基于^(13)C NMR技术的桦甸油页岩热解行为

Pyrolysis behavior of Huadian oil shale based on ^(13)C NMR technology

基于13C NMR技术,研究了桦甸油页岩及其不同终温下的热解固体残余物中有机质的化学结构,对典型页岩油与热解气的有机组分进行了简要分析。通过对油页岩及其热解固体残余物的谱图分峰拟合分析,获得了芳碳率、脂碳率等11个基本结构参数和平均亚甲基链的碳数、芳环取代度、桥接芳碳与周碳之比3个重要结构参数,探讨了热解过程中相应结构参数的变化特性。结果表明,油页岩在生油阶段开始之前就已经有部分亚甲基基团析出生成烃气或缩合成为芳环,而油页岩的热解过程是芳环不断缩合的过程。结合化学结构与热解固体残余物的潜在产物产率之间的关系可知,油页岩热解固体残余物的热解半焦、热解气的潜在产率分别与油页岩芳碳率、脂碳率成线性关系,而热解油的潜在产率与亚甲基基团率有直接关系。

In this study,the chemical structure of Huadian oil shale and its pyrolysis solid residues were investigated using the solid state 13C NMR spectroscopy. The typical organic components of shale oil and gas were also analyzed. By fitting 13C NMR spectra,a series of chemical structural parameters were derived,including aromatic carbon rate fa,fat rate of carbon fal,Cn,etc,and the variation characteristics of those structural parameters were discussed. A part of methylene group was transformed into gas or condensed to the aromatic ring before they transformed into oil. Moreover,the aromatic ring was condensed continuously during pyrolysis of oil shale. The potential yields of semi-coke and gas were proportional with fa and fal. The potential yield of the shale oil was related to methylene group rate directly.