摘要
利用钌离子催化氧化方法(RICO)研究了渣油中沥青质的化学结构,定量测定了与沥青质芳香核相连的烷基侧链和烷基桥链的分布,推断了沥青质中芳香环系的缩合形式,讨论了沥青质组分在加氢处理过程中的结构变化规律。结果表明,渣油组分的芳香环都带有C1~C27的烷基侧链,并且主要是正构烷基侧链;也存在与2个芳香核相连接的C2~C16烷基桥链,它们的摩尔浓度随链长增加而下降。沥青质的RICO氧化产物中检测出从邻苯二甲酸到苯六甲酸的一系列苯多甲酸。沥青质芳香核结构中存在着渺位缩合、迫位缩合和联苯结构,其中联苯结构较少,迫位缩合最多,所以可以将沥青质看作是纯粹的迫位缩合体。随着加氢处理深度的增加,沥青质组分的化学结构发生变化,较大的芳香核在沥青质中富集,使得沥青质组分中的芳香结构逐渐增多,芳香核缩合程度逐渐增加。
The chemical structure of asphaltenes in petroleum residue was investigated by using ruthenium ions catalyzed oxidation (RICO). The distributions of alkyl side chains and bridges connected to aromatic rings were quantified, and the condensed type of aromatic rings was deduced. The structural changes of asphaltene during hydrotreating were discussed. The results showed that there were abundant alkyl side chains(C1-C27), mainly n-alkyl side chains, attached to aromatic carbons of asphaltene and polymethylene bridges(C2-C16 ) connected to at least two aromatic ring systems, whose molar concentrations were declined as the increase of chain length. Various isomeric benzenepolycarboxylic acids from dito hexacarboxylic acids were identified in the RICO products of asphaltene. Cata-condensed, peri-condensed and biphenyl types aromatic structures coexisted in asphaltene fraction, among which the proportion of biphenyl type structure was relatively small, and the peri-condensed was the most, so asphaltene could be regarded as pericondensed system. The chemical structure of asphaltene in residue changed as the increase of hydrotreating degree. The enrichment of large aromatic unit made asphaltene have more aromatic structures and higher condensed degree.
出处
《石油学报(石油加工)》
EI
CAS
CSCD
北大核心
2007年第4期32-38,共7页
Acta Petrolei Sinica(Petroleum Processing Section)
基金
中国石油化工股份有限公司项目(104024)资助
关键词
钌离子催化氧化
沥青质
化学结构
加氢处理
ruthenium ions catalyzed oxidation
asphaltene
strueture
hydrotreating