生物质是一种丰富、清洁和可再生的有机燃料，生物质能的开发和利用可有效解决环境污染和能源问题。然而生物质热解油、气的热值低等问题抑制了其开发利用。生物质与重油共热处理改变了单一的生物质热解和重油加氢裂化加工模式，降低了重油加工的难度，一定程度上改善生物质热解油、气热值低等问题。采用热重-质谱联用技术对生物质(玉米杆)和重油(FCC油浆)的单独热解和不同掺混比例下混合样品共热解特性进行研究。通过将混合样品共热解的实验失重率与理论失重率进行比较，研究玉米杆与FCC油浆共热解的相互作用特性。结果表明，玉米杆与FCC油浆主反应温区较为接近，均在200~400 ℃发生明显失重，但二者发生的反应类型并不相同。玉米杆主要发生热裂解反应，伴随着大量H2，CH4，CO，CO2，H2O(g)等小分子的逸出。而FCC油浆更多是发生挥发或蒸馏反应，仅在温度高于400 ℃时发生热裂解缩聚成焦反应，并伴随着少量CH4气体的逸出。玉米杆与FCC油浆共热解的实验曲线与理论曲线基本一致，并未有突变现象发生，但在热解主反应区(＜400 ℃)存在相互作用，且随玉米杆比例增加，相互作用增强，而在焦结构演变区，混合样品之间的相互作用较弱。结合在线质谱分析，共热解过程中气体逸出随玉米杆添加量的增加而规律性增加，说明生物质与FCC油浆共热解过程中相互作用所产生的改变较为温和。通过玉米杆灰与FCC油浆共热解实验验证发现，玉米杆灰具有促进FCC油浆热解的效果，而FCC油浆与脱灰玉米杆共热解则几乎没有相互作用。

Biomass is an energy source that is abundant,clean and renewable,and the development and utilization of biomass can effectively solve the environmental pollution and energy problems.However,there are a series of problems such as the low calorific value of produced gas and oil inhibited its exploration.Co-processing of biomass and heavy oil is believed as a good way for which could reduce the difficulty of heavy oil processing and solve the problems of the low calorific value of the gas and oil produced from biomass.In this paper,the pyrolysis and co-pyrolysis characteristics of corn stalk and a petroleum residue obtained from fluid catalytic cracking process (FCC) at different blending ratios were studied via thermogravimetry coupled with mass spectrometry.The intrinsic thermal reactions of the co-processing of corn stalk and FCC were investigated by comparing the experimental and calculated values.The results show that the main reaction temperature regions of corn stalk and FCC are close,and both of them have severe weight loss at 200-400 ℃,while the intrinsic reactions are different.Corn stalk’s pyrolysis mainly occurs as thermal cracking reactions,which is accompanied by the emission of small molecules such as H2,CH4,CO,CO2,H2O(g),etc.However,the thermal conversion of FCC is more likely to undergo volatilization or pyrolysis reactions,with only severe cracking reactions occur at a temperature above 400 ℃,accompanied by the emission of CH4.The experimental curve of co-pyrolysis is basically consistent with theoretical curve,and no mutation is observed.The positive synergistic effect exists in the main reaction temperature regions of pyrolysis (400 ℃.Combined with online mass spectrometry data,the amount of gas emission increases regularly with the increase of corn stalk addition,indicating that the change caused by the interaction of biomass and FCC is mild during co-pyrolysis.The co-pyrolysis of corn stalk ash and FCC shows that the corn stalk ash promotes the pyrolysis of FCC,while the FCC almost has no catalytic effect on the co-pyrolysis of FCC with de-ashed corn stalk.

1 实验部分

   1.1 实验原料

   1.2 样品制备

   1.3 实验方法

   1.4 数据处理方法

2 实验结果与讨论

   2.1 生物质与FCC油浆单独热解反应特性

   2.2 生物质与FCC油浆共热解反应特性

   2.3 生物质与FCC油浆共热解相互作用分析

   2.4 生物质与FCC油浆共热解气体产物组成

   2.5 FCC油浆与生物质中矿物质及脱灰生物质热解

3 结论