphics for off-line use. Using the example of petroleum related data, it is then visualized according to heteroatom class, carbon number, double bond equivalents, and retention time. The algorithm also gives the ability to screen for isomeric contributions and to follow homologous series or compound classes, instead of individual components, as a function of time.

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“…ESI is prone to ionize compounds with low DBE but more oxygen atoms. In a recent work, Palacio-Lozanoa et al reported the characterization of bio-crudes by using FT-ICR MS with (±)ESI and APPI ionization sources and combined with the NMR analysis.…”

Section: Characterization Of Alternative Fuelsmentioning

confidence: 99%

Molecular Characterization of Fossil and Alternative Fuels Using Electrospray Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry: Recent Advances and Perspectives

et al. 2021

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Molecular composition analysis of petroleum and alternative fuels has been considered as one of the greatest challenges in analytical chemistry. The rapid development of Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) has provided an opportunity to solve this problem. High mass resolution power and mass accuracy enable the separation of isobaric compounds in a complex mixture and assignment of their molecular composition. The combination of electrospray ionization (ESI) with FT-ICR MS achieves direct analysis of polar compounds in petroleum even if they are in trace amounts in the complex matrix. FT-ICR MS has made a great contribution to the chemical understanding of petroleum and alternative fuels; the relevant application is sometimes called “petroleomic analysis”. Hundreds of journal articles have been published over the past two decades using FT-ICR MS instruments to study the molecular composition of petroleum and alternative fuels, in which most of them used ESI as the ionization source. This review will present an overview of the studies regarding the petroleomic characterization of fossil and alternative fuels by FT-ICR MS coupled with ESI and a critical review of their main findings relevant to the chemical composition. Special features of this review are (1) covering the entire historical period; (2) focusing on ESI ionization; (3) a systematic review of the composition of almost all the components and compound classes, including but not limited to petroleum, coal-derived liquids, biofuels, and their distillates; asphaltenes, heavy residues, interfacial active substances; hydrocarbons and heteroatoms; and polar and nonpolar compounds. In addition, the challenges and further research directions will be proposed. This review focuses on the advances enabled by ultrahigh resolving power FT-ICR MS in a tribute to Professor Alan G. Marshall.

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Characterization of bio-crude components derived from pyrolysis of soft wood and its esterified product by ultrahigh resolution mass spectrometry and spectroscopic techniques

Abstract: Please refer to published version for the most recent bibliographic citation information. If a published version is known of, the repository item page linked to above, will contain details on accessing it.

Cited by 24 publications

References 46 publications

Revealing the Reactivity of Individual Chemical Entities in Complex Mixtures: the Chemistry Behind Bio-Oil Upgrading

Revealing the Reactivity of Individual Chemical Entities in Complex Mixtures: the Chemistry Behind Bio-Oil Upgrading

KairosMS: A New Solution for the Processing of Hyphenated Ultrahigh Resolution Mass Spectrometry Data

Molecular Characterization of Fossil and Alternative Fuels Using Electrospray Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry: Recent Advances and Perspectives

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