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甲醛对HZSM-5分子筛催化甲苯和苯转化反应积炭失活的影响
Effect of formaldehyde on coke-induced deactivation of HZSM-5 zeolite during catalytic conversion of toluene and benzene
- 低碳化学与化工 2026, 51(2): 59-65.
- 作者机构：
1.中国科学院 大连化学物理研究所 低碳催化技术国家工程研究中心，辽宁 大连 116023
2.中国科学院大学，北京 100049
- 作者简介：
赫英俊（2000—），硕士研究生，研究方向为分子筛催化，E-mail：yingjunhe@dicp.ac.cn。
郅玉春（1984—），博士，研究员，研究方向为分子筛催化与C1化学，E-mail：yuchunzhi@dicp.ac.cn。
- 基金信息：国家自然科学基金(22372164;22402190;22288101;22072148)
DOI：10.12434/j.issn.2097-2547.20250183
中图分类号： TQ426.95;O643.36收稿：2025-04-16，
修回：2025-05-11，
纸质出版：2026-02-25
- 稿件说明：
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赫英俊,陈祎瑶,林杉帆等.甲醛对HZSM-5分子筛催化甲苯和苯转化反应积炭失活的影响[J].低碳化学与化工,2026,51(2):59-65.
HE Yingjun,CHEN Yiyao,LIN Shanfan,et al.Effect of formaldehyde on coke-induced deactivation of HZSM-5 zeolite during catalytic conversion of toluene and benzene[J].Low-Carbon Chemistry and Chemical Engineering,2026,51(2):59-65.
赫英俊,陈祎瑶,林杉帆等.甲醛对HZSM-5分子筛催化甲苯和苯转化反应积炭失活的影响[J].低碳化学与化工,2026,51(2):59-65. DOI： 10.12434/j.issn.2097-2547.20250183.
HE Yingjun,CHEN Yiyao,LIN Shanfan,et al.Effect of formaldehyde on coke-induced deactivation of HZSM-5 zeolite during catalytic conversion of toluene and benzene[J].Low-Carbon Chemistry and Chemical Engineering,2026,51(2):59-65. DOI： 10.12434/j.issn.2097-2547.20250183.
摘要
甲醇制烃（MTH）反应是衔接煤化工与石油化工及天然气化工的“桥梁”。HZSM-5分子筛因其独特的孔道结构和中强酸性在MTH反应中表现出良好的催化性能。甲醛可通过Prins反应加速MTH反应进程，同时也能促进多甲基苯交联缩合形成稠环芳烃（PAH），然而其具体作用机制尚未得到深入研究。通过设计甲苯、苯分别与甲醛在HZSM-5分子筛上的共进料实验，结合气相色谱-质谱联用技术和TGA分析，发现甲苯与甲醛共转化的关键中间体为二苯甲烷，揭示了甲醛与甲苯相互作用的关键路径，即甲苯与甲醛经酸位点作用生成苯甲醇衍生物，苯甲醇衍生物脱水形成二苯甲烷。二苯甲烷既可加速甲苯转化过程，又能作为“桥梁分子”显著促进甲苯的交联反应。
Abstract
Methanol-to-hydrocarbons (MTH) reaction serves as a “bridge” connecting coal chemical industry with petrochemical and natural gas chemical industries. HZSM-5 zeolite exhibits excellent catalytic performance in MTH reaction due to its unique pore structure and moderate to strong acidity. Formaldehyde can accelerate the MTH reaction process via the Prins reaction and also promote the cross-linking and condensation of poly-methyl benzenes to form polyaromatic hydrocarbons (PAH). However
the mechanism has not been thoroughly investigated. By designing a co-feeding experiment of toluene
benzene with formaldehyde on HZSM-5 zeolite
respectively
with combining gas chromatography-mass spectrometry and TGA
it is found that the key intermediate in the co-transformation of toluene and formaldehyde is diphenylmethane
which reveals the key interaction pathway between formaldehyde and toluene: Toluene and formaldehyde react at acid sites to form benzyl alcohol derivatives
which then dehydrate to form diphenylmethane. Diphenylmethane can not only accelerate the toluene conversion process but also act as a “bridge molecule” to significantly promote the cross-linking reaction of toluene.
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references
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