Gas Chromatography/Atmospheric Pressure Chemical Ionization-Fourier Transform Ion Cyclotron Resonance Mass Spectrometry of Pyrolysis Oil from German Brown Coal

Abstract

Pyrolysis oil from the slow pyrolysis of German brown coal from Schöningen, obtained at a temperature of 500°C, was separated and analyzed using hyphenation of gas chromatography with an atmospheric pressure chemical ionization source operated in negative ion mode and Fourier transform ion cyclotron resonance mass spectrometry (GC-APCI-FT-ICR-MS). Development of this ultrahigh-resolving analysis method is described, that is, optimization of specific GC and APCI parameters and performed data processing. The advantages of GC-APCI-FT-ICR-MS hyphenation, for example, soft ionization, ultrahigh-resolving detection, and most important isomer separation, were demonstrated for the sample liquid. For instance, it was possible to separate and identify nine different propylphenol, ethylmethylphenol, and trimethylphenol isomers. Furthermore, homologous series of different acids, for example, alkyl and alkylene carboxylic acids, were verified, as well as homologous series of alkyl phenols, alkyl dihydroxy benzenes, and alkoxy alkyl phenols.

Analytical Strategies Involved in the Detailed Componential Characterization of Biooil Produced from Lignocellulosic Biomass

“…FT-ICR MS provides nonspecific identification of molecular species within a wide range of MW (200–1000 Da) with considerable high mass resolution (better than 0.003 Da) and elucidates the detailed composition of complex samples, such as crude oils, biooils, and liquefied products of coals [ 28 , 50 , 74 , 76 , 159 , 160 ]. The species to be determined should be ionized to fragments first by an ionization source without structural changes that could potentially lead to misinterpretation of the acquired data.…”

“…To determine the functional groups and chemical bonds distribution, and individual species in biooil, distinct separation and detection methodologies were applied. After preseparation of moieties in biooil [ 21 , 33 , 49 ], such as liquid-liquid extraction (LLE), distillation, and column chromatography, both spectroscopic and chromatographic methods are applied to the qualitative analysis and quantitative analysis of the species in biooil [ 17 , 44 , 50 – 53 ]. For spectroscopic methods, Fourier transform infrared (FTIR) spectroscopy [ 29 , 54 – 56 ] and nuclear magnetic resonance (NMR) spectroscopy [ 56 – 59 ] are mostly used, which can provide information on the functional groups of species in biooil.…”

Comprehensive chemical comparison of fuel composition and aerosol particles emitted from a ship diesel engine by gas chromatography atmospheric pressure chemical ionisation ultra-high resolution mass spectrometry with improved data processing routines

“…26,27 Most recently, the advantages of a sophisticated data analysis for brown coal pyrolysis oil was demonstrated. 28 The authors pointed out that negative polarity atmospheric pressure chemical ionisation (APCI) reveals particular advantages for highly oxygenated compounds. 28 In this study, we present an improved data processing routine in addition to the concept previously discussed.…”

“…28 The authors pointed out that negative polarity atmospheric pressure chemical ionisation (APCI) reveals particular advantages for highly oxygenated compounds. 28 In this study, we present an improved data processing routine in addition to the concept previously discussed. 26,27 The quality of the processed data is significantly enhanced by incorporating the transient information directly, which allows for advanced apodisation, noise and peak detection.…”

“…28 The authors pointed out that negative polarity atmospheric pressure chemical ionisation (APCI) reveals particular advantages for highly oxygenated compounds. 28…”