Origins of Thiadiamondoids and Diamondoidthiols in Petroleum
Origins of Thiadiamondoids and Diamondoidthiols in Petroleum
复制标题
DOI：
10.1021/ef7003333
复制
发表时间：
2007-09
期刊：
影响因子：
5.3
通讯作者：
Zhibin Wei;J. Moldowan;F. Fago;J. Dahl;C. Cai;K. Peters
中科院分区：
文献类型：
--
作者：
Zhibin Wei;J. Moldowan;F. Fago;J. Dahl;C. Cai;K. Peters
硫代二胺类化合物和金刚石二硫醇在硫酸盐热化学还原（TSR）蚀变的油中比在未蚀变的油中含量高几个数量级。这表明在TSR过程中形成了硫代金刚石和金刚石二硫醇。为了证明这一假设，我们在酸性条件下（pH = 4），使用硫酸钠作为氧化剂，在200°C和350°C的单质硫和去离子水存在下，对多种有机化合物进行了实验室TSR实验。结果表明，用TSR法可以从不含硫的金刚石合成硫代金刚石和硫代金刚石。金刚石类很可能是硫代金刚石和金刚石二硫醇的有机前体。此外，当用蒙脱石在200°C加热时，硫胆固醇产生微量的二甲基-2-硫烷，这表明这些金刚石衍生物可能部分源于多环硫化物和硫醇在酸性粘土矿物存在下的分子重排，因为它们也存在于未经过TSR的原油中。目前对这些杂原子笼状化合物的研究提高了对TSR的认识，并可用于降低石油勘探中的风险。
Thiadiamondoids and diamondoidthiols are orders of magnitude more abundant in oil altered by thermochemical sulfate reduction (TSR) than they are in nonaltered oil. This suggests that thiadiamondoids and diamondoidthiols form during TSR. In order to prove this hypothesis, we perform laboratory TSR experiments on diverse organic compounds using sodium sulfate as an oxidant in the presence of elemental sulfur and deionized water at 200 and 350 °C for 48 and 96 h under acidic conditions (pH = 4). Our results show that thiadiamondoids and diamondoidthiols can be created from non-sulfur-containing diamondoids by TSR. It seems likely that diamondoid species are organic precursors of thiadiamondoids and diamondoidthiols. In addition, thiocholesterol yields trace quantities of dimethyl-2-thiaadamantanes when heated with montmorillonite at 200 °C, suggesting that these diamondoid derivatives may partly originate by molecular rearrangement of polycyclic sulfides and thiols in the presence of acidic clay minerals since they also exist in crude oil that has not undergone TSR. The present study of these heteroatomic cage compounds improves understanding of TSR and can be used to reduce risk in petroleum exploration.