马瑞常压渣油悬浮床加氢裂化反应生焦过程  

The Coke Formation Process During Slurry-Bed Hydrocracking of Merey Atmospheric Residue

作　　者：邓文安 王磊[1] 李传 韩亚鹏 王兴旺 DENG Wenan WANG Lei LI Chuan HAN Yapeng WANG Xingwang(State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Qingdao 266580, Chin)

机构地区：[1]中国石油大学重质油国家重点实验室,山东青岛266580

出　　处：《石油学报（石油加工）》2017年第2期291-302,共12页Acta Petrolei Sinica(Petroleum Processing Section)

基　　金：国家自然科学青年基金项目(21106186)资助

摘　　要：采用高压反应釜,以马瑞常压渣油为原料,考察了渣油在420℃时的悬浮床加氢裂化反应生焦过程,采用显微镜、SEM观察焦炭的微观形貌,采用元素分析、~1H-NMR、SEM和XRD等手段研究反应过程中正庚烷沥青质结构组成变化,并与体系的生焦状况进行关联。结果表明,在生焦诱导期内(<50min),随着反应时间延长,沥青质的质量分数、金属元素质量分数、数均相对分子质量及缩合程度增加,芳香片层间距减小;总生焦质量分数和悬浮焦质量分数缓慢增加,沉积焦质量分数基本不变;当反应进行50min时,沥青质的质量分数达到极值,与此同时部分片层堆积紧密且芳香度较高的沥青质缩聚体转化为焦炭;随着反应时间的进一步延长,沥青质的质量分数开始减小,总生焦质量分数明显增加,剩余沥青质的金属元素质量分数、数均相对分子质量、缩合程度及芳香片层间距减小,分散在反应体系中的焦炭缩合成粒径较大的聚集体;当反应超过80min,粒径较大的悬浮焦聚沉转化为沉积焦,致使沉积焦质量分数迅速增加,悬浮焦质量分数及粒径都降低。The process of coke formation during slurry-bed hydrocracking of Merey atmospheric residue was studied in the autoclave at 420℃,in which the microstructures of coke were observed by microscope and SEM,and the composition and structure of asphaltene were investigated by element analysis,~1H-NMR,SEM and XRD,to discuss the relevance between coke formation and asphaltene properties.The results showed that the mass fraction,metal mass fraction,molecular mass and condensation of asphaltene increased,while the slice spacing of asphaltene became short with the increase of reaction time during the coke induction period（50min）,and the yield of suspended coke and total coke increased slowly,the yield of depositional coke was almost invariant.When reaction time reached 50 min,the mass fraction of asphaltene reached its maximum value,and a few of asphaltene polymers with high degree of condensation and closely aromatic layers started to convert into coke fast.With the extending of reaction time the asphaltene mass fraction,metal mass fraction,molecular mass,condensation degree and the slice spacing started to decline,while suspended coke gathered to be bigger aggregations.When the reaction time was over 80 min,the bigger suspended coke transformed into depositional coke,leading to the increase of depositional coke mass fraction,and the decreases of suspended coke size and mass fraction.

关 键 词：渣油悬浮床加氢裂化 生焦过程 沥青质 悬浮焦 沉积焦 

分 类 号：TE624.4[石油与天然气工程—油气加工工程]