Control of aluminum distribution in ZSM-5 zeolite for enhancement of its catalytic performance for propane aromatization

Abstract

Regulation of aluminum distribution in zeolite framework is an effective method for improving its catalytic performance for propane aromatization. Herein, we found that recrystallization and post-realuminization of ZSM-5 cannot only create hollow structures to enhance the diffusion ability, but also adjust the content and position of paired aluminum species in its framework. Various characterizations results confirmed that increase of paired aluminum content and inducement of more aluminum atoms sited in the intersection cavity are beneficial to the formation of aromatic products in propane aromatization. As a result, the hollow-structured ZSM-5 zeolite with more paired aluminum (H-200-hollow) showed higher propane conversion and aromatics selectivity than other samples at the same conditions. The catalytic performance of H-200-hollow can be further improved by ion-exchanging with a small amount of Ga(III) species. The propane conversion and aromatics selectivity of Ga-200-hollow reached as high as 95% and 70%, respectively, at 540 °C and 1 atm.

Key words： propane aromatization; zeolite; aluminum distribution; recrystallization and post-realuminization

Competing interests

The authors declare that they have no competing interests.

Acknowledgements

This research was supported by the National Key R & D Program of China (Grant No. 2023YFB4103700), National Natural Science Foundation of China (Grant Nos. U1910203; 21991090; 21991092; 22322208; 22272195; U22A20431), Natural Science Foundation of Shanxi Province of China (Grant No. 202203021224009), Innovation foundation of Institute of Coal Chemistry, Chinese Academy of Sciences (Grant No. SCJC-DT-2023-06); Youth Innovation Promotion Association CAS (Grant No. 2021172).

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://doi.org/10.1007/s11705-024-2439-8 and is accessible for authorized users.

References

1 Biscardi J A , Iglesia E . Structure and function of metal cations in light alkane reactions catalyzed by modified H-ZSM-5. Catalysis Today, 1996, 31(3–4): 207–231

2 RodriguesV OFaroJúnior A C. On catalyst activation and reaction mechanisms in propane aromatization on Ga/H-ZSM-5 catalysts. Applied Catalysis A, General, 2012, 435–436: 68–77

3 Choudhary V R , Devadas P , Banerjee S , Kinage A K . Aromatization of dilute ethylene over Ga-modified ZSM-5 type zeolite catalysts. Microporous and Mesoporous Materials, 2001, 47(2–3): 253–267

4 Phadke N M , Mansoor E , Bondil M , Head-Gordon M , Bell A T . Mechanism and kinetics of propane dehydrogenation and cracking over Ga/H-MFI prepared via vapor-phase exchange of H-MFI with GaCl₃. Journal of the American Chemical Society, 2018, 141(4): 1614–1627

5 Song C , Li X J , Zhu X X , Liu S L , Chen F C , Liu F , Xu L Y . Influence of the state of Zn species over Zn-ZSM-5/ZSM-11 on the coupling effects of cofeeding n-butane with methanol. Applied Catalysis A: General, 2016, 519: 48–55

6 BaerlocherCMcCuskerL B. Database of Zeolite Structures, 2013.

7 Xing M J , Zhang L , Cao J , Han Y L , Wang F , Hao K , Huang L H , Tao Z C , Wen X D , Yang Y . . Impact of the aluminum species state on Al pairs formation in the ZSM-5 framework. Microporous and Mesoporous Materials, 2022, 334: 111769

8 Liang T Y , Chen J L , Qin Z F , Li J F , Wang P F , Wang S , Wang G F , Dong M , Fan W B , Wang J G . Conversion of methanol to olefins over H-ZSM-5 zeolite: reaction pathway is related to the framework aluminum siting. ACS Catalysis, 2016, 6(11): 7311–7325

9 Biligetu T , Wang Y , Nishitoba T , Otomo R , Park S , Mochizuki H , Kondo J N , Tatsumi T , Yokoi T . Al distribution and catalytic performance of ZSM-5 zeolites synthesized with various alcohols. Journal of Catalysis, 2017, 353: 1–10

10 Yokoi T , Mizuno S , Imai H , Tatsumi T . Synthesis and structural characterization of Al-containing interlayer-expanded-MWW zeolite with high catalytic performance. Dalton Transactions, 2014, 43(27): 10584–10592

11 Li C G , Vidal-Moya A , Miguel P J , Dedecek J K , Boronat M , Corma A . Selective introduction of acid sites in different confined positions in ZSM-5 and its catalytic implications. ACS Catalysis, 2018, 8(8): 7688–7697

12 Kim S , Park G , Woo M H , Kwak G , Kim S K . Control of hierarchical structure and framework-Al distribution of ZSM-5 via adjusting crystallization temperature and their effects on methanol conversion. ACS Catalysis, 2019, 9(4): 2880–2892

13 Feng R , Liu B , Zhou P , Yan X L , Hu X Y , Zhou M , Yan Z F . Influence of framework Al distribution in HZSM-5 channels on catalytic performance in the methanol to propylene reaction. Applied Catalysis A, General, 2022, 629: 118422

14 Al-Nahari S , Dib E , Cammarano C , Saint-Germes E , Massiot D , Sarou-Kanian V , Alonso B . Impact of mineralizing agents on aluminum distribution and acidity of ZSM-5 zeolites. Angewandte Chemie International Edition, 2023, 62(7): e202217992

15 Li J L , Gao M K , Yan W F , Yu J H . Regulation of the Si/Al ratios and Al distributions of zeolites and their impact on properties. Chemical Science, 2023, 14(8): 1935–1959

16 Wang S , Wang P F , Qin Z F , Chen Y Y , Dong M , Li J F , Zhang K , Liu P , Wang J G , Fan W B . Relation of catalytic performance to the aluminum siting of acidic zeolites in the conversion of methanol to olefins, viewed via a comparison between ZSM-5 and ZSM-11. ACS Catalysis, 2018, 8(6): 5485–5505

17 Sazama P , Dedecek J , Gabova V , Wichterlova B , Spoto G , Bordiga S . Effect of aluminium distribution in the framework of ZSM-5 on hydrocarbon transformation. Cracking of 1-butene. Journal of Catalysis, 2008, 254(2): 180–189

18 Song C , Chu Y , Wang M , Shi H , Zhao L , Guo X , Yang W , Shen J , Xue N , Peng L . . Cooperativity of adjacent Brønsted acid sites in MFI zeolite channel leads to enhanced polarization and cracking of alkanes. Journal of Catalysis, 2017, 349: 163–174

19 Tabor E , Bernauer M , Wichterlová B , Dedecek J . Enhancement of propene oligomerization and aromatization by proximate protons in zeolites; FT-IR study of the reaction pathway in ZSM-5. Catalysis Science & Technology, 2019, 9(16): 4262–4275

20 XingM JChenY LCaoJHanY LTaoZ CWangFHaoKZhangLZhengW TXiangH W, . Are olefin aromatization reactions structure sensitive over Al pairs and single Al in H-ZSM-5 Zeolite? Fuel, 2023, 333: 126541

21 Shi D Z , Wang S , Wang H , Wang P F , Zhang L , Qin Z F , Wang J G , Zhu H Q , Fan W B . Synthesis of HZSM-5 rich in paired Al and its catalytic performance for propane aromatization. Catalysts, 2020, 10(6): 622

22 Dědeček J , Kaucky D , Wichterlova B , Gonsiorova O . Co²⁺ ions as probes of Al distribution in the framework of zeolites. ZSM-5 study. Physical Chemistry Chemical Physics, 2002, 4(21): 5406–5413

23 Groen J C , Peffer L A A , Moulijn J A , Javier P R . Mechanism of hierarchical porosity development in MFI zeolites by desilication: the role of aluminium as a pore-directing agent. Chemistry, 2005, 11: 4983–4994

24 Zhou Y N , Liu H Y , Rao X R , Yue Y Y , Zhu H B , Bao X J . Controlled synthesis of ZSM-5 zeolite with an unusual Al distribution in framework from natural aluminosilicate mineral. Microporous and Mesoporous Materials, 2020, 305: 110357

25 Dedecek J , Balgova V , Pashkova V , Klein P , Wichterlova B . Synthesis of ZSM-5 zeolites with defined distribution of Al atoms in the framework and multinuclear MAS NMR analysis of the control of Al distribution. Chemistry of Materials, 2012, 24(16): 3231–3239

26 Yokoi T , Mochizuki H , Namba S , Kondo J N , Tatsumi T . Control of the Al distribution in the framework of ZSM-5 zeolite and its evaluation by solid-state NMR technique and catalytic properties. Journal of Physical Chemistry C, 2015, 119(27): 15303–15315

27 Borodina E , Meirer F , Lezcano-González I , Mokhtar M , Asiri A M , Al-Thabaiti S A , Basahel S N , Ruiz-Martinez J , Weckhuysen B M . Influence of the reaction temperature on the nature of the active and deactivating species during methanol to olefins conversion over H-SSZ-13. ACS Catalysis, 2015, 5(2): 992–1003