Gao Jing, Cao Yang, Wu Tao, Li Yujiang
Shandong Key Laboratory of Environmental Processes and Health, School of Environmental Science and Engineering, Shandong University, Qingdao, 266237, PR China.
Key Laboratory of Colloid and Interface Science of Education Ministry, Shandong University, Jinan, 250100, PR China.
Environ Res. 2023 Apr 1;222:115359. doi: 10.1016/j.envres.2023.115359. Epub 2023 Jan 24.
In this study, roasted spent HDS ash (sHDSc-A) was used for the first time to catalytically pyrolyze oily spent HDS catalysts (sHDSc) to improve the yield and quality of pyrolysis oil. The results showed that sHDSc-A promoted the decomposition of coke in oily sHDSc, resulting in the recovery of more oil and gas. Meanwhile, sHDSc-A significantly improved the quality of the pyrolysis oil. They inhibited the aromatization of alkanes to increase the saturation of the pyrolysis oil from 59.39% to 74.25% and the H/C radio from 1.62 to 1.72; promoted the decomposition of long-chain alkanes to increase the content of C11-C22 from 41.97% to 61.99%; enhanced the conversion of carboxylic acids to ketones led to the reduction of heteroatomic compounds such as N (56.10%-45.39%), S (66.95%-56.59%), and O (45.26%-26.70%) in the pyrolysis oil. The promotion of sHDSc-A in the pyrolysis process is attributed to the catalytic effect of the metal oxides in sHDSc-A. Among them, AlO and FeO can promote decarboxylation of carboxylic acids and reduce O mobility, while MoO and FeO play a significant role in reducing coke and increasing pyrolysis oil. NiO can also promote methane vapor reforming, and thus increase the production of H in non-condensable gas. This study achieves self-circulation of oily sHDSc with a "waste-treatment-waste" strategy that presents the advantage of value-added energy recovery and waste reuse.
在本研究中，首次使用焙烧后的废加氢脱硫灰（sHDSc-A）对含油废加氢脱硫催化剂（sHDSc）进行催化热解，以提高热解油的产率和质量。结果表明，sHDSc-A促进了含油sHDSc中焦炭的分解，从而回收了更多的油气。同时，sHDSc-A显著提高了热解油的质量。它们抑制了烷烃的芳构化，使热解油的饱和度从59.39%提高到74.25%，H/C比从1.62提高到1.72；促进了长链烷烃的分解，使C11-C22的含量从41.97%增加到61.99%；增强了羧酸向酮的转化，导致热解油中N（56.10%-45.39%）、S（66.95%-56.59%）和O（45.26%-26.70%）等杂原子化合物的减少。sHDSc-A在热解过程中的促进作用归因于sHDSc-A中金属氧化物的催化作用。其中，AlO和FeO可促进羧酸的脱羧反应并降低O的迁移率，而MoO和FeO在减少焦炭和增加热解油方面发挥着重要作用。NiO还可促进甲烷蒸汽重整，从而增加非冷凝气中H的产量。本研究采用“废物处理废物”策略实现了含油sHDSc的自循环，具有增值能源回收和废物再利用的优势。
