富油煤模拟原位加压热解三相产物理化特性研究

Experimental study on physical-chemical characteristics of three-phase products during simulated in-situ pressurized pyrolysis of tar-rich coal

  • 摘要: 富油煤作为一种特殊的煤基油气资源,其高效清洁利用对实现我国“双碳”目标意义重大。富油煤原位热解是一种将煤转化为油气资源并分级利用的新途径。目前该技术尚处于起步阶段,关于富油煤热解产物理化性质的研究仍然有限。通过自搭建的加压热解实验系统,选择富油煤原位热解工艺的常见温度区间,微米级到毫米级的粒径样品以及N2、CO2以及50% N2+50% CO2 3种热解气氛,关注了三种影响因素对富油煤热解产物理化性质的影响。采用微米及毫米级别的样品,重点关注富油煤“热解−氧化”三相产物分布特性,排除了力学作用的影响,更为精确地研究富油煤热解过程的热效应影响。结果表明:大粒径的煤样热解后质量损失较高,表现出更强的热解反应性。煤样粒径从2.00 mm增加至10.00 mm时,CH4的体积分数从17.64%升高至37.92%。热解温度的升高提高了热解气及焦油的产率同时促进了芳香环的缩聚,然而过高的温度可能导致二次反应加剧,焦油产率降低。加压热解环境中,CO2气氛下热解水的生成消耗了更多的H自由基,因而CO2气氛下H2产量(14.64 mL/g,8.54%)低于N2气氛(23.01 mL/g,16.37%)。CO2气氛促进了单环芳烃的氧化和醚键的断裂,抑制了脂肪族的缩聚反应和裂解,使得芳香烃及酚类的含量有所降低,脂肪烃含量升高。有助于为富油煤原位热解工业化应用提供数据支撑。

     

    Abstract: As a special coal-based hydrocarbon resource, the efficient and clean utilization of tar-rich coal is of great significance to realizing the "dual carbon" target in China. In-situ pyrolysis of tar-rich coal is a brand-new method to convert coal into oil and gas resources and contribute to the classification and utilization. At present, this technology is still in its infancy, and the research on the physical and chemical properties of pyrolysis products of tar-rich coal is still limited. The common temperature range of in-situ pyrolysis of tar-rich coal, the particle size samples from micron to millimeter, and three pyrolysis atmospheres of N2, CO2 and 50% N2+50% CO2 were selected. The effects of these three impacting factors on the physical and chemical properties of three-phase products of tar-rich coal pyrolysis were focused on through a self-built experimental system of pressurized pyrolysis. To better understand the thermal impact of the tar-rich coal pyrolysis process, the distribution features of the "pyrolysis-oxidation" three-phase products of tar-rich coal are examined using micron and millimeter samples, ignoring the effects of mechanical action. The results show that the mass loss of coal samples with large particle sizes is higher after pyrolysis, showing stronger pyrolysis reactivity. The volume fraction of CH4 increased from 17.64% to 37.92% when the particle size of the coal sample increased from 2.00 mm to 10.00 mm. The increase in pyrolysis temperature improves the yield of gas and tar. meanwhile promotes the polycondensation of aromatic nuclei, however, excessive temperature may lead to the intensification of secondary reaction and the decrease of tar yield. In the pressure pyrolysis conditions, the generation of pyrolysis water in the CO2 atmosphere consumes more H radicals, so the yield of H2 in CO2 atmosphere (14.64 mL/g, 8.54%) is lower than that in N2 atmosphere (23.01 mL/g, 16.37%). The CO2 atmosphere promotes the oxidation of monocyclic aromatic hydrocarbons and the cleavage of ether bonds. Simultaneously, it inhibits the polycondensation and cracking of aliphatic hydrocarbons so that the contents of aromatic hydrocarbons and phenols decrease and the contents of aliphatic hydrocarbons increase. Data support for the industrial application of in-situ pyrolysis of tar-rich coal is helpful in being provided.

     

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