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    Co-hydrothermal Liquefaction of Lignocellulosic Biomass with Kukersite Oil Shale
    (Amer Chemical Soc, 2019) Akalin, Ece; Kim, Young-Min; Alper, Koray; Oja, Vahur; Tekin, Kubilay; Durukan, Ilknur; Siddiqui, Muhammad Zain
    The co-hydrothermal liquefaction of black pine wood (BPW) with Kukersite oil shale (KOS) at different blend ratios of BPW/KOS (1:1, 1:2, and 2:1) was conducted at 300 degrees C for 30 min. No synergistic effects on oil yields from the co-hydrothermal processing have been observed. However, when the methanol was substituted with hot compressed water as the solvent, positive synergistic effects on the oil yields were observed for all blend ratios, but the heating values of the oils from hydrothermal processing were higher than those from supercritical methanol processing under identical conditions. Co-hydrothermal liquefaction of BPW with KOS produced oils with less oxygen than those from co-supercritical methanol processing of BPW with KOS under identical conditions. The highest heating value from co-processing was 30.22 MJ/kg, which was obtained from the co-hydrothermal liquefaction of BPW with KOS at a blend ratio of 1:2. Oils from the co-hydrothermal liquefaction of BPW with KOS contained phenols, acids, ketones, and aldehydes. Guaiacol was the primary compound detected in the oils from co-hydrothermal processing. The relative yield of this compound was highest at a blend ratio of 1:2 (BPW/KOS). The prominent compounds in oils from the co-supercritical methanol processing were esters and phenols.
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    In-situ catalytic co-pyrolysis of kukersite oil shale with black pine wood over acid zeolites
    (Elsevier, 2021) Park, Young-Kwon; Siddiqui, Muhammad Zain; Karagoz, Selhan; Han, Tae Uk; Watanabe, Atsushi; Kim, Young-Min
    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.