Sub-critical water is an environment-friendly solvent. It is widely used for the extraction of various organic compounds. It can be used to dissolve and transport organic matter in oil shale. In this study, the conversion of oil shale was synergistically catalyzed by the addition of Fe or Ni to the Fe inherent in samples under sub-critical water conditions. Oil shale can be converted to gas, oil and residues of oil. Thermogravimetric (TG) analysis results presented that the weight loss of raw oil shale was up to 15.85%. After sub-critical water extraction, the weight loss rate of the residues was reduced to 8.41%. With the application of a metal catalyst, Fe or Ni, the weight loss of residues was further reduced to 7.43% and 6.57%, respectively. According to DTG curves, it was found that there were two weight-loss rate peaks. The decomposition process of kerogen in oil shale could be divided into two cracking processes. One is decomposed at a high velocity at around 420 °C, and another is decomposed at a low velocity at around 515 °C. Gas chromatography (GC) results of gas products indicated that Fe or Ni could contribute to producing normal alkanes, such as methane, ethane, propane, etc., which are produced by the hydrogenation of alkenes via hydrogen transfer during the conversion process of kerogen. Gas chromatography-mass spectrometry (GC–MS) was conducted to analyze the components of the liquid products. The results showed that n-alkanes, iso-alkane, oxygenated hydrocarbons and aromatic compounds were the major components of the kerogen cracking products. When Ni was introduced as a catalyst, the contents of aromatic compounds and oxygenated hydrocarbons in the liquid products were increased from 19.55% and 6.87% to 22.38% and 13.77%, respectively. This is due to the synergistic effect of the addition of Ni with the inherent Fe in oil shale under sub-critical water which ensures kerogen is more easily cracked to produce aromatic compounds and oxygenated hydrocarbons.
Aromatics assume a paramount role as indispensable organic chemical feedstock within diverse industrial domains. Simultaneously, the global aromatics market is scarce, particularly with the exorbitant demand for high-value aromatics. Generating aromatics via coal-based methanol and low-carbon hydrocarbon coupling reactions has become a novel green and sustainable development trajectory. In this study, HZSM-5 catalysts featuring different Si/Al ratios and active metal-functionalized modifications were utilized to explore the aromatization effect in light of the Si/Al ratio, types of active components, and metal-loading content in a fixed-bed reactor. The outcomes were that the conversion ratios for methanol and n-pentane attained 99.9% and 83.1%, respectively. Remarkably, an oil phase yield of 32.1% was accomplished, along with an aromatic content of approximately 74.2%, while xylene selectivity reached approximately 37.6% for the 1.0%-ZnO/ZSM-5 (50) catalyst. Ultimately, a reaction mechanism for the coupling of methanol and n-pentane to yield aromatics using a 1.0%-ZnO/ZSM-5(50) catalyst is postulated.
The conversion of polycyclic aromatic hydrocarbons (PAHs) to monocyclic aromatic hydrocarbons holds significant importance in the petrochemical and coal chemical industries, as it enables the production of high-value-added chemicals. In this study, we investigated the methane-assisted hydroconversion of PAHs to monocyclic aromatic hydrocarbons with methyl side chains over Zn-based catalysts from Hβ zeolites treated with citric acid (CA) at different concentrations. The CA-modified Hβ catalysts were characterized using X-ray diffraction (XRD), N2 adsorption–desorption, pyridine–Fourier transform infrared spectroscopy (Py-FTIR), and ammonia temperature-programmed desorption (NH3-TPD). The results show that low CA concentrations facilitate the removal of amorphous aluminum from the zeolite framework, thereby increasing the specific surface area, pore volume, and pore diameter of the Zn/Hβ catalyst, as well as improving its Lewis/Brønsted (L/B) acid ratio. In contrast, excessive CA treatment causes the undesirable removal of framework aluminum and leads to structural collapse in the mesoporous regions formed at the interfaces between certain crystal aggregates. This, in turn, has a negative impact on the catalyst’s specific surface area, pore volume, pore size distribution, total acidity, and L/B ratio. Experimental data further indicate that the optimal Zn/Hβ catalyst, prepared using Hβ treated with 0.08 M CA, achieves a naphthalene conversion rate of up to 99% and a benzene–toluene–xylene (BTX) selectivity of 60% in the liquid product over a 10 h reaction period. These findings confirm that CA treatment not only enhances the catalytic activity of Zn/Hβ but also significantly improves its operational stability. This work provides new insights into the rational design of catalysts for the efficient conversion of PAHs to monocyclic aromatic hydrocarbons and the utilization of methane resources.