skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Determining aromatic and aliphatic carboxylic acids in biomass-derived oil samples using 2,4-dinitrophenylhydrazine and liquid chromatography-electrospray injection-mass spectrometry/mass spectrometry

Abstract

Here, converting biomass to a useful fuel commonly incorporates the pyrolysis of the biomass feed stock. The base liquid fraction usually contains high concentrations of ketones, aldehydes and carboxylic acids, of which each can cause detrimental issues related to the storage and upgrading process. Knowing the carbonyl species and the concentration of each will provide value information to the pyrolysis researchers, specifically as that community branches into more targeted end-products such as jet fuel or biogenic-derived oxygenate-containing fuel products. The analysis of aldehydes, ketones and small alkyl carboxylic acids using 2,4-dinitrophenylhydrazine (DNPH) derivation method has been well documented and the method is commonly used the analytical community. By using liquid chromatograph coupled to tandem mass spectrometry, biomass sample analysis can be complete with identification of most carbonyl species. The issue of identifying isobaric ketone and aldehyde compounds can be resolved by utilizing differences in retention time or characteristic fragment ions of ketones and aldehydes. One issue which could not resolved using published methods was identifying aromatic or large non-aromatic carboxylic acids from their corresponding hydroxyl aldehyde or ketone analogs. By modifying the current method for determining carbonyls in biomass samples, carboxylic and hydroxyl-carbonyl can be determined. A careful adjustment ofmore » the pH during the extraction procedure and extended heating time of the DNPH solution allowed for the successful derivation of aromatic carboxylic acids. Like other dinitrophenylhydrazones, carboxylic acid derivatives also produce a unique secondary ion pattern, which was useful to distinguish these species from the non-acid analogs.« less

Authors:
ORCiD logo [1]; ORCiD logo [1];  [2]; ORCiD logo [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE)
OSTI Identifier:
1412049
Grant/Contract Number:
AC05-00OR22725
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Biomass and Bioenergy
Additional Journal Information:
Journal Volume: 108; Journal Issue: C; Journal ID: ISSN 0961-9534
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
09 BIOMASS FUELS; Biomass; Pyrolysis oil; Derivatization of carboxylic acids; 2,4-Dinitrophenylhydrazine (DNPH); Carbonyl speciation; Tandem mass spectrometry

Citation Formats

Lewis, Sr., Samuel A., Connatser, Raynella M., Olarte, Mariefel V., and Keiser, James R. Determining aromatic and aliphatic carboxylic acids in biomass-derived oil samples using 2,4-dinitrophenylhydrazine and liquid chromatography-electrospray injection-mass spectrometry/mass spectrometry. United States: N. p., 2017. Web. doi:10.1016/j.biombioe.2017.10.043.
Lewis, Sr., Samuel A., Connatser, Raynella M., Olarte, Mariefel V., & Keiser, James R. Determining aromatic and aliphatic carboxylic acids in biomass-derived oil samples using 2,4-dinitrophenylhydrazine and liquid chromatography-electrospray injection-mass spectrometry/mass spectrometry. United States. doi:10.1016/j.biombioe.2017.10.043.
Lewis, Sr., Samuel A., Connatser, Raynella M., Olarte, Mariefel V., and Keiser, James R. Wed . "Determining aromatic and aliphatic carboxylic acids in biomass-derived oil samples using 2,4-dinitrophenylhydrazine and liquid chromatography-electrospray injection-mass spectrometry/mass spectrometry". United States. doi:10.1016/j.biombioe.2017.10.043.
@article{osti_1412049,
title = {Determining aromatic and aliphatic carboxylic acids in biomass-derived oil samples using 2,4-dinitrophenylhydrazine and liquid chromatography-electrospray injection-mass spectrometry/mass spectrometry},
author = {Lewis, Sr., Samuel A. and Connatser, Raynella M. and Olarte, Mariefel V. and Keiser, James R.},
abstractNote = {Here, converting biomass to a useful fuel commonly incorporates the pyrolysis of the biomass feed stock. The base liquid fraction usually contains high concentrations of ketones, aldehydes and carboxylic acids, of which each can cause detrimental issues related to the storage and upgrading process. Knowing the carbonyl species and the concentration of each will provide value information to the pyrolysis researchers, specifically as that community branches into more targeted end-products such as jet fuel or biogenic-derived oxygenate-containing fuel products. The analysis of aldehydes, ketones and small alkyl carboxylic acids using 2,4-dinitrophenylhydrazine (DNPH) derivation method has been well documented and the method is commonly used the analytical community. By using liquid chromatograph coupled to tandem mass spectrometry, biomass sample analysis can be complete with identification of most carbonyl species. The issue of identifying isobaric ketone and aldehyde compounds can be resolved by utilizing differences in retention time or characteristic fragment ions of ketones and aldehydes. One issue which could not resolved using published methods was identifying aromatic or large non-aromatic carboxylic acids from their corresponding hydroxyl aldehyde or ketone analogs. By modifying the current method for determining carbonyls in biomass samples, carboxylic and hydroxyl-carbonyl can be determined. A careful adjustment of the pH during the extraction procedure and extended heating time of the DNPH solution allowed for the successful derivation of aromatic carboxylic acids. Like other dinitrophenylhydrazones, carboxylic acid derivatives also produce a unique secondary ion pattern, which was useful to distinguish these species from the non-acid analogs.},
doi = {10.1016/j.biombioe.2017.10.043},
journal = {Biomass and Bioenergy},
number = C,
volume = 108,
place = {United States},
year = {Wed Nov 22 00:00:00 EST 2017},
month = {Wed Nov 22 00:00:00 EST 2017}
}

Journal Article:
Free Publicly Available Full Text
This content will become publicly available on November 22, 2018
Publisher's Version of Record

Save / Share: