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超临界水条件下水油比对渣油加氢反应性能的影响
孙昱东, 杨朝合, 刘波, 韩忠祥
中国石油大学化学工程学院, 山东青岛 266580
摘要:
研究超临界水(SCW)对渣油加氢反应过程的影响。结果表明:增加SCW,反应的转化率、气体、轻油及VGO收率先增加后降低,而焦炭和残渣油收率先降低后增加;加入适量SCW时,其增溶作用有利于沥青质在体系中的分散,气化作用可为加氢过程提供活性氢原子,抑制了沥青质的聚集和缩合生焦反应,随着SCW对催化剂酸性位的改变,提高了加氢催化剂的活性,有利于改善渣油加氢产物分布;高水油比下,SCW的萃取作用及竞争吸附作用加剧,恶化了反应环境,使产物分布变差;SCW条件下的脱硫率和脱氮率也会因焦炭对杂原子的富集作用、催化剂活性的变化及竞争吸附作用等而下降。
关键词:  超临界水  渣油加氢  产物分布  催化剂活性
DOI:10.3969/j.issn.1673-5005.2018.02.020
分类号:TE624.43
基金项目:国家自然科学基金面上项目(21376266)
Effect of water-oil ratio on residue hydrotreating in presence of supercritical water
SUN Yudong, YANG Chaohe, LIU Bo, HAN Zhongxiang
College of Chemical Engineering in China University of Petroleum, Qingdao 266580, China
Abstract:
The reaction performance of residue in hydrotreating in presence of supercritical water (SCW) was studied. It is found that with the increasing of SCW, the conversions, gas yields, light oil yields and VGO yields increase at first and then decrease. On the contrary, the coke yields and residue yields decrease firstly and then increase. The results indicate that the proper addition of SCW is beneficial to improve the asphaltene distribution in the system due to the solubilization of SCW. And the gasification effect of SCW can provide active hydrogen atom for hydrogenation. All of these are able to inhibit the aggregation and condensation of asphaltene in residue hydrotreating. Also, SCW can change the acid sites of catalyst, which improves the hydrogenation activity of catalyst and the product distribution of residue hydrotreating. It is also found that the product distribution is deteriorated with high water-oil ratio because the reaction environment is unfavorable to the hydrotreating under the extraction and competitive adsorption of SCW. The desulfurization and denitrification rate also decrease under the influence of enrichment of heteroatom in coke, activity changes of catalyst and competitive adsorption of SCW.
Key words:  supercritical water  residue hydrotreating  product distribution  catalyst activity
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