渣油悬浮床加氢裂化反应机理.docVIP

石油学报(石油加工 2009年4月 ACT A PET ROLEI SINICA(PET ROLEU M PROCE SSING S ECTION 第25卷第2期 文章编号:1001 8719(200902 0145 05 渣油悬浮床加氢裂化反应机理 张数义,邓文安,罗 辉,刘 东,阙国和 (中国石油大学重质油国家重点实验室,山东东营257061 摘要:在高压反应釜中模拟悬浮床加氢裂化反应,考察了辽河稠油在H2氛围下的热裂化反应和油溶性分散型N i 催化剂存在下的悬浮床加氢裂化反应结果的差别,也对比了两者的气体产物组成、反应生焦及催化剂的SEM形貌和反应生焦的元素分析结果,以探讨渣油悬浮床加氢裂化反应机理。结果表明,悬浮床加氢裂化反应与热裂化反应相比,气体产物分布没有差别,轻油收率略有降低,但其生焦量却大幅降低,说明悬浮床加氢裂化反应主要按自由基热反应机理进行,分散型催化剂的存在只是起到促进加氢反应速率的作用。加氢裂化反应生焦的N i含量显著增加,其来源应为催化剂,由此可以断定催化剂在反应前期促进加氢反应速率,抑制反应的裂化和生焦,反应后期被反应过程中生成的焦炭严密包裹,成为焦炭沉积的场所,因此减少了反应器壁的结焦。 关 键 词:稠油;分散型催化剂;悬浮床加氢裂化;机理 中图分类号:T E624.4 文献标识码:A MEC HANISM OF SLURRY PHAS E HYDROC RACKING RESIDUE REAC TION ZH AN G Shu y i,DEN G Wen an,LU O H ui,LIU Dong,QU E Guo he (S tate K e y L aborator y of H eav y Oil P rocessing,China Univ ersity of P etrole um,Dongy ing257061,China Abstract:In order to study the reaction mechanism of slurr y phase hydrocracking,a slurr y phase hy dro cracking reaction w as sim ulated in an autoclav e,and the difference o f the thermal cracking reactio n under the presence of H2of Liaohe heavy oil(LH H Oand the slurry phase hydr ocracking reactio n catalyzed by the oil so luble dispersed Ni catalyst w ere inv estig ated,also the compositions of gas products,the SEM im ag es of coke and catalyst and the element analy ses o f cokes pro duced fro m the tw o reactions w ere co mpar ed.The results show ed that there w as no difference betw een the com positio ns of g as pro ducts of the two reactions,but the lig ht oil yield of hy dro cracking reactio n decreased a little and its coke y ield decr eased m ore gr eatly,indicating that the slur ry phase hy dro cracking reaction w as follow ing the free radical therm al cracking mechanism.The action o f disperser cataly st w as only to prom ote the hy drog enation speed.The Ni content of slurry phase hy dro cracking coke w as r em ar kable increased,w hich should be fro m the oil so luble dispersed Ni catalyst.Thus it is concluded that the effect of catalyst in reactio n w as to prom ote