煤油共炼改变了单一的煤炭直接液化和重油加氢裂化加工模式，降低了煤液化的操作难度，开辟了煤直接液化和重油轻质化的新途径，为推动煤炭和重油高效清洁转化、保障国家能源安全提供了技术支撑。然而煤油共炼常在高压、催化、加氢的条件下进行，难以直接获得共转化过程中煤和共炼油热裂解行为匹配特性，也不利于区分不同组分间的相互作用。选取一种低变质烟煤和一种催化裂化油浆(FCC油浆)为原料，利用热重-质谱联用技术研究了煤与FCC油浆单独热解和不同掺混比例下共热解的反应特性，探讨了煤和油浆本征热解的匹配性。结果表明，FCC油浆热解的起始温度，峰值温度和结束温度要远低于煤样，其产生的挥发分量则明显高于煤样。共热解实验曲线与计算反应曲线分析发现，反应初始阶段(200~400 ℃)，煤样与油浆混合样品的热解曲线明显向低温区偏移，表明该阶段煤与FCC油浆共热解反应有协同作用，但当反应温度大于400 ℃后，由于此时大部分FCC油浆已经挥发，生成的残焦与煤共热解没有明显的相互作用。结合在线质谱，发现在FCC油浆热解温区，出现煤热解反应产生的CO2和CO气体逸出峰，分析可能是由于FCC油浆的溶剂效应，或是其含有的活性金属，使煤中的部分醚键、羟基或含氧杂环分子发生了断键反应。通过煤灰与FCC油浆共热解没有相互作用、而FCC油浆对脱灰煤在低温区(200~400 ℃)的热解有一定促进作用，进一步验证了上述结论。

The co-processing of coal and oil changes the processing modes of direct coal liquefaction and heavy oil hydrocracking,reducing the difficulty of coal liquefaction,opening up new ways of direct coal liquefaction and heavy oil upgrading.It also provides technical support to promote the efficient and clean conversion of coal and heavy oil,which ensures the national energy security.However,the co-processing of coal and oil is often carried out under the conditions of high pressure,catalysis and hydrogenation.It is difficult to directly obtain the matching characteristics of thermal cracking behavior of coal and oil during the reaction,and not conducive to distinguish the interaction between different components.The pyrolysis and co-pyrolysis characteristics of a low metamorphic coal and a fluid catalytic cracking slurry (FCC) at different blending ratios were studied via thermogravimetry coupled with mass spectrometry.The intrinsic thermal reactions between the co-processing of coal and FCC was investigated by comparing the experimental and theoretical values.The results showed that the initial,peak and final pyrolysis temperature of the FCC are much lower than that of the coal,and the volatile content is significantly higher than the coal sample.At the initial stage of the reaction (200-400 ℃),the co-pyrolysis curves of coal and FCC is obviously shifted to a lower temperature region,indicating that synergetic effect exists during the co-pyrolysis of the coal and the FCC.When the reaction temperature is higher than 400 ℃,most of the FCC has volatilized,there is no obvious synergetic effect.Combined with online mass spectrometry data,the peaks of CO2 and CO was found in the pyrolysis temperature region of the FCC,at which mainly the FCC pyrolysis.It could be deduced to the solvent effect or the active metal contained in the FCC,which catalyzed the breaking of ether bond,hydroxyl or oxygen-containing molecule in coal.No interaction was observed during the co-pyrolysis of the coal ash and the FCC,while synergetic effect was observed during the co-pyrolysis of the FCC and the demineralized coal at 200-400 ℃,which further verifies the above deduction.

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 煤与FCC油浆单独热解反应特性

   2.2 煤与FCC油浆共热解反应特性

   2.3 煤与FCC油浆共热解协同作用分析

   2.4 煤与FCC油浆共热解气体产物组成

   2.5 FCC油浆与煤中矿物质及脱灰煤热解

3 结论