Shurong Wang,Qinjie Cai,Xiangyu Wang,Li Zhang,Yurong Wang,Zhongyang Luo
Acids and ketones in biomass pyrolysis oil (bio-oil) can be readily cracked to produce hydrocarbons. They can also be enriched in the distilled fraction using molecular distillation techniques. To simulate the actual composition of the distilled fraction, the co-cracking performance of mixtures of hydroxypropanone, cyclopentanone, and acetic acid with ethanol in a fixed-bed reactor over an HZSM-5 catalyst was studied. The influences of reaction temperature and pressure on the reactant conversion, selectivity, and composition of the oil phase were investigated. At a low reaction temperature of 340 °C, the conversions of acetic acid and ethanol were as low as 67.9% and 74.4%, respectively, and the oil phase had a low hydrocarbon content of 59.8%, with large amounts of oxygenated byproducts. Cracking under atmospheric pressure also generated a low-quality oil phase with a very low selectivity of only 10.8%. Increasing the reaction temperature promoted reactant conversion and improved the deoxygenation efficiency, whereas increasing the reaction pressure significantly promoted hydrocarbon production. The optimum conditions for biogasoline production were 400 °C and 2 MPa. Under these conditions, the reactant conversion reached 100% and the oil phase selectivity was 31.5 wt%. This oil phase consisted entirely of hydrocarbons, 91.5 wt% of which were aromatic hydrocarbons , indicating that the HZSM-5 catalyst had high activity for deoxygenation and aromatization reactions during cracking. In addition, characterization of the spent catalysts and stability tests showed that the catalyst was deactivated after a long reaction time. However, the catalytic activity was recovered by catalyst regeneration.
In order to enhance the thermal stability of polyvinyl alcohol (PVA), a modification scheme involving a dimethyl methyl phosphate (DMMP) impregnation-coating treatment was adopted in this article. Initially, the interfacial compatibility of DMMP with PVA was characterized using scanning electron microscopy (SEM), inductively coupled plasma spectroscopy, elemental analysis and Fourier transform infrared spectroscopy (FTIR). Subsequently, the pyrolysis and combustion properties of DMMP-coated PVA were evaluated via non-isothermal thermogravimetric experiments and cone calorimeter tests. The pyrolysis products were then analyzed using a combination of thermogravimetric infrared chromatography and pyrolysis gas chromatography/mass spectrometry (Py-GC/MS). Finally, a reaction model function closer to the actual co-pyrolysis mechanism at high temperatures was established through thermal kinetics. The results indicated that the impregnation-coating treatment could effectively distribute the DMMP molecules on the surfaces of PVA particles. Meanwhile, the DMMP coating could clearly slow the peak degradation rate of PVA grains and inhibit the combustion of PVA under fire conditions. Furthermore, the pyrolysis of DMMP-coated PVA resulted in the formation of over 40 distinct compounds. The kinetic analysis revealed that the reaction model function established in this article could better characterize the actual reaction mechanism of the co-pyrolysis of DMMP and PVA. Graphical
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