甲醇制烯烃(MTO)反应积炭演化和再生研究进展

doi:10.6023/A26030072

化学学报 ›› 2026, Vol. 84 ›› Issue (6): 987-1002.DOI: 10.6023/A26030072 上一篇下一篇

综述

甲醇制烯烃(MTO)反应积炭演化和再生研究进展

张琴^a^,^b^,^c^,^†, 陈祎瑶^a^,^b^,^c^,^†, 牛晶^a^,^b, 郅玉春^a^,^b^,^c^,^*(), 徐舒涛^a^,^b^,^c^,^*(), 魏迎旭^a^,^b^,^c, 刘中民^a^,^b^,^c

^a 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
^b 中国科学院大连化学物理研究所能源催化转化全国重点实验室辽宁大连 116023
^c 中国科学院大学北京 100049

投稿日期:2026-03-12 发布日期:2026-05-18

作者简介:

张琴, 中国科学院大连化学物理研究所研究生. 本科毕业于宁夏大学化学化工学院. 主要研究方向为甲醇和烃类耦合反应机理研究.

陈祎瑶, 中国科学院大连化学物理研究所博士生. 本科毕业于浙江工业大学化工学院. 主要研究方向为甲醇制烯烃积炭失活机理研究.

牛晶, 中国科学院大连化学物理研究所博士后. 2023年博士毕业于兰州大学化学化工学院, 毕业后至大连化学物理研究所从事博士后研究. 研究方向为通过先进固体核磁共振技术阐明分子筛催化醇类及其耦合反应机制.

郅玉春, 中国科学院大连化学物理研究所研究员. 2007年本科毕业于山东大学材料学院, 2010年硕士毕业于山东大学晶体材料国家重点实验室, 2015年博士毕业于德国慕尼黑工业大学, 毕业后在大连化学物理研究所工作, 主要研究方向围绕甲醇制烯烃过程, 从事甲醇转化机理研究、分子筛积炭失活机制及产物选择性调控机理研究.

徐舒涛, 中国科学院大连化学物理研究所研究员, 优青. 2004年本科毕业于复旦大学化学系, 2010年博士毕业于中国科学院大连化学物理研究所. 现为大连化物所低碳催化技术国家工程研究中心科研骨干. 2016年获第16届国际催化大会青年科学家奖(Young Scientist Prize), 2023年获中国化学会分子筛青年奖, 2025年获辽宁省自然科学一等奖(2024年度). 主要研究方向为原位固体核磁谱学技术在分子筛催化中的应用.

魏迎旭, 中国科学院大连化学物理研究所研究员. 1993年学士毕业于上海交通大学应用化学系, 2001年博士毕业于中科院大连化学物理研究所物理化学专业, 毕业后在大连化学物理研究所工作, 期间于2003~2004年赴比利时Namur大学进行博士后研究. 现为低碳催化技术国家工程研究中心研究员, 催化反应机理和新反应探索研究组组长. 从事分子筛催化、甲醇制烯烃、烷烃转化及二氧化碳耦合烷烃转化制高值化学品的基础和应用研究. 入选科技部创新人才推进计划中青年科技创新领军人才、大连化学物理研究所首席研究员、张大煜优秀学者等, 获辽宁省自然科学一等奖(2024年度).

刘中民, 中国工程院院士, 中国科学院大连化学物理研究所所长、低碳催化技术国家工程研究中心主任、国家能源低碳催化与工程研发中心主任. 1983年学士毕业于郑州大学, 1986年硕士毕业于中科院大连化物所, 1990年在中科院大连化物所获得博士学位, 1996年3月至1996年10月, 在法国科研中心CNRS418(Montpellier)开展博士后工作. 刘中民院士长期从事应用催化研究, 作为技术总负责人合作完成了多项创新成果并实现产业化. 完成了世界首次甲醇制烯烃(DMTO)技术工业性试验及首次工业化; 完成了世界首套10万吨/年煤基乙醇(DMTE)工业示范项目, 引领了我国新兴煤制大宗化学品和清洁燃料产业的发展.

基金资助:
国家自然科学基金(U25A20555); 国家自然科学基金(22241801); 国家自然科学基金(U25D9013); 国家自然科学基金(22288101); 国家自然科学基金(22372164); 辽宁国际联合实验室项目(2024JH2/102100005)

Recent Progress on Coking and Regeneration in the Methanol-to-Olefins (MTO) Reaction

Qin Zhang^a^,^b^,^c, Yiyao Chen^a^,^b^,^c, Jing Niu^a^,^b, Yuchun Zhi^a^,^b^,^c^,^*(), Shutao Xu^a^,^b^,^c^,^*(), Yingxu Wei^a^,^b^,^c, Zhongmin Liu^a^,^b^,^c

^a National Engineering Research Center of Lower-Carbon Catalysis Technology, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
^b State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
^c University of Chinese Academy of Sciences, Beijing 100049, China

Received:2026-03-12 Published:2026-05-18
Contact: *E-mail: yuchunzhi@dicp.ac.cn; xushutao@dicp.ac.cn
About author:
^† Zhang qin and Chen Yiyao contribute equally to this work.
Supported by:
National Natural Science Foundation of China(U25A20555); National Natural Science Foundation of China(22241801); National Natural Science Foundation of China(U25D9013); National Natural Science Foundation of China(22288101); National Natural Science Foundation of China(22372164); Liaoning International Joint Laboratory Project(2024JH2/102100005)

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摘要/Abstract

甲醇制烯烃(MTO)技术打破了烯烃生产对石油资源的依赖, 是非石油路线获取乙烯、丙烯等低碳烯烃的关键路径, 已成功实现大规模工业化应用. 然而, SAPO-34分子筛和HZSM-5分子筛作为MTO反应最理想的催化剂, 在实际操作中会因积炭生成而失活, 影响烯烃产率及选择性. 这些制约装置长周期运行的因素仍有较大的优化空间. 本综述聚焦MTO反应过程与催化剂体系, 重点关注积炭的形成、生长过程, 深入解析积炭的性质, 系统梳理积炭对催化性能的影响, 进一步总结延缓催化剂失活和促进再生策略的研究进展, 最终对现有技术进行展望.

关键词: 甲醇制烯烃(MTO), 积炭, SAPO-34, HZSM-5, 催化剂失活, 催化剂再生

The methanol-to-olefins (MTO) technology, as a non-petroleum-dependent low-carbon olefin production route, has successfully broken through the reliance of traditional olefin industries on petroleum resources. It has become an important way to obtain key chemical raw materials such as ethylene and propylene, and has achieved large-scale industrial application. During the MTO reaction process, SAPO-34 and HZSM-5 molecular sieves are the most representative catalysts. However, under actual operating conditions, they are prone to deactivation caused by coke deposition, which compromises the olefin yield and selectivity, thereby restricting the stable, long-term operation of the unit. This review systematically summarizes the research progress of the MTO reaction process and its core catalyst system, with a focus on the formation and evolution mechanism of coke species. By deeply analyzing the structure, composition, and dynamic change characteristics of coke, it reveals that coke deposition is not a single component but a continuous mixture that gradually evolves from soluble aromatic hydrocarbons to insoluble fused-ring aromatic hydrocarbons. Based on the systematic analysis of the coke deposition behavior of SAPO-34 and HZSM-5 molecular sieves, the "cage-passing growth" mechanism for SAPO-34 molecular sieves and the "channel intersection-passing growth" mechanism for HZSM-5 molecular sieves are proposed, revealing the essential similarity in the coke evolution paths. On this basis, the influence of coke deposition on catalyst activity, stability, and olefin selectivity is further summarized, and the main progress in regulatory strategies is systematically summarized from two dimensions: delaying catalyst deactivation and optimizing the regeneration process. Finally, the development direction of the existing technology system is prospected to provide a reference for the development of efficient anti-coke deposition catalysts and the continuous improvement of the MTO process.

Key words: methanol-to-olefins (MTO), coke, SAPO-34, HZSM-5, catalyst deactivation, catalyst regeneration

引用此文

张琴, 陈祎瑶, 牛晶, 郅玉春, 徐舒涛, 魏迎旭, 刘中民. 甲醇制烯烃(MTO)反应积炭演化和再生研究进展[J]. 化学学报, 2026, 84(6): 987-1002.

Qin Zhang, Yiyao Chen, Jing Niu, Yuchun Zhi, Shutao Xu, Yingxu Wei, Zhongmin Liu. Recent Progress on Coking and Regeneration in the Methanol-to-Olefins (MTO) Reaction[J]. Acta Chimica Sinica, 2026, 84(6): 987-1002.

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图/表 10

图1. 甲醇制烃(MTH)路线

Figure 1. Methanol to hydrocarbons (MTH) route

图2. MTO基础研究和应用研究的里程碑进展(基于文献[10]进行补充修改)

Figure 2. Landmark progress in fundamental and applied research of methanol-to-olefins (MTO) (Modified and supplemented based on Ref. [10])

图3. MTH反应网络和历程. MTH转化三循环(a)[30], 甲醛对MTH反应的影响(b)[32], MTH反应动态自催化反应历程(c)[31]

Figure 3. Reaction network and process of MTH. Proposed three-cycle of MTH reaction (a)[30]. Effect of formaldehyde on the mechanistic pathways of MTH reaction (b)[32]. Dynamic autocatalytic process of MTH reaction (c)[31]

图4. HZSM-5和SAPO-34分子筛在660 K、不同MTH反应时间下的共聚焦荧光显微图像和切片示意图(a)[43]. SAPO-34分子筛中碳质物种的时空分布(b)[44]. 基于直接电子衍射技术对HZSM-5微孔积炭直接成像, 积炭物种富集于孔道交叉处并沿直孔道延伸(c)[48]. HZSM-5不同晶面的积炭HAADF-STEM图像, 直孔道(010)面的积炭更趋石墨化(d)[49]. 固定床反应器上积炭的TEM图(e)[42]

Figure 4. Confocal fluorescence microscopy images and sectional diagrams of HZSM-5 and SAPO-34 crystals at 660 K and varying MTH reaction time (a)[43]. Spatial and temporal distribution of carbonaceous species in SAPO-34 molecular sieve (b)[44]. Direct imaging of carbon species accumulated inside HZSM-5 channel based on direct electron diffraction. Carbon accumulation signal is enriched at the channel intersection and extends along the straight channel (c)[48]. The HAADF-STEM images of carbon deposits on different crystal planes of HZSM-5, with the carbon deposits on the straight channel (010) plane being more graphite-like (d)[49].TEM diagram of carbon deposition in fixed bed reactor (e)[42]

图5. 673 K不同反应时间下新鲜和失活SAPO-34催化剂HP 129Xe核磁共振谱(a)[46]. 分离出的不溶性积炭的13C固态核磁共振光谱图(b)[2]. 300 ℃甲醇转化反应不同时间SAPO-34笼内留存的有机物的GC-MS谱图(c)[59]. 程序升温甲醇转化反应中SAPO-34催化剂上积炭物种的生成和随温度的演变(d)[58]. 不同温度下反应后SAPO-34笼内留存的有机物的GC-MS谱图(e)[57]

Figure 5. Temperature-dependent HP 129Xe NMR spectra of fresh and spent SAPO-34 catalysts after MTO reaction at 673 K for various reaction times (a)[46]. 13C solid‑state NMR spectrum of the insoluble coke (b)[2]. GC-MS spectra of retained organics in SAPO-34 after methanol reaction at 300 ℃ for different times (c)[59]. Coke species evolution in the temperature-programmed methanol conversion over SAPO-34 (d)[58]. GC-MS analysis for the extracted species in SAPO-34 after different reaction temperatures (e)[57]

图6. SAPO-34催化剂上提取的积炭物种的MALDI FT-ICR MS图(a)[2]. SAPO-34上MTO反应的积炭和水蒸气再生路径(b)[60]. HZSM-5上积炭物种的STM与nc-AFM图(c)和MALDI FT-ICR MS图(d)[3]

Figure 6. MALDI FT-ICR MS spectrum of released carbonaceous deposits on SAPO-34 catalyst (a)[2]. The coking route of MTO reaction and the decoking route of steam regeneration of the spent SAPO-34 (b)[60]. Direct atomic-resolution imaging of carbon species on HZSM-5 by STM and nc-AFM (c) and MALDI FT-ICR MS spectrum analysis (d)[3]

图7. SAPO-34分子筛积炭分子生长路径(a)[2], HZSM-5分子筛积炭分子生长路线(b)[3]

Figure 7. The molecular evolution route of PAHs on SAPO-34 molecular sieve (a)[2], and the growth route of coke molecules on HZSM-5 molecular sieve (b)[3]

图8. 流化床反应器(a)[74]及DMTO放大装置(b)[73]示意图. 固定床反应器示意图(c). 流化床反应器中不同操作条件下积炭含量随时间的变化情况, 通过积炭沉积模型, 可模拟固定床反应器(d)[71]

Figure 8. Diagram of fluidized bed reactor (a)[74] and DMTO amplifier (b)[73]. Fixed bed reactor (c). The variation of coke content over time under different operating conditions in a fluidized bed reactor can be simulated for a fixed bed reactor through a coke deposition model (d)[71]

图9. SAPO-34晶体中活性烃池物种的定向构建示意图(a). 蒸气处理过程中生成的小分子气体含量(b). 698 K、WHSV为1.0 h−1的MTO转化过程中, 商用SA-34-Ⅰ催化剂在处理前后(即预积炭5 min, 随后水蒸气处理5 h的SAPO-34)甲醇转化率, 以及反应100 min时乙烯和丙烯的选择性(c)[98]

Figure 9. Schematic diagrams of the directional construction of active hydrocarbon pool species within SAPO-34 crystals (a). The content of small molecular gases produced during vapor treatment (b). Time-dependent methanol conversion over the commercial SA-34-I catalyst before and after treatments (precoking for 5 min followed by steaming for 5 h) during the MTO conversion at 698 K with a WHSV of 1.0 h−1, and the selectivity of ethylene and propylene at TOS=100 min (c)[98]

图10. 积炭转化为特定中间体的示意图(a), 953 K氮气和蒸气裂解过程中分子质量小于200 Da的碳质中间体分布(b), 953 K氮气和蒸气裂解过程中分子量大于200 Da的碳质物质随时间演化的MALDI FT-ICR MS图(c), 923 K下用蒸气处理的失活分子筛的原位UV-Raman光谱(d), 953 K下失活分子筛蒸气裂解过程中分子筛微孔体积和积炭量的变化(e)[79]

Figure 10. Schematic diagram of coke transformation into specific intermediates (a). Evolution of detailed distribution of carbonaceous intermediates with molecular mass smaller than 200 Da during nitrogen and steam cracking at 953 K, which is analyzed by GC-MS (b). Evolution of carbonaceous species with molecular mass larger than 200 Da during nitrogen and steam cracking at 953 K, which is analyzed by MALDI FT-ICR MS (c). Operando UV-Raman spectra of ZEOS-Coked samples treated by steam at 923 K with different time (d). Evolution of textual property and coke quantity of ZEOS-Coked samples during steam cracking at 953 K (e)[79]

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甲醇制烯烃(MTO)反应积炭演化和再生研究进展

Recent Progress on Coking and Regeneration in the Methanol-to-Olefins (MTO) Reaction

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