Characterization of Heavy Products from Lignocellulosic Biomass Pyrolysis by Chromatography and Fourier Transform Mass Spectrometry: A Review

Abstract

Bio-oils obtained from lignocellulosic biomass pyrolysis are promising energetic resources. However, their high oxygen content is responsible for storage and corrosion issues and does not allow their direct use as biofuels. Therefore, upgrading treatments are necessary to reduce the oxygen content and to give them physiochemical properties close to those of fossil fuels. To monitor the efficiency of both conversion and upgrading processes, the extensive molecular composition of bio-oil is needed. In that sense, two approaches can be applied for bio-oil characterization. The non-targeted one, using high-resolution mass spectrometry, ensures to distinguish and assign tens of thousands features at the isobaric level. On the other hand, targeted analyses, especially with chromatography hyphenated to mass spectrometry, allow quantifying and obtaining isomeric information on the bio-oil species. In this review, both approaches will be discussed through the different studies performed in that field. Particular interest will be given to heavy compounds analysis by Fourier transform mass spectrometry (FTMS) and liquid and supercritical fluid chromatographies. Most of the analyses are performed either by FTMS or by chromatography. Only a limited number of works report bio-oil characterization by liquid chromatography hyphenated to FTMS. These hyphenated methods are complementary and ensured to highlight hitherto unknown bio-oil species. It therefore represents the next step for deciphering the complex molecular composition of bio-oil.

Review on Evolved Gas Analysis Mass Spectrometry with Soft Photoionization for the Chemical Description of Petroleum, Petroleum-Derived Materials, and Alternative Feedstocks

“…Here, particularly, the occurrence of certain heteroelements, not reported in classical fossil fuel analysis, such as phosphorus, silicon, halogens, and boron, will make sum formula attribution strategies using HRMS as a prerequisite to study those matrices. Boron-containing species can frequently be found in bio-oils, whereas halogen- and silicon-containing species are prominent in certain polymer waste pyrolysis oils and caused by additives, flame retardants, and plasticizers. , …”

“…Boron-containing species can frequently be found in bio-oils, whereas halogen-and silicon-containing species are prominent in certain polymer waste pyrolysis oils and caused by additives, flame retardants, and plasticizers. 182,183 From an applicative perspective, some research fields have not or only rarely been touched by EGA−PIMS. Engineering developments in the field of recycling and attempts at a circular economy (bio-oils and other pyrolysis oils) can be strongly supported by elucidation of the molecular profile by EGA− PIMS.…”

2021 Pioneers in Energy Research: Alan Marshall

“…■ CHARACTERIZATION OF PROCESSING PRODUCTS Hertzog, Afonso, and co-workers 47 reviewed the application of FT-ICR MS characterization of heavy (high-boiling) products from lignocellulosic biomass pyrolysis. By surveying many important papers published over the past decade, these authors highlighted the use of hyphenated liquid chromatography mass spectroscopy as a promising approach in deciphering the complex composition of bio-oils.…”

Speciation and Semiquantification of Nitrogen-Containing Species in Complex Mixtures: Application to Plastic Pyrolysis Oil

“…Such a procedure is usually used with separation methods such as liquid or gas chromatography. However, in the case of ultracomplex mixtures such as bio-oils, − plastic pyrolysis oils, and other mixtures, , the huge amount of different isomers may yield a very low concentration per molecule. The use of direct infusion mass spectrometry (DI-MS) can remove the isomeric dispersion and thus very significantly improve the detection limit per molecular formula.…”