SAPO-14催化的甲醇制丙烯反应: 反应机理与失活

doi:10.1016/S1872-2067(22)64123-8

催化学报 ›› 2022, Vol. 43 ›› Issue (8): 2259-2269.DOI: 10.1016/S1872-2067(22)64123-8

• 论文 • 上一篇

SAPO-14催化的甲醇制丙烯反应: 反应机理与失活

王冶^a^,^b, 韩晶峰^a, 王男^a^,^c, 李冰^a, 杨淼^a^,^*(), 吴一墨^a^,^c, 江子潇^a^,^c, 魏迎旭^a, 田鹏^a, 刘中民^a^,^#()

^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郑州大学化学学院, 绿色催化中心, 河南郑州450001
^c中国科学院大学, 北京100049

收稿日期:2022-02-28 接受日期:2022-04-22 出版日期:2022-08-18 发布日期:2022-06-20
通讯作者: 杨淼,刘中民
基金资助:
国家自然科学基金(22171259);国家自然科学基金(21991090);国家自然科学基金(21991091);国家自然科学基金(22172166);中国科学院大连化学物理研究所创新研究基金(DICP I201909);中国科学院青年创新促进会基金(2021182)

Conversion of methanol to propylene over SAPO-14: Reaction mechanism and deactivation

Ye Wang^a^,^b, Jingfeng Han^a, Nan Wang^a^,^c, Bing Li^a, Miao Yang^a^,^*(), Yimo Wu^a^,^c, Zixiao Jiang^a^,^c, Yingxu Wei^a, Peng Tian^a, Zhongmin Liu^a^,^#()

^aNational Engineering Research Center of Lower-Carbon Catalysis Technology, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
^bGreen Catalysis Centre, College of Chemistry, Zhengzhou University, Zhengzhou 450001, Henan, China
^cUniversity of Chinese Academy of Sciences, Beijing 100049, China

Received:2022-02-28 Accepted:2022-04-22 Online:2022-08-18 Published:2022-06-20
Contact: Miao Yang, Zhongmin Liu
Supported by:
National Natural Science Foundation of China(22171259);National Natural Science Foundation of China(21991090);National Natural Science Foundation of China(21991091);National Natural Science Foundation of China(22172166);Innovation Research Foundation of Dalian Institute of Chemical Physics, Chinese Academy of Sciences(DICP I201909);Youth Innovation Promotion Association CAS(2021182)

摘要/Abstract

摘要：

甲醇制烯烃(MTO)反应作为重要的非石油路线生产低碳烯烃途径, 其乙烯加丙烯的选择性可高达80%以上. 然而, 由于乙烯和丙烯的收率接近, 如何调控单乙烯或丙烯的选择性以满足市场波动需求仍充满挑战. 小孔SAPO-14分子筛是本课题组最近报道的一种具有AFN拓扑结构的新型MTO催化剂, 其单程的丙烯选择性可超过70%, 丙烯/乙烯比为4-8. 研究SAPO-14分子筛的MTO催化机制、揭示其高丙烯选择性背后的原因, 有助于深入理解分子筛结构和物性与MTO催化性能之间的关联规律, 还将为开发新型甲醇制丙烯(MTP)催化剂提供新思路.

本文采用秒级采样固定床反应器对催化反应的选择性进行了监测, 结合原位红外光谱、原位紫外拉曼光谱和¹²C/¹³C甲醇切换实验研究反应路径演变. 还通过多种非原位表征手段考察了SAPO-14的失活过程, 对甲醇碳资源利用效率进行评估, 为设计和开发特色MTP催化剂提供理论依据.

产物分布变化, 特别是低活性期的变化可以反映出甲醇转化反应路径的一些重要信息. 从秒级采样固定床的反应结果可以看出, SAPO-14催化的MTO反应初期主要产物是甲烷. 随着自催化反应的启动, 甲烷选择性开始下降, 丙烯的选择性迅速上升, 达到70%以上并保持到反应结束. 反应前40 s, 乙烯与丙烯的选择性变化趋势相近, 40 s后乙烯选择性迅速降低、与丙烯选择性变化呈相反趋势. 相比之下, SAPO-18催化MTO反应时, 丙烯的选择性一直高于乙烯. 表明SAPO-14上的催化反应在40 s附近经历了巨大的转变. 而SAPO-18的反应路径相对平稳. 由于SAPO-14反应空间有限, 芳烃循环在自催化启动过程中受到了严重的限制, 因此乙烯的选择性呈现先增加后降低的趋势. 进一步通过原位紫外拉曼光谱和¹²C/¹³C甲醇同位素切换实验研究MTO反应细节. 当¹³C甲醇切换成¹²C甲醇后, 紫外拉曼光谱中只出现烯烃物种的信号, 证实了烯烃循环在SAPO-14的MTO反应过程中的主导性. 上述结果表明SAPO-14上的MTO反应路径经历了从双循环到烯烃循环为主的演变.

本文还利用多种表征手段研究了SAPO-14催化剂的失活行为. 氮气物理吸附结果表明, 随着积碳量的增加, SAPO-14催化剂的微孔孔容逐渐下降. 反应前6 min的孔容下降最快, 这说明反应初期形成的物种即可快速堵塞SAPO-14的孔道. 利用紫外可见光谱、气-质谱联用仪和傅里叶变换离子回旋共振质谱鉴定了反应中形成的积碳物种. 结果表明, 早期形成的多甲基苯物种即是失活物种, 另外还有可能形成跨笼积碳物种, 导致催化剂失活. 最后, 对甲醇的碳资源利用效率进行了评估, SAPO-14的碳资源利用效率为74%, 虽然低于SAPO-34的, 但是由于其较高的丙烯选择性, SAPO-14分子筛仍然是一个优秀的MTP催化剂.

烯烃循环和芳烃循环是否可以独立运转是MTO反应机理研究中一个有趣的问题. 如果可以最大限度地提升烯烃循环, 则有机会进一步提升丙烯选择性. SAPO-14分子筛的拓扑结构和酸性质已控制在可以催化MTO反应的临界点. 通过孔、笼择形, 可以有效地抑制芳烃循环, 实现丙烯的超高选择性. 但是芳烃物种的形成仍不可避免, 从而导致催化剂快速失活. 合成纳米级或多级孔SAPO-14, 从而改善其传质效率, 提升容碳能力, 将有助于制得更优的MTP分子筛催化剂.

关键词: 甲醇制丙烯, SAPO-14分子筛, 紫外拉曼光谱, 双循环机理, 失活

Abstract:

Methanol to olefins (MTO) reaction as an important non-oil route to produce light olefins has been industrialized, and received over 80% ethylene plus propylene selectivity. However, to achieve high single ethylene or propylene selectivity towards the fluctuated market demand is still full of challenge. Small-pore SAPO-14 molecular sieve is a rare MTO catalyst exhibiting extra-high propylene selectivity. It provides us a valuable clue for further understanding of the relationship between molecular sieve structure and MTO catalytic performance. In this work, a seconds-level sampling fixed-bed reactor was used to capture real-time product distributions, which help to achieve more selectivity data in response to very short catalytic life of SAPO-14. Changes in product distribution, especially during the low activity stage, reflect valuable information on the reaction pathway. Combined with in situ diffuse reflectance infrared Fourier-transform spectroscopy, in situ ultraviolet Raman measurements and ¹²C/¹³C isotopic switch experiments, a reaction pathway evolution from dual cycle to olefins-based cycle dominant was revealed. In addition, the deactivation behaviors of SAPO-14 were also investigated, which revealed that polymethylbenzenes have been the deactivated species in such a situation. This work provides helpful hints on the development of characteristic methanol to propylene (MTP) catalysts.

Key words: Methanol to propylene, SAPO-14 molecular sieve, UV Raman spectroscopy, Dual-cycle mechanism, Deactivation

王冶, 韩晶峰, 王男, 李冰, 杨淼, 吴一墨, 江子潇, 魏迎旭, 田鹏, 刘中民. SAPO-14催化的甲醇制丙烯反应: 反应机理与失活[J]. 催化学报, 2022, 43(8): 2259-2269.

Ye Wang, Jingfeng Han, Nan Wang, Bing Li, Miao Yang, Yimo Wu, Zixiao Jiang, Yingxu Wei, Peng Tian, Zhongmin Liu. Conversion of methanol to propylene over SAPO-14: Reaction mechanism and deactivation[J]. Chinese Journal of Catalysis, 2022, 43(8): 2259-2269.

×
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(22)64123-8

https://www.cjcatal.com/CN/Y2022/V43/I8/2259

图/表 6

Fig. 1. The views and sizes of cage-defining rings (red colored) for AEI, LEV, ERI, and AFN topologies.

Fig. 2. Seconds-level MTO product distribution and conversion and selectivity profiles of propylene, ethylene and propylene/ethylene ratios over SAPO-14 (a,b) and SAPO-18 (c,d). Reaction condition: 673 K, weight hourly space velocity: 0.5 h-1, methanol partial pressure: 5 kPa.

Fig. 3. In situ diffuse reflectance infrared Fourier-transform spectra recorded during methanol conversion over SAPO-14 at 673 K. The spectra were recorded from 0 to 20 min.

Fig. 4. Time-resolved UV Raman spectra, the selected typical UV Raman spectra and their peak fittings of SAPO-14 catalyst in 12C-methanol conversion (a?c), and 13C-methanol conversion followed by 12C-methanol switch at a TOS of 6 min (d?f). Reaction condition: 673 K; methanol partial pressure: 5 kPa; ultraviolet excitation line: 244 nm.

Fig. 5. The coke amount as a function of time on stream (a). The micropore volume (blue line) and Brunauer-Emmett-Teller (BET) surface area (black line) of spent SAPO-14 catalysts as functions of coke amount (b).

Fig. 6. Ultraviolet-visible spectra of SAPO-14 at different reaction times (a). Gas chromatography-mass spectrometry chromatograms of organic species in SAPO-14 at different reaction times (b). Matrix-assisted laser desorption/ionization Fourier-transform ion cyclotron resonance mass spectra for extracts obtained from SAPO-14 and the deduced possible molecular structure of polycyclic aromatic hydrocarbons (c). The indicated molecular structures are representative examples of possible structures. Reaction conditions: 673 K for 37 min; weight hourly space velocity: 0.5 h?1.

参考文献

[1]	M. Stöcker, Microporous Mesoporous Mater., 1999, 29, 3-48.
[2]	J. Q. Chen, A. Bozzano, B. Glover, T. Fuglerud, S. Kvisle, Catal. Today, 2005, 106, 103-107.
[3]	I. Yarulina, A. D. Chowdhury, F. Meirer, B. M. Weckhuysen, J. Gascon, Nat. Catal., 2018, 1, 398-411.
[4]	P. Tian, Y. X. Wei, M. Ye, Z. M. Liu, ACS Catal., 2015, 5, 1922-1938.
[5]	M. Yang, D. Fan, Y. X. Wei, P. Tian, Z. M. Liu, Adv. Mater., 2019, 31, 192181.
[6]	B. P. C. Hereijgers, F. Bleken, M. H. Nilsen, S. Svelle, K. -P. Lillerud, M. Bjorgen, B. M. Weckhuysen, U. Olsbye, J. Catal., 2009, 264, 77-87.
[7]	S. Teketel, U. Olsbye, K. -P. Lillerud, P. Beato, S. Svelle, Microporous Mesoporous Mater., 2010, 136, 33-41.
[8]	U. Olsbye, S. Svelle, M. Bjørgen, P. Beato, T. V. W. Janssens, F. Joensen, S. Bordiga, K. P. Lillerud, Angew. Chem., Int. Ed., 2012, 51, 5810-5831.
[9]	J. Z. Li, Y. X. Wei, J. R. Chen, S. T. Xu, P. Tian, X. F. Yang, B. Li, J. B. Wang, Z. M. Liu, ACS Catal., 2015, 5, 661-665.
[10]	P. Ferri, C. G. Li, C. Paris, A. Vidal-Moya, M. Moliner, M. Boronat, A. Corma, ACS Catal., 2019, 9, 11542-11551.
[11]	J. W. Zhong, J. F. Han, Y. X. Wei, Z. M. Liu, J. Catal., 2021, 396, 23-31.
[12]	S. Wang, Z. K. Li, Z. F. Qin, M. Dong, J. F. Li, W. B. Fan, J. G. Wang, Chin. J. Catal., 2021, 42, 1126-1136.
[13]	J. R. Chen, J. Z. Li, C. Y. Yuan, S. T. Xu, Y. X. Wei, Q. Y. Wang, Y. Zhou, J. B. Wang, M. Z. Zhang, Y. L. He, S. L. Xu, Z. M. Liu, Catal. Sci. Technol., 2014, 4, 3268-3277.
[14]	I. Pinilla-Herrero, U. Olsbye, C. Marquez-Alvarez, E. Sastre, J. Catal., 2017, 352, 191-207.
[15]	S. S. Gao, Z. Q. Liu, S. T. Xu, A. M. Zheng, P. F. Wu, B. Li, X. S. Yuan, Y. X. Wei, Z. M. Liu, J. Catal., 2019, 377, 51-62.
[16]	J. Z. Li, Y. X. Wei, J. R. Chen, P. Tian, X. Su, S. T. Xu, Y. Qi, Q. Y. Wang, Y. Zhou, Y. L. He, Z. M. Liu, J. Am. Chem. Soc., 2012, 134, 836-839.
[17]	W. N. Zhang, J. R. Chen, S. T. Xu, Y. Y. Chu, Y. X. Wei, Y. C. Zhi, J. D. Huang, A. M. Zheng, X. Q. Wu, X. J. Meng, F. S. Xiao, F. Deng, Z. M. Liu, ACS Catal., 2015, 8, 10950-10963.
[18]	J. H. Kang, F. H. Alshafei, S. I. Zones, M. E. Davis, ACS Catal. 2019, 9, 6012-6019.
[19]	M. A. Deimund, J. E. Schmidt, M. E. Davis, Top. Catal., 2015, 58, 416-423.
[20]	M. Yang, B. Li, M. B. Gao, S. F. Lin, Y. Wang, S. T. Xu, X. B. Zhao, P. Guo, Y. X. Wei, M. Ye, P. Tian, Z. M. Liu, ACS Catal., 2020, 10, 3741-3749.
[21]	N. Wang, Y. C. Zhi, Y. X. Wei, W. N. Zhang, Z. Q. Liu, J. D. Huang, T. T. Sun, S. T. Xu, S. F. Lin, Y. L. He, A. M. Zheng, Z. M. Liu, Nat. Commun., 2020, 11, 1079-1091.
[22]	J. W. Zhong, J. F. Han, Y. X. Wei, S. T. Xu, T. T. Sun, S. Zeng, X. W. Guo, C. S. Song, Z. M. Liu, Chin. J. Catal., 2019, 40, 477-485.
[23]	W. P. Zhao, B. Z. Zhang, G. R. Wang, H. C. Guo, J. Energy Chem., 2014, 23, 201-206.
[24]	L. Qi, Y. X. Wei, L. Xu, Z. M. Liu, ACS Catal., 2015, 5, 3973-3982.
[25]	C. M. Wang, Y. D. Wang, Z. K. Xie, Chin. J. Catal., 2018, 39, 1272-1279.
[26]	S. M. Campbell, X.-Z. Jiang, R. F. Howe, Microporous Mesoporous Mater., 1999, 29, 91-108.
[27]	T. R. Forester, R. F. Howe, J. Am. Chem. Soc., 1987, 109, 5076-5082.
[28]	X. Q. Wu, S. T. Xu, Y. X. Wei, W. N. Zhang, J. D. Huang, S. L. Xu, Y. L. He, S. F. Lin, T. T. Sun, Z. M. Liu, ACS Catal., 2018, 8, 7356-7361.
[29]	I. B. Minova, S. K. Matam, A. Greenaway, C. R. A. Catlow, M. D. Frogley, G. Cinque, P. A. Wright, R. F. Howe, ACS Catal., 2019, 9, 6564-6570.
[30]	S. F. Lin, Y. C. Zhi, W. Chen, H. Li, W. N. Zhang, C. Y. Lou, X. Q. Wu, S. Zeng, S. T. Xu, J. P. Xiao, A. M. Zheng, Y. X. Wei, Z. M. Liu, J. Am. Chem. Soc., 2021, 143, 12038-12052.
[31]	S. S. Shao, H. Y. Zhang, R. Xiao, X. H. Li, Y. X. Cai, J. Anal. Appl. Pyrolysis, 2017, 127, 258-268.
[32]	D. S. Wragg, R. E. Johnsen, M. Balasundaram, P. Norby, H,. Fjellvå. A. Grønvold, T. Fuglerud, J. Hafizovic, Ø. B. Vistad, D. Akporiaye, J. Catal., 2009, 268, 290-296.
[33]	D. Rojo-Gama, M. Signorile, F. Bonino, S. Bordiga, U. Olsbye, K.P. Lillerud, P. Beato, S. Svelle, J. Catal., 2017, 351, 33-48.
[34]	M. Signorile, D. R. Gama, F. Bonino, S. Svelle, P. Beato, S. Bordiga, Catal. Today, 2019, 336, 203-209.
[35]	C. L. Angell, J. Phys. Chem., 1973, 77, 222-227.
[36]	N. Sheppard, D. M. Simpson, Q. Rev. Chem. Soc., 1952, 6, 1-33.
[37]	H. Y. An, F. Zhang, Z. H. Guan, X. B. Liu, F. T. Fan, C. Li, ACS Catal., 2018, 8, 9207-9215.
[38]	S. S. Gao, S. T. Xu, Y. X. Wei, Q. L. Qiao, Z. C. Xu, X. Q. Wu, M. Z. Zhang, Y. L. He, S. L. Xu, Z. M. Liu, J. Catal., 2018, 367, 306-314.
[39]	K. Y. Lee, H. -J. Chae, S. -Y. Jeong, G. Seo, Appl. Catal., A, 2009, 369, 60-66.
[40]	W. L. Dai, G. J. Wu, L. D. Li, N. J. Guan, M. Hunger, ACS Catal., 2013, 3, 588-596.
[41]	L. Pinard, S. Hamieh, C. Canaff, F. F. Madeira, I. Batonneau-Gener, S. Maury, O. Delpoux, K. B. Tayeb, Y. Pouilloux, H. Vezin, J. Catal., 2013, 299, 284-297.
[42]	N. Chaouati, A. Soualah, M. Chater, M. Tarighi, L. Pinard, J. Catal., 2016, 344, 354-364.
[42]	Y. X. Wei, C. Y. Yuan, J. Z. Li, S. T. Xu, Y. Zhou, J. R. Chen, Q. Y. Wang, L. Xu, Y. Qi, Q. Zhang, Z. M. Liu, ChemSusChem, 2012, 5, 906-912.

SAPO-14催化的甲醇制丙烯反应: 反应机理与失活

Conversion of methanol to propylene over SAPO-14: Reaction mechanism and deactivation

RichHTML

PDF

Supporting Information

可视化

摘要/Abstract

引用本文

使用本文

扫码分享

图/表 6

参考文献

相关文章 15

编辑推荐

Metrics

[1]	Enara Fernandez, Laura Santamaria, Irati García, Maider Amutio, Maite Artetxe, Gartzen Lopez, Javier Bilbao, Martin Olazar. 不同固定床位置生物质热解挥发物蒸汽催化重整反应中焦炭的形成和演化[J]. 催化学报, 2023, 48(5): 101-116.
[2]	林杉帆, 郅玉春, 张文娜, 袁小帅, 张成伟, 叶茂, 徐舒涛, 魏迎旭, 刘中民. 氢转移反应对分子筛催化甲醇和二甲醚动态自催化反应历程的贡献: 深入理解甲醛的生成机理和作用机制[J]. 催化学报, 2023, 46(3): 11-27.
[3]	王梦茹, 王奕, 牟效玲, 林荣和, 丁云杰. 1,3-丁二烯选择性加氢催化剂的设计策略以及构效关系[J]. 催化学报, 2022, 43(4): 1017-1041.
[4]	吕宏伟, 国文馨, 陈敏, 周煌, 吴宇恩. 热稳定单原子催化剂的理性构筑: 从原子级结构到实际应用[J]. 催化学报, 2022, 43(1): 71-91.
[5]	任栎, 王博文, 陆琨, 彭如斯, 关业军, 蒋金刚, 徐浩, 吴鹏. 脱铝丝光分子筛应用于MTP反应: Al的落位和晶体形貌的影响[J]. 催化学报, 2021, 42(7): 1147-1159.
[6]	雷念, 苗治理, 刘菲, 王华, 潘晓丽, 王爱琴, 张涛. 甘油氢解反应中Pt/WO₃/Al₂O₃催化剂的失活行为[J]. 催化学报, 2020, 41(8): 1261-1267.
[7]	周吉彬, 赵建平, 张今令, 张涛, 叶茂, 刘中民. 积碳失活催化剂的再生[J]. 催化学报, 2020, 41(7): 1048-1061.
[8]	于东霓, 戴卫理, 武光军, 关乃佳, 李兰冬. 分子筛稳定的Cu物种催化乙醇脱氢制乙醛[J]. 催化学报, 2019, 40(9): 1375-1384.
[9]	张娟, 褚月英, 刘小龙, 徐好, 冯兆池, 孟祥举, 肖丰收. 紫外拉曼光谱研究FAU到CHA和MFI分子筛的转晶过程[J]. 催化学报, 2019, 40(12): 1854-1859.
[10]	赵学斌, 洪杨, 王林英, 樊栋, 闫娜娜, 刘晓娜, 田鹏, 郭新闻, 刘中民. 高硅ZSM-5原粉的外表面改性及其在甲醇制丙烯反应中的应用[J]. 催化学报, 2018, 39(8): 1418-1426.
[11]	常化振, 史传宁, 李明冠, 张涛, 王驰中, 江莉龙, 王秀云. 不同阳离子(NH₄⁺,Na⁺,K⁺,Ca²⁺)溴化物对商用SCR催化剂化学中毒影响机制研究[J]. 催化学报, 2018, 39(4): 710-717.
[12]	张默之, 徐舒涛, 魏迎旭, 李金哲, 王金棒, 张雯娜, 高树树, 刘中民. 调变MTO反应中双循环机理的比重:ZSM-5分子筛上不同接触时间的作用[J]. 催化学报, 2016, 37(8): 1413-1422.
[13]	M. Khanmohammadi, Sh. Amani, A. Bagheri Garmarudi, A. Niaei. 甲醇制丙烯:最重要的催化剂及其性能[J]. 催化学报, 2016, 37(3): 325-339.
[14]	Solomon Legese Hailu, Balachandran Unni Nair, Mesfin Redi-Abshiro, Isabel Diaz, Rathinam Aravindhan, Merid Tessema. 封装Fe(III),Ni(II)和Cu(II)的N,N'-双邻羟苯亚甲基-1,2-苯二胺络合物的Y分子筛催化4-氯-3-甲基苯酚氧化反应[J]. 催化学报, 2016, 37(1): 135-145.
[15]	陈昶名, 吴晓东, 尉文超, 高宇曦, 翁端, 石磊, 耿春雷. 氧化钛负载脱硝催化剂的碱中毒过程: 氧化钒的保留和氧化钨的牺牲[J]. 催化学报, 2015, 36(8): 1287-1294.