铈改性磁性核壳HZSM-5催化富油煤热解研究

Exploring the pyrolysis of tar-rich coals under the catalysis of cerium-modified magnetic core-shell HZSM-5

  • 摘要: 【目的】富油煤是集煤、油气属性为一体的宝贵煤炭资源,催化热解是实现其绿色低碳开发的重要途径。然而,高效可回收催化剂的研发仍面临着极大的挑战。【方法】以HZSM-5@SiO2@MgFe2O4 (HSMF)为原料,采用水热法与碱改性制备具有多级孔结构的HZSM-5@SiO2@MgFe2O4 (mHSMF),再通过沉淀法制备铈改性mHSMF (5-CeO2/mHSMF);并利用固定床反应器考察了5-CeO2/mHSMF对神府富油煤热解产物的调控作用及其抗积炭性能。【结果和结论】结果表明,CeO2改性有助于在HSMF表面形成微−介孔多级孔道结构;在5-CeO2/mHSMF催化剂上,650 ℃、N2气氛、反应1 h的条件下,神府富油煤焦油产率达到13.38%,是格金试验焦油产率的176%;相较于原煤热解,催化热解得到的焦油中脂肪烃类及苯类化合物含量分别增加了3.04%和3.07%,煤气中H2和CH4含量提高了10.49%;经CeO2改性后,催化剂的抗积炭性能增幅达86.1%,积炭量仅为11.60 mg/g,且积炭趋于稳定的石墨化结构。5-CeO2/mHSMF对神府富油煤催化热解产物的分布及组成具有明显调控作用,并表现出良好的抗积炭效果和磁性可回收性能。

     

    Abstract:
    Objective  Tar-rich coals are valuable resources integrating coal, tar, and gas properties. Catalytic pyrolysis serves as a significant approach for achieving green and low-carbon development of tar-rich coals. However, the research and development of efficient and recyclable catalysts for the pyrolysis of tar-rich coals remains highly challenging.
    Methods  With HZSM-5@SiO2@MgFe2O4 (HSMF) as the raw material, this study prepared HZSM-5@SiO2@MgFe2O4 (mHSMF) with a hierarchical porous structure using the hydrothermal method and alkali modification, followed by the preparation of cerium-modified mHSMF (5-CeO2/mHSMF) using the precipitation method. Employing a fixed-bed reactor, this study investigated the regulatory effects of 5-CeO2/mHSMF on the pyrolysis products of tar-rich coals from the Shenfu block, along with the anti-carbon deposition performance of 5-CeO2/mHSMF.
    Results and Conclusions The results indicate that the CeO2-based modification of HSMF was conducive to the formation of a hierarchical porous structure comprising micropores and mesopores on the surface of HSMF. Through pyrolysis at 650°C in the N2 atmosphere for 1 hr using 5-CeO2/mHSMF as a catalyst, the coals exhibited a tar yield of 13.38%, equivalent to a tar yield of 176% in the Gray-King assay. Compared to the pyrolysis of raw coals, the catalytic pyrolysis exhibited increases in the aliphatic-hydrocarbon and benzene-compound contents in tar of 3.04% and 3.07%, respectively and an increase in the H2 and CH4 content in coal gas of 10.49%. Through CeO2-based modification, the catalyst enhanced the anti-carbon deposition performance by 86.1%, with carbon deposits of merely 11.60 mg/g and tending to form a stable graphitized structure. Overall, 5-CeO2/mHSMF manifests significant regulation of the distribution and composition of the products from the catalytic pyrolysis of coals in the Shenfu block, along with encouraging anti-carbon deposition performance and magnetic recyclability.

     

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