CAJ | 학술논문

以煤焦油常压渣油( CTAR)为原料在3000 mL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TI及焦炭进行对比分析,明确了TI的结构组成并将其与加氢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-C、C-H、C-O-C、C-OH结构中,N主要以吡咯和胺的形式存在,S主要以脂肪类S存在。 TI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。
이매초유상압사유( CTAR)위원료재3000 mL배류반응기현부상가경장치상진행료중시실험,병분별종CTAR화가경산물중제취료갑분불용물( TI)급초탄,통과원소분석、SEM、XRD、FT-IR、XPS등수단대TI급초탄진행대비분석,명학료TI적결구조성병장기여가경열화생초정황진행료관련。결과표명,CTAR현부상가경공예구유경유수솔고、생초총량소、몰유벽상초적특점。 TI유매초유생산과정중대입적탄질、광물질과립급주배방경유궤물구성,O시기중함량최고적잡원자,Ca、Si、Al、Na래원우매초유중광물질,C화O주요존재우C-C、C-H、C-O-C、C-OH결구중,N주요이필각화알적형식존재,S주요이지방류S존재。 TI구유명현적편층퇴적결구,재작용력하용역파쇄위구유교대비표면적급흡부능력적미미급미정급탄질과립,화류화후적최화제과립일기위가경반응제공재초중심,우선흡부대분자자유기종이명현감소벽상초적생성。
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 CTAR and hydrogenation product, respectively. The properties of TI and coke were analyzed by means of element analysis, SEM, XRD, FT-IR and XPS;the relevance of TI structure to the coking behavior in the hydrogenation process was then investigated. 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. TI consists of 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.