煤焦油重组分甲苯不溶物结构组成及对悬浮床加氢裂化生焦的影响.pdf

第43卷第8期
燃料化学学报
2015年8月
Journal of Fuel Chemistry and Technology
Aug,2015
文章编号:0253-2409(2015)08-0923-09
煤焦油重组分甲苤不溶物结构组成
及对悬浮床加氢裂化生焦的影响
吴乐乐…,李金,邓文安,张英红,李传
(1.中国石油大学(华东)重质油国家重点实验室,山东青岛26580;
2.中海油能源发展股份有限公司安全环保分公司,天津300456
摘要:以煤焦油常压渣油(CTAR)为原料在3000mL环流反应器悬浮床加氢装置上进行了中试实验,并分别从CTAR和加
氢产物中提取了甲苯不溶物(TI)及焦炭,通过元素分析、SEM、XRD、FT-IR、XPS等手段对及焦炭进行对比分析,明确了T
的结构组成并将其与加裂化生焦情况进行了关联。结果表明,CTAR悬浮床加氢工艺具有轻油收率高、生焦总量小、没有壁
相焦的特点。TI由煤焦油生产过程中带入的碳质、矿物质颗粒及稠环芳烃有机物构成,O是其中含量最高的杂原子,Ca、Si
Al、Na来源于煤焦油中矿物质,C和O主要存在于C-CC-H、C-0-C、C-OH结构中,N主要以吡略和胺的形式存在,S主要
以脂肪类S存在。Ⅶ具有明显的片层堆积结构,在作用力下容易破碎为具有较大比表面积及吸附能力的微米级微晶及碳质
颗粒,和硫化后的催化剂颗粒一起为加氢反应提供载焦中心,优先吸附大分子自由基从而明显减少壁相焦的生成。
关键词:煤焦油重组分;悬浮床加氢;甲苯不溶物;生焦
中图分类号:TQ524;TE662文献标识码:A
Structure of toluene insoluble coal tar heavy fraction and its relevance
to the coking behavior in slurry-bed hydrocracking
WU Le-le", LI Jin-lu DENG Wen-an, ZHANG Ying-hong, LI Chuan
(1. State Key Laboratory of Heavy Oil Processing, China versity of Petroleum( Huadong), Qingdao 266580, China
2. CNOOC Ener Tech-safety Environmental Protection Co. Tianjin 300456, China
Abstract: The hydrogenation of coal tar atmospheric residue(CTAR was conducted in a slurry-bed
hydrocracking pilot plant with a 3 000 ml loop reactor; the toluene insoluble(TI) fraction and coke were
separated from TAR and hydrogenation product, respectively. The properties of TI and coke were analyzed b
means of element analysis, SEM, XRD, FT-IR and XPS; the relevance of TI structure to the coking behavior in
the hydro enation process was then investi ed. The results show that the slurry-bed hydrocracking of CTAR has
the features of high light oil yield, little coke, and almost no coke on the reactor surface. TT consists o
carbonaceous, mineral particles and polycyclic aromatic hydrocarbons originated from the coal tar production
process. O is the dominant heteroatom, whereas Ca, Si, Al, and Na are derived from minerals in CTAR
Furthermore, C and O are mainly present as C-C, C-H, C-O-C and C-OH, whereas N-containing groups
appear as pyrrole and amine and S is mainly in the form of aliphatic sulfur. Obviously, TI has a layered stack
structure, which can be easily broken to smaller carbonaceous and mineral particles( several microns ) with larger
specific surface area and adsorption capacity. These particles, together with the sulfurized catalyst, act as the
coke centers, which are effective to adsorb macromolecular radicals and then reduce the opportunity of coking on
the reactor surface
Key words coal tar heavy fraction; slurry-bed hydrocracking; toluene insoluble; coking
煤焦油是煤干馏的副产品,中国的煤焦油年产者提出煤焦油加氢制取轻质油品的思路?,并利
量呈逐年递增趋势り,一直以来,煤焦油的利用都用目前广泛应用的固定床加氢技术实现了部分轻质
是研究的热点问题2,虽然煤焦油具有许多类似煤焦油的加氢处理?。但在煤焦油中,常压渣油等
于石油的性质,但由于其源于煤炭,成分复杂,从中较重组分一般占全馏分油比例较大,并且油品差,难
提取酚、萘、葸等化工产品是其主要的利用方向,但以加工,所以实现这一部分油品的加工利用是解决
该利用方法成本较高,利用率较低。近几年,有研究煤焦油轻质化的关键。
收稿日期:2015-01-15;修回日期:201503-05。
基金项目:国家重点基础研究发展规划(973计划,2012CB214901,2014CB238905);国家自然科学基金(41214D0208);中央高校
基本科研业务费专项资金(14CX05032A)。
联系作者:邓文安,博土,教授,Tel:18605460968,E-mail:dengwenant@upc.euu.Cno