热解产物分析，尤其是热解初级产物的原位检测与分析是认识煤热解反应机理的重要途径。综述了热重分析与质谱联用（TG-MS）、热裂解仪与气相色谱-质谱联用（Py-GC-MS）和原位热解-真空紫外单光子/电子轰击双电离与飞行时间质谱（in-situ Py-PI/EI-TOF-MS）3种在线热解-质谱联用技术在煤热解及催化热解方面的应用，并分析其优缺点。TG-MS可获得煤转化率与热解气相挥发物（尤其是轻质组分）随热解温度的逸出特性，Py-GC-MS能够实现快速升温速率下热解挥发物的定性与定量分析，而in-situ Py-PI/EI-TOF-MS具有原位分析性好、灵敏度高、弱电离和易清洗等优点，可实现对类煤模型化合物、原煤及其萃取组分、生物质、废塑料等单独热解或共热解过程初级产物的原位检测以及二次演化行为的认识，也适用于热解挥发物的催化反应研究，是一种具有前途的、从分子水平上认识煤炭等含碳有机物热转化反应机理的有效手段。

The analysis of pyrolysis products,especially in-situ detection and analysis of primary pyrolysis products is an important way to understand the mechanism of coal pyrolysis. In this paper,the application of three kinds of on-line pyrolysis coupled with mass spectrometry（MS)techniques,including thermogravimetric-mass spectrometry（TG-MS),flash pyrolysis-gas chromatography-mass spectrometry analysis（Py-GC-MS),and in-situ pyrolysis time-of-flight mass spectrometry（Py-PI/EI-TOF-MS)combined with vacuum ultraviolet photoionization（PI)and electron ionization（EI)in coal pyrolysis were reviewed,and their advantages and disadvantages were compared. TG-MS can be used to analyze the coal conversion and the escape characteristics of pyrolysis gas volatiles（especially the light components)with the pyrolysis temperature. The compositions and distribution of pyrolysis products at rapid heating rate can be acquired by Py-GC-MS. In comparison,due to the characteristic of in-situ analysis,high sensitivity,soft ionization and easy cleaning,Py-PI/EI-TOF-MS can be used to in-situ detect the primary products from individual or co-pyrolysis of coal-model compounds,raw coal and its extraction,biomass as well as waste plastics. The evolution behaviors of primary products and the catalytic pyrolysis can be also implemented. The in-situ Py-PI/EI-TOF-MS provides a promising method to understand the pyrolysis mechanism of carbonaceous organic matters in a molecular level.

0 引言

1 TG-MS的应用

   1.1 用于煤热解研究

   1.2 用于煤催化热解研究

2 热裂解-气相色谱-质谱的应用

   2.1 用于煤的热解研究

   2.2 用于煤的催化热解研究

3 原位热解-真空紫外单光子/电子轰击双电离与飞行时间质谱联用的应用

   3.1 在煤/生物质等热解方面的应用

   3.2 在煤催化热解方面的应用

4 结论与展望