In-situ Catalytic Co-pyrolysis of Kukersite Oil Shale with Black Pine Wood over Acid Zeolites

Abstract The thermal and catalytic co-pyrolysis of black pine wood (BPW) and Kukersite oil shale (KOS) over acid zeolites were investigated by thermogravimetric analysis (TGA) and tandem micro reactor-gas chromatography/mass spectrometry (TMR-GC/MS). TGA showed that BPW and KOS had different decomposition temperature regions due to differences in compositions. The maximum decomposition temperature (Tmax) of BPW was not changed by co-pyrolysis with KOS or additional catalyst. Although co-pyrolysis did not change the Tmax of KOS with BPW or the additional use of HZSM-5 (Si/Al2O3: 23), the Tmax was lowered to 424 °C and 428 °C using HBeta(25) and HY(30), respectively. The TMR-GC/MS results showed that oxygenates and light hydrocarbons were produced mainly by the non-catalytic pyrolysis of BPW and KOS, respectively. By applying catalytic pyrolysis (CP), these oxygenates and light hydrocarbons were converted to aromatic hydrocarbons over acid zeolites. HZSM-5(23) had the highest efficiency in the formation of aromatics from the CP of BPW and KOS, followed by HBeta(25) and HY(30) because of the catalyst acidity and pore properties. The co-feeding of KOS on the CP of BPW enhanced the synergistic effects on the formation of aromatics because of the effective Diels-Alder reaction between the CP intermediates of BPW and KOS.