酸性分子筛上CO2与丙烷制芳烃中碳原子高效利用

doi:10.1016/S1872-2067(25)64680-8

催化学报 ›› 2025, Vol. 72: 314-322.DOI: 10.1016/S1872-2067(25)64680-8

酸性分子筛上CO₂与丙烷制芳烃中碳原子高效利用

李诚^a^,^b, 房旭东^a^,^*(), 李斌^a^,^b, 闫思杨^c, 陈之旸^a, 杨磊磊^a^,^b, 郝邵雯^a^,^b, 刘红超^a, 刘家旭^c^,^*(), 朱文良^a^,^*()

^a中国科学院大连化学物理研究所, 低碳催化国家工程研究中心, 辽宁大连 116023
^b中国科学院大学, 北京 100049
^c大连理工大学化工学院, 精细化工国家重点实验室, 智能材料前沿科学中心, 辽宁大连 116012

收稿日期:2025-01-24 接受日期:2025-03-26 出版日期:2025-05-18 发布日期:2025-05-20
通讯作者: *电子信箱: xdfang@dicp.ac.cn (房旭东),liujiaxu@dlut.edu.cn (刘家旭),wlzhu@dicp.ac.cn (朱文良).
基金资助:
国家自然科学基金(22402179);国家自然科学基金(22472016);国家自然科学基金(21991094);国家自然科学基金(21991090);中国科学院战略先导专项“清洁能源转化技术与示范”(XDA21030100);大连市高层次人才创新支持计划(2017RD07);国家高层次人才专项支持计划(SQ2019RA2TST0016)

Efficient carbon integration of CO₂ in propane aromatization over acidic zeolites

Cheng Li^a^,^b, Xudong Fang^a^,^*(), Bin Li^a^,^b, Siyang Yan^c, Zhiyang Chen^a, Leilei Yang^a^,^b, Shaowen Hao^a^,^b, Hongchao Liu^a, Jiaxu Liu^c^,^*(), Wenliang Zhu^a^,^*()

^aNational Engineering Research Center of Lower-Carbon Catalysis Technology, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
^bUniversity of Chinese Academy of Sciences, Beijing 100049, China
^cState Key Laboratory of Fine Chemicals, Frontier Science Center for Smart Materials, School of Chemical Engineering, Dalian University of Technology, Dalian 116012, Liaoning, China

Received:2025-01-24 Accepted:2025-03-26 Online:2025-05-18 Published:2025-05-20
Contact: *E-mail: xdfang@dicp.ac.cn (X. Fang), liujiaxu@dlut.edu.cn (J. Liu), wlzhu@dicp.ac.cn (W. Zhu).
Supported by:
National Natural Science Foundation of China(22402179);National Natural Science Foundation of China(22472016);National Natural Science Foundation of China(21991094);National Natural Science Foundation of China(21991090);“Transformational Technologies for Clean Energy and Demonstration”, Strategic Priority Research Program of the Chinese Academy of Sciences(XDA21030100);Dalian High Level Talent Innovation Support Program(2017RD07);National Special Support Program for High Level Talents(SQ2019RA2TST0016)

摘要/Abstract

摘要：

芳烃作为现代工业体系的关键基础化学品, 在合成树脂、纤维、医药等领域应用广泛. 传统石油基生产路线高度依赖石脑油催化重整, 面临石油资源短缺与碳排放双重压力. 与此同时, CO₂作为典型温室气体, 其资源化利用兼具减排与碳资源高效转化的战略价值, 但受限于其热力学稳定性, 通过加氢路径高选择性制芳烃仍存在挑战. 丙烷作为天然气、页岩气的主要成分, 直接芳构化时因碳氢比失衡导致大量小分子烷烃副产物生成, 限制了芳烃选择性. 因此, 开发CO₂与丙烷耦合转化制芳烃新路线, 突破碳氢限制, 定向提高芳烃选择性, 实现低碳烷烃资源高值化利用, 对构建绿色低碳的芳烃生产技术体系具有重要科学意义和工业应用潜力.

本文创新性地提出酸性分子筛催化CO₂与丙烷耦合定向转化制芳烃的新策略. 选用具有十元环孔道结构的H-ZSM-5分子筛为催化剂, 系统对比了丙烷在Ar/CO₂气氛下的转化行为. 实验结果表明, CO₂的引入显著提升芳烃选择性, 在723 K, 3.0 MPa, C₃H₈/CO₂ = 1:120条件下, 丙烷转化率达48.8%, 芳烃选择性提升至60.2%, 较Ar气氛下提高约30%. 通过调控分子筛Brönsted酸量发现, 提高Brönsted酸量可抑制小分子烷烃生成, 促进丙烷向芳烃的定向转化. 这表明CO₂氛围下的丙烷芳构化过程是有异于传统氢转移机理的Brönsted酸催化过程. 通过双光束原位红外光谱、¹³C同位素标记实验、丙烷程序升温表面反应实验和探针分子实验, 证明了烯烃和内酯是关键中间物种, 且CO₂中的碳原子直接参与芳环形成, 提出了CO₂与丙烷在酸性分子筛上基于烯烃和内酯的耦合转化新机制, 即“丙烷裂解/脱氢→烯烃-CO₂耦合形成内酯→芳烃”的多步反应机制, 其中CO₂通过与烯烃结合调控氢转移过程, 突破传统芳构化反应的碳氢平衡限制.

综上, 本文为CO₂与低碳烷烃耦合制芳烃提供了新思路, 通过揭示含氧中间体介导的反应机制, 深化了对复杂耦合反应过程的理解. 未来可进一步优化分子筛孔道结构与酸性位点分布, 提高芳烃收率. 本工作不仅为石化行业“减油增化”转型提供新的思路, 也为实现CO₂大规模资源化利用和“双碳”目标贡献了催化科学新方案.

关键词: CO₂利用, 丙烷芳构化, 耦合效应, 酸性分子筛, 内酯

Abstract:

Direct converting carbon dioxide (CO₂) and propane (C₃H₈) into aromatics with high carbon utilization offers a desirable opportunity to simultaneously mitigate CO₂ emission and adequately utilize C₃H₈ in shale gas. Owing to their thermodynamic resistance, converting CO₂ and C₃H₈ respectively remains difficult. Here, we achieve 60.2% aromatics selectivity and 48.8% propane conversion over H-ZSM-5-25 via a zeolite-catalyzing the coupling of CO₂ and C₃H₈. Operando dual-beam FTIR spectroscopy combined with ¹³C-labeled CO₂ tracing experiments revealed that CO₂ is directly involved in the generation of aromatics, with its carbon atoms selectively embedded into the aromatic ring, bypassing the reverse water-gas shift pathway. Accordingly, a cooperative aromatization mechanism is proposed. Thereinto, lactones, produced from CO₂ and olefins, are proven to be the key intermediate. This work not only provides an opportunity for simultaneous conversion of CO₂ and C₃H₈, but also expends coupling strategy designing of CO₂ and alkanes over acidic zeolites.

Key words: CO₂ utilization, Propane aromatization, Coupling effect, Acidic zeolites, Lactone

李诚, 房旭东, 李斌, 闫思杨, 陈之旸, 杨磊磊, 郝邵雯, 刘红超, 刘家旭, 朱文良. 酸性分子筛上CO₂与丙烷制芳烃中碳原子高效利用[J]. 催化学报, 2025, 72: 314-322.

Cheng Li, Xudong Fang, Bin Li, Siyang Yan, Zhiyang Chen, Leilei Yang, Shaowen Hao, Hongchao Liu, Jiaxu Liu, Wenliang Zhu. Efficient carbon integration of CO₂ in propane aromatization over acidic zeolites[J]. Chinese Journal of Catalysis, 2025, 72: 314-322.

×
扫码分享

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(25)64680-8

https://www.cjcatal.com/CN/Y2025/V72/I5/314

图/表 5

Fig. 1. CO2-C3H8 co-conversion to aromatics over acidic zeolites with varied framework structures. (a) Schematic illustration of the co-conversion strategy. (b) Catalytic performances of different zeolitic topologies in propane aromatization, with and without CO2 co-feeding. (c) Propane conversion and product distribution over H-ZSM-5 at 0.1 MPa under various gas atmospheres. (d) Aromatic selectivity profiles over H-ZSM-5 at 3.0 MPa under different reaction environments. Reaction conditions: (b,d) 723 K, 20 kPa C3H8, (2570 kPa CO2, 410 kPa Ar solid) or (2980 kPa Ar dash), 1000 mL/gcat/h; (c) 723 K, 0.72 kPa C3H8, (86.85 kPa CO2, 13.43 kPa Ar) or (100.28 kPa Ar), 1000 mL/gcat/h. Note that olefins represent C2=-C4=, alkanes represent C1-C40 (apart from C3H8), and others represent C5+ hydrocarbon excluding aromatics.

Fig. 2. Catalytic behavior of H-ZSM-5 catalysts with varying SiO2/Al2O3 ratios on the co-conversion of CO2 and C3H8. (a) Selectivity distribution of main products. (b) Correlation between aluminum content in H-ZSM-5 and the selectivity toward aromatics, alkanes, and olefins. Reaction conditions: (a) 723 K, 20 kPa C3H8, (2570 kPa CO2, 410 kPa Ar) or (2980 kPa Ar), 1000 mL/gcat/h; (b) 723 K, 20 kPa C3H8, 2570 kPa CO2, 410 kPa Ar, 1000 mL/gcat/h; Note that olefins represent C2=-C4=, alkanes represent C1-C40 (apart from C3H8), and others represent C5+ hydrocarbon excluding aromatics.

Fig. 3. Impact of reaction parameters on the co-conversion of CO2 and C3H8 over H-ZSM-5-25. (a) Variation in propane conversion and product distribution with total reaction pressure. (b) Dependence of C3H8 conversion and product selectivity on reaction temperature. (c) Effect of CO2 partial pressure on selectivity trends and converted CO2/ C3H8 ratios. (d) Product profile and propane conversion as a function of contact time. Reaction conditions: (a) 723 K, C3H8:CO2 = 1:120, 1000 mL/gcat/h; (b) 20 kPa C3H8, 2570 kPa CO2, 410 kPa Ar, 1000 mL/gcat/h; (c) 723 K, 20 kPa C3H8, 0-2570 kPa CO2, 1000 mL/gcat/h, Ar as balance gas; (d) 723 K, 20 kPa C3H8, 2570 kPa CO2, 410 kPa Ar. Note that olefins represent C2=-C4=, alkanes represent C1-C40 (apart from C3H8), and others represent C5+ hydrocarbon excluding aromatics.

Fig. 4. Mechanistic investigation of the CO2-C3H8 co-conversion over H-ZSM-5-25. (a) Correlation between contact time and light hydrocarbon formation. (b) Effect of contact time on residual surface species and aromatic selectivity. (c) Operando dual-beam FTIR spectra of propane conversion under different gas atmospheres. (d) 13C isotope distribution in aromatic products. (e) 13C liquid-state NMR spectra of products derived from the coupling reaction between 13CO2 and C3H8. Reaction conditions: (a,b) 723 K, 20 kPa C3H8, 2570 kPa CO2, 410 kPa Ar; (c) 423-723 K, 1.0 MPa, C3H8:CO2 = 1:99 (up), C3H8 : Ar = 1:99 (down), 40000 mL/gcat/h; (d,e) 723 K, 1.5 kPa C3H8, 500 kPa CO2, 798.5 kPa Ar, 1300 mL/gcat/h.

Fig. 5. Schematic illustration of the CO2-C3H8 coupling aromatization over H-ZSM-5.

参考文献

[1]	B. M. Tackett, E. Gomez, J. G. Chen, Nat. Catal., 2019, 2, 381-386.
[2]	T. Sakakura, J.-C. Choi, H. Yasuda, Chem. Rev., 2007, 107, 2365-2387.
[3]	C. Hepburn, E. Adlen, J. Beddington, E. A. Carter, S. Fuss, N. Mac Dowell, J. C. Minx, P. Smith, C. K. Williams, Nature, 2019, 575, 87-97.
[4]	G. Tian, X. Liang, H. Xiong, C. Zhang, F. Wei, EES Catal., 2023, 1, 677-686.
[5]	D. Wang, Z. Xie, M. D. Porosoff, J. G. Chen, Chem, 2021, 7, 2277-2311.
[6]	R.-P. Ye, J. Ding, W. Gong, M. D. Argyle, Q. Zhong, Y. Wang, C. K. Russell, Z. Xu, A. G. Russell, Q. Li, M. Fan, Y.-G. Yao, Nat. Commun., 2019, 10, 5698.
[7]	S. Dabral, T. Schaub, Adv. Synth. Catal., 2019, 361, 223-246.
[8]	A. Behr, Chem. Ing. Tech., 1985, 57, 893-903.
[9]	S. Fukuoka, M. Kawamura, K. Komiya, M. Tojo, H. Hachiya, K. Hasegawa, M. Aminaka, H. Okamoto, I. Fukawa, S. Konno, Green Chem., 2003, 5, 497-507.
[10]	M. A. Pacheco, C. L. Marshall, Energy Fuels, 1997, 11, 2-29.
[11]	Y. Wang, X. Gao, M. Wu, N. Tsubaki, EcoMat, 2021, 3, e12080.
[12]	A. Ramirez, A. Dutta Chowdhury, A. Dokania, P. Cnudde, M. Caglayan, I. Yarulina, E. Abou-Hamad, L. Gevers, S. Ould-Chikh, K. De Wispelaere, V. van Speybroeck, J. Gascon, ACS Catal., 2019, 9, 6320-6334.
[13]	S. Wang, L. Zhang, P. Wang, X. Liu, Y. Chen, Z. Qin, M. Dong, J. Wang, L. He, U. Olsbye, W. Fan, Chem, 2022, 8, 1376-1394.
[14]	J. Zuo, W. Chen, J. Liu, X. Duan, L. Ye, Y. Yuan, Sci. Adv., 2020, 6, eaba5433.
[15]	X. Niu, X. Nie, C. Yang, J. G. Chen, Catal. Sci. Technol., 2020, 10, 1881-1888.
[16]	S.-K. Ihm, Y.-K. Park, S.-W. Lee, Appl. Organometal. Chem., 2000, 14, 778-782.
[17]	J.-B. Zhang, H.-H. He, H.-F. Tian, J.-K. Liao, F. Zha, X.-J. Guo, X. Tang, Y. Chang, Can. J. Chem., 2021, 99, 619-627.
[18]	H. Fan, X. Nie, C. Song, X. Guo, Ind. Eng. Chem. Res., 2022, 61, 10483-10495.
[19]	J. Guo, H. Lou, H. Zhao, L. Zheng, X. Zheng, J. Mol. Catal. A, 2005, 239, 222-227.
[20]	K. Bu, Y. Kang, Y. Li, Y. Zhang, Y. Tang, Z. Huang, W. Shen, H. Xu, Appl. Catal. B, 2024, 343, 123528.
[21]	C. Wei, W. Zhang, K. Yang, X. Bai, S. Xu, J. Li, Z. Liu, Chin. J. Catal., 2023, 47, 138-149.
[22]	X. Ren, Z.-P. Hu, J. Han, Y. Wei, Z. Liu, Front. Chem. Sci. Eng., 2023, 17, 1801-1808.
[23]	X. Fang, B. Li, H. Liu, M. Xie, Z. Chen, L. Yang, J. Han, W. Zhu, Z. Liu, Chem Catal., 2023, 3, 100689.
[24]	M. Guisnet, S. N. Gnep, D. Aittaleb, J. Y. Doyemet, Appl. Cata. A, 1992, 87, 255-270.
[25]	Y. Song, Z.-P. Hu, H. Feng, E. Chen, L. Lv, Y. Wu, Z. Liu, Y. Jiang, X. Su, F. Xu, M. Zhu, J. Han, Y. Wei, S. Mintova, Z. Liu,, J. Energy Chem., 2024, 97, 513-519.
[26]	J. Liu, J. Wang, W. Zhou, C. Miao, G. Xiong, Q. Xin, H. Guo, Chin. J. Catal., 2017, 38, 13-19.
[27]	Q. Zhang, J. Yu, A. Corma, Adv. Mater., 2020, 32, 2002927.
[28]	L. Lin, J. Liu, X. Zhang, J. Wang, C. Liu, G. Xiong, H. Guo, Ind. Eng. Chem. Res., 2020, 59, 16146-16160.
[29]	J. A. van Bokhoven, M. Tromp, D. C. Koningsberger, J. T. Miller, J. A. Z. Pieterse, J. A. Lercher, B. A. Williams, H. H. Kung, J. Catal., 2001, 202, 129-140.
[30]	I. I. Ivanova, E. B. Pomakhina, A. I. Rebrov, E. G. Derouane, Top. Catal., 1998, 6, 49-59.
[31]	E. D. Hernandez, F. C. Jentoft, ACS Catal., 2020, 10, 5764-5782.
[32]	J.-Y. Zhou, G.-D. Lu, S.-H. Wu, Synth. Commun., 1992, 22, 481-487.
[33]	X. Fang, H. Liu, Z. Chen, Z. Liu, X. Ding, Y. Ni, W. Zhu, Z. Liu,, Angew. Chem. Int. Ed., 2022, 61, e202114953.
[34]	Z. Zhou, H. Liu, Y. Ni, F. Wen, Z. Chen, W. Zhu, Z. Liu, J. Catal., 2021, 396, 360-373.
[35]	C. Lievens, D. Mourant, M. He, R. Gunawan, X. Li, C.-Z. Li, Fuel, 2011, 90, 3417-3423.
[36]	Z. Chen, Y. Ni, Y. Zhi, F. Wen, Z. Zhou, Y. Wei, W. Zhu, Z. Liu, Angew. Chem. Int. Ed., 2018, 57, 12549-12553.
[37]	C. Wei, J. Li, K. Yang, Q. Yu, S. Zeng, Z. Liu, Chem Catal., 2021, 1, 1273-1290.

酸性分子筛上CO₂与丙烷制芳烃中碳原子高效利用

Efficient carbon integration of CO₂ in propane aromatization over acidic zeolites

RichHTML

PDF

Supporting Information

可视化

摘要/Abstract

引用本文

使用本文

扫码分享

图/表 5

参考文献

相关文章 15

编辑推荐

Metrics

[1]	姜建伟, Vinothkumar Ganesan, 崔仁洛, 申庭澈, 尹城镐, 朴纪映. 酰基钴基催化剂用于高活性高稳定性环氧化物羰基化制备β-内酯[J]. 催化学报, 2025, 68(1): 336-344.
[2]	孙旭科, 刘荣升, 范改丽, 刘昱含, 叶芳秀, 于政锡, 刘中民. Zn/ZSM-5催化剂中Zn物种与CO₂和正丁烷耦合反应间相关性研究[J]. 催化学报, 2024, 61(6): 154-163.
[3]	干雅梅, 柴甜甜, 张健, 高聪, 宋伟, 吴静, 刘立明, 陈修来. 利用光驱动的生物杂合系统实现CO₂转化生产化学品[J]. 催化学报, 2024, 60(5): 294-303.
[4]	郑颖滨, 张新宝, 李俊杰, 安杰, 徐龙伢, 李秀杰, 朱向学. 负载型多相金属催化剂用于二氧化碳辅助低碳烷烃氧化脱氢反应[J]. 催化学报, 2024, 65(10): 40-69.
[5]	Teera Chantarojsiri, Tassaneewan Soisuwan, Pornwimon Kongkiatkrai. 羧酸盐的绿色合成: 用于有机卤化物和烯烃电羧基化反应电极上的反应及其机理[J]. 催化学报, 2022, 43(12): 3046-3061.
[6]	田井清, 李浩成, 曾馨, 王子春, 黄骏, 赵晨. 限域Ni/MCM-41催化抗积碳和金属烧结的甲烷干重整反应[J]. 催化学报, 2019, 40(9): 1395-1404.
[7]	曹雪娟, 刘淮, 魏珺楠, 唐兴, 曾宪海, 孙勇, 雷霆宙, 赵耿, 林鹿. CuO_x-CaCO₃催化剂高效催化生物质乙酰丙酸甲酯制备γ-戊内酯[J]. 催化学报, 2019, 40(2): 192-203.
[8]	王豪杰, 陈春, 张海民, 汪国忠, 赵惠军. 乙酰丙酸选择性加氢合成γ-戊内酯中高效和可循环使用的Ni₃Fe NPs@C双金属催化剂[J]. 催化学报, 2018, 39(10): 1599-1607.
[9]	Lorenzo Landenna, Alberto Villa, Rodolfo Zanella, Claudio Evangelisti, Laura Prati. Au-Ir催化剂用于生物质衍生物加氢[J]. 催化学报, 2016, 37(10): 1771-1775.
[10]	龙向东, 孙鹏, 李泽龙, 郎睿, 夏春谷, 李福伟. 水滑石基磁性Co/Al₂O₃催化剂在乙酰丙酸加氢制备γ-戊内酯反应中的应用[J]. 催化学报, 2015, 36(9): 1512-1518.
[11]	李娴, 郑嘉旻, 杨新丽, 戴维林, 范康年. 高活性Au/SnO₂催化剂的制备及其在1,4-丁二醇氧化制γ-丁内酯反应中的催化应用[J]. 催化学报, 2013, 34(5): 1013-1019.
[12]	杜贤龙, 刘永梅, 王建强, 曹勇, 范康年. 碳纳米管担载纳米Ir催化生物质基乙酰丙酸合成γ-戊内酯[J]. 催化学报, 2013, 34(5): 993-1001.
[13]	康自华, 刘海鸥, 张雄福. 杂原子 Sn-β 分子筛的脱铝补位两步法制备、表征及其催化环己酮 Baeyer-Villiger 氧化性能[J]. 催化学报, 2012, 33(5): 898-904.
[14]	杨志旺, 马振宏, 牛棱渊, 马国富, 马恒昌, 雷自强. SBA-15 负载硅钨酸催化环己酮 Baeyer-Villiger 氧化[J]. 催化学报, 2011, 32(3): 463-467.
[15]	杨燕萍, 张因, 高春光, 赵永祥. TiO_x(x < 2) 表面修饰 Ni/TiO₂-SiO₂ 催化顺酐液相选择加氢合成 γ-丁内酯[J]. 催化学报, 2011, 32(11): 1768-1774.