Volatility and catalysis of trace elements during oil shale pyrolysis

doi:10.11949/j.issn.0438-1157.20170297

Abstract

Abstract:

Inductively coupled plasma mass spectrometer (ICP-MS) has been used to determine the concentration of Li,V,Cr,Co,Ni,Cu,Zn,Sr,Mo,Cd,Sb,Ba,and Pb in oil shale samples and semi-cokes pyrolyzed at different final temperatures.The results show that Balikun oil shale contains more trace elements,especially Ba,Cd,Li,V and Sb,compared with Longkou oil shale which is only rich in Ba and Cd,and that most trace elements volatilize at around 500℃.In addition,the influence of trace elements on kerogen pyrolysis was studied.Thermogravimetric analyzer was used to investigate pyrolysis kinetics of kerogen with trace elements in different forms.The kinetic parameters (apparent activation energy E and frequency factor A) were calculated using overall n order reaction procedure.The relative content of alkane products was characterized by pyrolysis-gas chromatography/mass spectrometer (PY-GC/MS).The results indicate that Ni (NO₃)₂ can catalyse kerogen pyrolysis by increasing its conversion,rate and yields of light alkane products and decreasing yields of heavy alkane products.

Key words: oil shale, pyrolysis, trace elements, volatility, kinetics, catalysis

摘要：

利用电感耦合等离子质谱仪（ICP-MS）测定油页岩样品和不同终温下热解半焦中13种金属微量元素的含量，分析这些元素在样品中的含量分布特征及其迁移规律。结果显示：龙口油页岩中富集Ba、Cd，巴里坤油页岩中富集Ba、Cd、Li、V、Sb，且样品中多数微量元素在500℃时挥发性最强。将不同形态的微量元素负载于干酪根上并进行热重分析，根据热重结果计算其动力学，再通过裂解气质联用实验（PY-GC/MS）测定干酪根和浸渍硝酸镍的干酪根热解时烷烃类产物的相对含量，研究微量元素对干酪根热解生烃转化率、热解速率以及产物分布的影响。结果表明：微量元素的盐类可以催化干酪根热解生烃，增大其热解转化率和热解速率，提高轻组分烷烃产率，降低重组分烷烃产率。

关键词: 油页岩, 热解, 微量元素, 迁移规律, 动力学, 催化作用

CLC Number:

TQ51

HE Lu, WANG Li, MA Yue, LI Shuyuan. Volatility and catalysis of trace elements during oil shale pyrolysis[J]. CIESC Journal, 2017, 68(10): 3912-3922.

何璐, 王丽, 马跃, 李术元. 油页岩热解过程中微量元素迁移及其作用规律[J]. 化工学报, 2017, 68(10): 3912-3922.

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