石油炼制与化工 ›› 2026, Vol. 57 ›› Issue (6): 88-98.

• 催化剂 • 上一篇    下一篇

渣油临甲烷改质催化剂NiMoZn/ γ-Al2O3的制备及其催化性能研究

宋正浩1,史沛然1,吴冲冲2,李永恒2,杨国明2,杨修洁1,陈坤1   

  1. 1. 中国石油大学(华东)化学化工学院,重质油国家重点实验室
    2. 中海油化工与新材料科学研究院(北京)有限公司
  • 收稿日期:2025-10-11 修回日期:2026-01-30 出版日期:2026-06-12 发布日期:2026-05-22
  • 通讯作者: 杨修洁 E-mail:yangxiujie@upc.edu.cn
  • 作者简介:2026-01-20
  • 基金资助:
    中国海洋石油有限公司项目;山东省自然科学基金资助项目

STUDY ON PREPARATION AND CATALYTIC PERFORMANCE OF NiMoZn/γ-Al2O3 CATALYST FOR METHANE-ASSISTED RESIDUE UPGRADING

  • Received:2025-10-11 Revised:2026-01-30 Online:2026-06-12 Published:2026-05-22

摘要: 以γ-Al2O3为载体,采用浸渍法制备了负载Ni、Mo及不同金属助剂M(M=Zn,Co,Ce,Ag)的催化剂。利用扫描电镜、X射线衍射、N2吸附-脱附、吡啶吸附红外光谱和NH3程序升温脱附等手段对催化剂进行表征,并考察了反应气氛(CH4/N2,N2/H2,CH4/H2)、金属助剂种类(Zn,Co,Ce,Ag)以及反应温度(390~420 ℃)等因素对渣油改质效果的影响。结果表明,在CH4/H2混合气氛中,少量H2有助于促进甲烷活化,提升渣油临甲烷改质反应性能。NiMo/γ-Al2O3催化剂中Ni和Mo物种高度分散,B酸酸性位增加、L酸酸性位减少,Ni和Mo的最佳负载量(w)分别为10%和20%。金属助剂的引入有利于渣油的改质,其中Zn助剂效果最佳,可增加L酸酸性位,并与活性金属Ni、Mo产生协同作用,提升甲烷活化能力。适当提高反应温度有利于改善油品改质效果,在420 ℃时改质效果最佳,改质油黏度降低98.55%,沥青质质量分数下降88.41%,脱硫率为38.65%,脱氮率为37.14%。

关键词: 渣油改质, 甲烷活化, NiMo/γ-Al2O3催化剂, 金属助剂

Abstract: Metal catalysts loaded with Ni, Mo, and different metal promoters M (M = Zn, Co, Ce, Ag) were prepared using mesoporous γ-Al2O3 as a support via the impregnation method. The catalyst was characterized using scanning electron microscopy, X-ray diffraction, nitrogen adsorption-desorption, pyridine infrared, and NH? programmed temperature desorption. The effects of different mixed reaction atmospheres (methane-nitrogen, nitrogen-hydrogen, methane-hydrogen) and various metal promoters M (M = Zn, Co, Ce, Ag) on catalytic performance. The effects of reaction temperature (390–420 ℃) and varying promoters metal loading on the reforming of residue oil were also systematically investigated. Results indicate that in methane-hydrogen mixed atmosphere, the introduction of a small amount of hydrogen aids methane activation and enhances the reforming effect of residue oil over methane. In the NiMo/γ-Al2O3 catalyst, Ni and Mo species are highly dispersed, exhibiting an increase in B acid sites and a decrease in L acid sites. The optimal loading amounts for Ni and Mo are 10% and 20%, respectively. The introduction of metal additives M improved residue oil quality, with Zn exhibiting the best reaction performance. Metal Zn increased L-acid sites in the catalyst and synergized with active metals Ni and Mo to enhance methane activation capacity. Moderately elevated reaction temperatures (390–420 ℃) enhance oil upgrading. Under 420 ℃ conditions, optimal upgrading yields were achieved: upgraded oil viscosity decreased by 98.55%, asphaltene content dropped by 88.41%, desulfurization rate reached 38.65%, and denitrification rate reached 37.14%.

Key words: residue oil upgrading, methane activation, NiMo/γ-Al2O3 catalyst, metal promoter