Nontarget Analysis of Oxygenates in Catalytic Fast Pyrolysis Biocrudes by Supercritical Fluid Chromatography High-Resolution Mass Spectrometry

Abstract

Catalytic fast pyrolysis (CFP) biocrudes can comprise up to 30 wt % of oxygen content in compounds such as polyphenols, acids, carbonyls, and anhydrosugars and thus require upgrading by, e.g., hydrotreatment, to produce transport fuels. The chemical characterization of phenolic and acidic compounds in biocrudes is of great importance to optimize the CFP process. In this study, an analytical workflow is proposed for nontarget chemical fingerprinting analysis of CFP biocrudes using supercritical fluid chromatography high-resolution mass spectrometry (SFC-HRMS) with negative electrospray ionization (ESI − ), followed by multivariate data analysis. The method was developed and tested on five biocrude samples from loblolly pine (Pinus taeda) with varying oxygen content (14.9−28.8 wt % wet basis) due to different CFP conditions. The pixel-based analysis displayed chemical variation between all samples. Twenty-four regions of interest were tentatively identified, including mono-and polyphenols, fatty acids, and methylated and methoxylated phenols. The identification workflow and MS/MS analysis were prioritized on the peaks with the highest relative concentration. The developed SFC-ESI − -HRMS method shows high repeatability and analyzed oxygen-containing compounds with hydroxyl and/or carboxyl moieties in combination with other moieties of up to 400 Da.

Integrated Reactive Catalytic Fast Pyrolysis: Biocrude Production, Upgrading, and Coprocessing

“…A more comprehensive understanding of the impact that the chemical composition of direct liquefaction biocrudes has on upgrading is becoming possible as more advanced methods are developed for characterizing biocrudes and the hydrotreated biocrude products. ,− Correlating the oxygen content of direct liquefaction intermediates with biocrude upgrading performance can be extended to evaluating the impact of individual components with specific oxygen functionality on the performance of hydrotreating catalysts. The various pyrolysis technologies being developed produce biocrude intermediates with a wide range of oxygen contents that depend on the catalyst, process conditions (temperature, pressure, hydrogen partial pressure), and feedstock. , …”

Ultra‐high‐performance supercritical fluid chromatography‐mass spectrometry for the analysis of organic contaminants in sediments

“…Ultra-high performance supercritical fluid chromatography (UHPSFC) is complementary to LC and GC utilizing normal-and reverse-phase columns and sub-or supercritical CO 2 as the mobile phase in combination with a modifier, for example, methanol [8]. Pharmaceuticals, chiral separation, and bioanalysis have been the main applications of UHPSFC [9,10]; it has also been applied to analyze complex matrices, for example, unconventional fuels [9,[11][12][13][14][15], natural products [16,17] and environmental samples [18,19].…”