ABSTRACT
This chapter discusses rates of oil shale pyrolysis, yields of pyrolysis products, characterization of pyrolysis products, mechanistic pyrolysis modeling, and changes in char aromaticity during pyrolysis. The samples used for these experiments and analyses are the same Green River oil shale and
CONTENTS
6.1 Background ................................................................................................. 120 6.2 Oil Shale Pyrolysis Rates .......................................................................... 121
6.2.1 Thermogravimetric Analysis Data .............................................. 121 6.2.2 Rate Determination ....................................................................... 121 6.2.3 CO2 Formation Rate ....................................................................... 123
6.3 Yields and Characterization of Pyrolysis Products .............................. 123 6.3.1 Experimental Methodology ......................................................... 123
6.3.1.1 Kerogen Retort ................................................................. 123 6.3.1.2 Elemental Analysis ......................................................... 125 6.3.1.3 13C NMR Analysis ........................................................... 126 6.3.1.4 GC/MS Analysis ............................................................. 127 6.3.1.5 FTIR Analysis .................................................................. 128
6.3.2 Analysis of Pyrolysis Products from Kerogen Retort ............... 128 6.3.2.1 Pyrolysis Product Yields ................................................ 128 6.3.2.2 NMR Analysis of Char ................................................... 128 6.3.2.3 Solution-state 13C NMR Analysis of Tars ..................... 134 6.3.2.4 GC/MS Analysis of Tars ................................................ 140 6.3.2.5 FTIR Analysis of Light Gases ........................................ 141 6.3.2.6 Discussion ........................................................................ 143
6.4 Modeling Kerogen Pyrolysis with the CPD Model .............................. 144 6.4.1 Chemical Structure Data .............................................................. 145 6.4.2 Model Description ......................................................................... 146 6.4.3 Results ............................................................................................. 147
6.5 Analysis of Changes in Char Aromaticity ............................................. 151 6.6 Summary and Conclusions ...................................................................... 152 References ............................................................................................................. 154
demineralized kerogen samples discussed in Chapter 5. Mass release rates of these samples during pyrolysis were measured in a thermogravimetric analyzer (TGA), and corresponding kinetic rates were determined. Product analyses were then performed by a combination of carbon-13 nuclear magnetic resonance (13C NMR) spectroscopy, gas chromatography/mass spectrometry (GC/MS), and Fourier transform infrared (FTIR) spectroscopy techniques, including solid-state 13C NMR analysis of the pyrolyzed kerogen char samples obtained at different temperatures and liquid-state 13C NMR analysis of the associated tars collected during pyrolysis.
