石油学报(石油加工)
石油學報(石油加工)
석유학보(석유가공)
Acta Petrolei Sinica (Petroleum Processing Section)
2015年
5期
1089-1096
,共8页
吴乐乐%杜俊涛%邓文安%王晓杰%李传
吳樂樂%杜俊濤%鄧文安%王曉傑%李傳
오악악%두준도%산문안%왕효걸%리전
煤焦油重组分%悬浮床加氢%生焦前驱体%生焦机理%吸附中心%载焦体
煤焦油重組分%懸浮床加氫%生焦前驅體%生焦機理%吸附中心%載焦體
매초유중조분%현부상가경%생초전구체%생초궤리%흡부중심%재초체
coal tar heavy fraction%slurry-bed hydrocracking%coke precursor%coke formation mechanism%adsorption center%coke trap
以中/低温煤焦油重组分(CTAR)为原料进行悬浮床加氢实验,采用1 H‐NMR、XRD、IR、元素分析及相对分子质量测定手段对生焦前驱体(HI)进行分析,并以显微镜观测、SEM、IR等方法对焦炭的官能团、堆积结构及表面形态进行了研究,推测CTAR加氢过程的生焦机理。结果表明,CTAR悬浮床加氢效果理想, HI中芳环稠度低,侧链少而短,平均相对分子质量低,分子间缔合性小,没有芳香片层堆积结构,不易裂化产生大分子自由基,是轻质生焦前驱体。焦炭为1μm左右的球状颗粒吸附于炭质颗粒而形成的10μm左右的聚合体。CTAR中分布的甲苯不溶物及硫化的催化剂颗粒在反应中提供的“2个结焦中心(催化剂和微晶粒子),1个吸附中心(炭质颗粒)”使焦粒变小、壁相焦减少。
以中/低溫煤焦油重組分(CTAR)為原料進行懸浮床加氫實驗,採用1 H‐NMR、XRD、IR、元素分析及相對分子質量測定手段對生焦前驅體(HI)進行分析,併以顯微鏡觀測、SEM、IR等方法對焦炭的官能糰、堆積結構及錶麵形態進行瞭研究,推測CTAR加氫過程的生焦機理。結果錶明,CTAR懸浮床加氫效果理想, HI中芳環稠度低,側鏈少而短,平均相對分子質量低,分子間締閤性小,沒有芳香片層堆積結構,不易裂化產生大分子自由基,是輕質生焦前驅體。焦炭為1μm左右的毬狀顆粒吸附于炭質顆粒而形成的10μm左右的聚閤體。CTAR中分佈的甲苯不溶物及硫化的催化劑顆粒在反應中提供的“2箇結焦中心(催化劑和微晶粒子),1箇吸附中心(炭質顆粒)”使焦粒變小、壁相焦減少。
이중/저온매초유중조분(CTAR)위원료진행현부상가경실험,채용1 H‐NMR、XRD、IR、원소분석급상대분자질량측정수단대생초전구체(HI)진행분석,병이현미경관측、SEM、IR등방법대초탄적관능단、퇴적결구급표면형태진행료연구,추측CTAR가경과정적생초궤리。결과표명,CTAR현부상가경효과이상, HI중방배주도저,측련소이단,평균상대분자질량저,분자간체합성소,몰유방향편층퇴적결구,불역열화산생대분자자유기,시경질생초전구체。초탄위1μm좌우적구상과립흡부우탄질과립이형성적10μm좌우적취합체。CTAR중분포적갑분불용물급류화적최화제과립재반응중제공적“2개결초중심(최화제화미정입자),1개흡부중심(탄질과립)”사초립변소、벽상초감소。
The slurry‐bed hydrocracking experiment of medium/low temperature coal tar heavy (>350℃) fraction (CTAR) was carried out in magnetic‐stirred autoclave ,and the properties of coke precursor (heptane insoluble ,HI) were analyzed with the help of 1 H‐NMR ,XRD ,IR ultimate analysis and average relative molecular mass determination (VPO ) . In addition , the functional groups ,stacking structure and microstructure of coke were characterized by means of microscope , SEM ,IR to speculate the coke formation mechanisms of CTAR in slurry‐bed hydrocracking .The results showed that hydrogenation effect of CTAR slurry‐bed hydrocracking was good .HI was a kind of lighter coke precursor with low aromatic ring consistency ,few and short aliphatic chains , small average relative molecular mass and no aromatic sheet stacking structures ,which was not easy to break to generate polycyclic aromatics radicals in the hydrocracking .Coke was the aggregate (about 10 μm) formed by globular particles (about 1μm) adsorbing on the surface of carbonaceous particles .The smaller coke particles and less amount of coke on the surface of reactor were observed in CTAR hydrocracking ,because the toluene insoluble (TI ) and sulfurized catalyst provided “two coke centers (catalyst and micro grain ) and one adsorption center (carbonaceous particles )”for reaction system .