In present work, bi-phases composite zeolites consisting of SAPO-5 and SAPO-34 (named as SSC) are prepared by a traditional hydrothermal way, and characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), N2 adsorption–desorption, intelligent gravimetric analyzer (IGA), intrusive mercury technology, and NH3-TPD techniques. The results display that the crystals in the as-synthesized composites have a hierarchical pore system with a size of about 3–130 nm, which displays a butterfly-like pattern on the crystal faces and runs throughout the whole crystal. Catalytic performances of the as-synthesized SSC catalysts are tested during methanol to olefin (MTO). As compared with a microporous composite catalyst, the hierarchical SSC composite catalyst displays excellent catalytic performances with a prolonged catalytic life and an elevated selectivity for light olefins.
This is a preview of subscription content, access via your institution.
Buy single article
Instant access to the full article PDF.
Tax calculation will be finalised during checkout.
Subscribe to journal
Immediate online access to all issues from 2019. Subscription will auto renew annually.
Tax calculation will be finalised during checkout.
J. Pérez-Ramírez, C.H. Christensen, K. Egeblad, C.H. Christensend, J.C. Groen, Hierarchical zeolites: enhanced utilisation of microporous crystals in catalysis by advances in materials design. Chem. Soc. Rev. 37, 2530 (2008)
Y.S. Tao, H. Kanoh, K. Kaneko, Synthesis of mesoporous zeolite A by resorcinol-formaldehyde aerogel templating. Langmuir 21, 504 (2005)
S. van Donk, A.H. Janssen, J.H. Bitter, K.P. de Jong, Generation, characterization, and impact of mespores in zeolite catalysts. Catal. Rev. Sci. Eng. 45, 297 (2003)
L.C. Zhang, X.B. Sun, M. Pan, X.N. Yang, Y.C. Liu, J.H. Sun, Q.H. Wang, J.J. Zheng, Y. Wang, J.H. Ma, W.L. Li, R.F. Li, Interfacial effects between carbon nanotube templates and precursors on fabricating a wall-crystallized hierarchical pore system in zeolite crystals. J. Mater. Sci. 55, 10412–10426 (2020)
X.Y. Cui, J.J. Wang, M. Pan, W.W. Ning, L.L. Yan, J.J. Zheng, R.F. Li, Hierarchical SAPO-34: Synthesis and Catalytic Performances in Methanol to Olefins. Chin. J. Inor. Chem. 34(2), 300–308 (2018)
D. Verboekend, J. Pérez-Ramírez, Design of hierarchical zeolite catalysts by desilication. Catal. Sci. Technol. 1(6), 879–890 (2011)
L. Wu, V. Degirmenci, P.C.M.M. Magusin, N.J.H.G.M. Lousberg, E.J.M. Hensen, Mesoporous SSZ-13 zeolite prepared by a dual-template method with improved performance in the methanol-to-olefins reaction. J. Catal. 298, 27–40 (2013)
A.K. Singh, R. Yadav, A. Sakthivel, Synthesis, characterization, and catalytic application of mesoporous SAPO-34 (MESO-SAPO-34) molecular sieves. Micropor. Mesopor. Mater. 181, 166–174 (2013)
A. Sayari, Catalysis by crystalline mesoporous molecular sieves. Chem. Mater. 8(8), 1840–1852 (1996)
A. Corma, From microporous to mesoporous molecular sieve materials and their use in catalysis. Chem. Rev. 97(6), 2373–2420 (1997)
Y.C. Liu, B. Qin, H.X. Gao, W.W. Ning, L.C. Zhang, J.J. Zheng, Y.Z. Du, Y. Wang, W.L. Li, R.F. Li, Core-shell Y zeolite with a mono-crystalline core and a loosely aggregating polycrystalline shell: a hierarchically cracking catalyst for large reactants. Catal. Sci. Technol. 10, 2303–2312 (2020)
Y.X. Li, Y.H. Huang, J.H. Guo, M.Y. Zhang, D.Z. Wang, F. Wei, Y. Wang, Hierarchical SAPO-34/18 zeolite with low acid site density for converting methanol to olefins. Catal. Today 233, 2–7 (2014)
S.Y. Liu, H.K. Zhang, H.M. Chen, Z.Q. Chen, L.W. Zhang, J. Ren, X.D. Wen, Y. Yang, Y.-W. Li, Fabrication of core-shell TON@MFI material and its enhanced catalytic performance for toluene alkylation. Catal. Sci. Technol. 10, 1281–1291 (2020)
N. Masoumifard, R. Guillet-Nicolas, F. Kleitz, Synthesis of Engineered Zeolitic Materials: From Classical Zeolites to Hierarchical Core-Shell Materials. Adv. Mater. 30, 1704439–1704479 (2018)
L. Huang, W. Guo, P. Deng, Z. Xue, Q. Li, Investigation of synthesizing mcm-41/zsm-5 composites. J. Phy. Chem. B 104(13), 2817–2823 (2000)
J.J. Zheng, X.W. Zhang, Y. Wang, Y.D. Bai, W.F. Sun, R.F. Li, Synthesis and catalytic performance of a bi-phase core-shell zeolite composite. J. Porous Mater. 16, 731–736 (2009)
Y.S. Ooi, R. Zakaria, A.R. Mohamed, S. Bhatia, Synthesis of composite material mcm-41/beta and its catalytic performance in waste used palm oil cracking. Appl. Catal. A Gen. 274(1–2), 15–23 (2004)
X. Li, F. Rezaei, D.K. Ludlow, A.A. Rownaghi, Synthesis of SAPO-34@ZSM-5 and SAPO-34@Silicalite-1 Core−Shell Zeolite Composites for Ethanol Dehydration. Ind. Eng. Chem. Res. 57, 1446–1453 (2018)
U. Olsbye, S. Svelle, M. Bj ø rgen, P. Beato, T.V.W. Janssens, F. Joensen, S. Bordiga, K.P. Lillerud, Conversion of methanol to hydrocarbons: how zeolite cavity and pore size controls product selectivity. Angew. Chem. Int. Ed. 51(24), 5810–5831 (2012)
J. Li, Y.X. Wei, J.R. Chen, S.T. Xu, Z. Liu, Cavity controls the selectivity: insights of confinement effects on MTO reaction. ACS Catal. 5(2), 661–665 (2014)
S. Teketel, L.F. Lundegaard, W. Skistad, S.M. Chavan, U. Olsbye, K.P. Lillerud, P. Beato, S. Svelle, Morphology-induced shape selectivity in zeolite catalysis. J. Catal. 327, 22–32 (2015)
G. Sastre, D.W. Lewis, C.R.A. Catlow, Modeling of Silicon Substitution in SAPO-5 and SAPO-34 Molecular Sieves. J. Phy. Chem. B 101(27), 5249–5262 (1997)
J.M. Campelo, F. Lafont, J.M. Marinas, Pt/sapo-5 and pt/sapo-11 as catalysts for the hydroisomerization and hydrocracking of n-octane. J. Chem. Soc. Faraday Trans. 91(10), 1551 (1995)
J.J. Zheng, X.B. Sun, Y.Z. Du, B. Qin, Y.Y. Zhang, H.Y. Zhang, M. Pan, R.F. Li, Structural features of core-shell zeolite-zeolite composite and its performance for methanol conversion into gasoline and diesel. J. Mater. Res. 31(15), 2302–2316 (2016)
G.S. Wang, Y.J. Liu, J.J. Zheng, M. Pan, H.Y. Zhang, B. Li, S. Yuan, Y.M. Yi, H.P. Tian, R.F. Li, Zeolite-zeolite composite fabricated by polycrystalline Y zeolite crystals parasitizing ZSM-5 zeolite. J. Mater. Res. 30(16), 2434–2446 (2015)
X.X. Chen, D.Y. Xi, Q.M. Sun, N. Wang, Z.Y. Dai, D. Fan, V. Valtchev, J.H. Yu, A top-down approach to hierarchical sapo-34 zeolites with improved selectivity of olefin. Micropor. Mesopor. Mater. 234, 401–408 (2016)
S.H. Jhung, J.S. Chang, J.S. Hwang, S.E. Park, Selective formation of sapo-5 and sapo-34 molecular sieves with microwave irradiation and hydrothermal heating. Micropor. Mesopor. Mater. 64(1), 33–39 (2003)
P. Concepción, J.M. López Nieto, A. Mifsud, J. Pérez-Pariente, Preparation and characterization of Mg-containing AFI and chabazite-type materials. Zeolites 16(1), 56–64 (1996)
J. Gong, F. Tong, X.B. Ji, C.F. Zeng, C.Q. Wang, Y.N. Lv, L.X. Zhang, Hollow SAPO-34 Cubes with Hierarchically Organized Internal Structure. Cryst. Growth Des. 14(8), 3857–3863 (2014)
T.M. Neves, J.O. Fernandes, L.M. Lião, E.D. da Silva, C.A. da Rosa, V.B. Mortola, Glycerol dehydration over micro- and mesoporous ZSM-5 synthesized from a one-step method. Micropor. Mesopor. Mater. 275, 244–252 (2019)
H.B. Zhang, Z.J. Hu, L. Huang, H.X. Zhang, K.S. Song, L. Wang, Z.P. Shi, J.X. Ma, Y. Zhuang, W. Shen, Y.H. Zhang, H.L. Xu, Y. Tang, Dehydration of glycerol to acrolein over hierarchical ZSM-5 zeolites: effects of mesoporosity and acidity. ACS Catal. 5, 2548–2558 (2015)
M.A. Carreon, S.G. Li, J.L. Falconer, R.D. Noble, Alumina-supported SAPO-34 membranes for CO2/CH4 separation. J. Am Chem. Soc. 130(16), 5412–5413 (2008)
S. Li, G. Alvarado, R.D. Noble, J.L. Falconer, Effects of impurities on CO2/CH4 separations through SAPO-34 membranes. J. Membrane Sci. 251(1–2), 59–66 (2005)
A. Martínez, E. Peris, M. Derewinski, A. Burkat-Dulak, Improvement of catalyst stability during methane dehydroaromatization (MDA) on Mo/HZSM-5 comprising intracrystalline mesopores. Catal. Today 169(1), 75–84 (2011)
X. Wang, Y. Li, C. Luo, B. Chen, Direct synthesis of hierarchical zeolites with oriented nanocrystals without adding extra templates. RSC Adv. 3(18), 6295–6298 (2013)
S. Wilson, P. Barger, The characteristics of SAPO-34 which influence the conversion of methanol to light olefins. Micropor. Mesopor. Mater. 29(1–2), 117–126 (1999)
This work is supported by NSFC (21975174, 21706177), National Key R&D Program of China (2020YFB0606405) and SinoPEC (116050).
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Below is the link to the electronic supplementary material.
About this article
Cite this article
Bai, Y., Zeng, Q., Sun, J. et al. Synthesis of composite zeolites composed of SAPO-5 and SAPO-34 and its application in methanol dehydration to light olefins. J Porous Mater (2021). https://doi.org/10.1007/s10934-021-01078-0
- Hierarchical pores
- Butterfly-like distribution
- Methanol to olefins