Abstract
Bifunctional catalysts on the basis of Ukrainian natural mordenite-clinoptilolite rocks modified by hydrochloric acid and by witness impregnation with nickel have been synthesized. Samples have been characterized by means of XRD, XRF, FTIR-spectroscopy, low temperature nitrogen adsorption/desorption, DTA/TG, TEM. Catalysts have been tested in micro pulse linear hexane isomerization. Hydrochloric acid treatment of natural zeolite rock leads to silica-to-alumina ratio increasing and raising the BET surface as well as the volumes of mesopores and micropores. The nickel nanoparticles deposited over zeolite crystals have a predominant size of 10 nm, but for some samples smaller ones of 5 nm and bigger ones of 20–50 nm have been found using TEM investigations. Pyridine sorption shows Brønsted and Lewis acidity of the catalysts, moreover the lower hydrochloric acid concentration using leads to practically equal Brønsted and Lewis acidity, the higher acid concentrations causes the Lewis acidity predominance. DTA/TG investigations show that water physically sorbed in the pores of the samples has been removed up to 200 °C from lager cavities of acid-treated catalysts and up to 500 °C from narrower cavities for untreated initial rock. Removing zeolite structure water up to 800 °C causes the dehydroxylation and Brønsted acidity transformation into Lewis acidity. The sample dealuminated by 1 mol dm−3 acid with nickel nanoparticles of 5–8 nm demonstrates the best performance in the isomerization of n-hexane. It is characterized by a 20% yield of hexane isomers at 250 °C and 70% selectivity.
Similar content being viewed by others
References
Afzal M, Yasmeen G, Saleem M, Butt PK, Khattak AK, Afzal J (2000) TG and DTA study of the thermal dehydration of metal-exchanged zeolite-4A samples. J Therm Anal Calorim 62:721–727. https://doi.org/10.1023/A:1026725509732
Alver BE, Sakizci M, Yörükoğullari E (2010) Investigation of clinoptilolite rich natural zeolites from Turkey: a combined XRF, TG/DTG, DTA and DSC study. J Therm Anal Calorim 100:19–26. https://doi.org/10.1007/s10973-009-0118-0
Bai R, Song Yu, Li Y, Yu J (2019) Creating hierarchical pores in zeolite catalysts. Trends Chem 1:601–611. https://doi.org/10.1016/j.trechm.2019.05.010
Bordiga S, Lamberti C, Bonino F, Thibault-Starzyk F (2015) Probing zeolites by vibrational spectroscopies. Chem Soc Rev 44:7262–7341. https://doi.org/10.1039/C5CS00396B
Corma A, Frontela J, Lazaro J, Perez M (1991) Alkylation, Aromatization, Oligomerization and Isomerization of Short Chain Hydrocarbons over Heterogeneous Catalysts. In: W.E. Haines (eds) Preprints Div. Petrol. Chem., ACS Symposium Series, vol. 36, New York, p. 833.
Devaraj A, Vijayakumar M, Bao J, Guo MF, Derewinski MA, Xu Z, Gray MJ, Prodinger S, Ramasamy KK (2016) Discerning the location and nature of coke deposition from surface to bulk of spent zeolite catalysts. Sci Rep 6:37586. https://doi.org/10.1038/srep37586
Feliczak-Guzik A (2018) Hierarchical zeolites: Synthesis and catalytic properties. Microp Mesopor Mater 259:33. https://doi.org/10.1016/j.micromeso.2017.09.030
Jordao MH, Simoes V, Cardoso D (2007) Zeolite supported Pt-Ni catalysts in n-hexane isomerization. Appl Catal A 319:1–6. https://doi.org/10.1016/j.apcata.2006.09.039
Khan W, Jia X, Wu Z, Choi J, Yip ACK (2019) Incorporating hierarchy into conventional zeolites for catalytic biomass conversions: a review. Catalysts 9(2):127–150. https://doi.org/10.3390/catal9020127
Kondo JN, Nishitani R, Yoda E, Yokoi T, Tatsumi T, Domen KA (2010) Comparative IR characterization of acidic sites on HYzeolite by pyridine and COprobes with silica–alumina and γ-alumina references. Phys Chem Chem Phys 12:11576–11586. https://doi.org/10.1039/C0CP00203H
Korkuna O, Leboda R, Skubiszewska-Zieba J, Vrublevska T, Gunko VM, Ryczkowski J (2006) Structural and physicochemical properties of natural zeolites:clinoptilolite and mordenite. Microporous Mesoporous Mater 87:243–254. https://doi.org/10.1016/j.micromeso.2005.08.002
Issa H, Chaouati N, Toufaily J, Hamieh T, Sachse A, Pinard L (2019) Toolbox of post-synthetic mordenite modification strategies: impact on textural, acidic and catalytic properties. ChemCatChem 11(18):4581–4592. https://doi.org/10.1002/cctc.201900927
Lima PM, Garetto T, Cavalcante CLJr, Cardoso D, (2011) Isomerization of n-hexane on Pt–Ni catalysts supported on nanocrystalline H-BEA zeolite. Catal Today 172:195–202. https://doi.org/10.1016/j.cattod.2011.02.031
Liu B, Slocombe D, AlKinany M, AlMegren H, Wang J, Arden J, Vai A, Gonzalez-Cortes S, Xiao T, Kuznetsov V, Edwards PP (2016) Advances in the study of coke formation over zeolite catalysts in the methanol-to-hydrocarbon process. Appl Petrochem Res 6:209–215. https://doi.org/10.1007/s13203-016-0156-z
Liu Z, Hua Y, Wang J, Dong X, Tian Q, Han Yu (2017) Recent progress in the direct synthesis of hierarchical zeolites: synthetic strategies and characterization methods. Mater Chem Front 1:2195–2212. https://doi.org/10.1039/C7QM00168A
Lukyanov DM, Vazhnova T, Cherkasov N, Casci JL, Birtill JJ (2014) Insights into brønsted acid sites in the zeolite mordenite. J Phys Chem C 118(41):23918–23929. https://doi.org/10.1021/jp5086334
Mansouri N, Rikhtegar N, Panahi HA, Atabi F, Shahraki BK (2013) Porosity, characterization and structural properties of natural zeolite—clinoptilolite—as a sorbent. Env Protec Eng 39:149–152. https://doi.org/10.5277/EPE130111
Martins GSV, dos Santos ERF, Rodrigues MGF, Pecchi G, Yoshioka CMN, Cardoso D (2013) n-Hexane isomerization on Ni-Pt/catalysts supported on mordenite. Modern Res Catal 2:119–126. https://doi.org/10.4236/mrc.2013.24017
Mikuła A, Król M, Mozgawa W, Koleżyński A (2018) New approach for determination of the influence of long-range order and selected ring oscillations on IR spectra in zeolites. Spectrochim Acta A Mol Biomol Spectrosc 95:62–67. https://doi.org/10.1016/j.saa.2018.01.044
Mitchell S, Pinar A, Kenvin J, Crivelli P, Kärger J, Pérez-Ramírez J (2015) Structural analysis of hierarchically organized zeolites. Nat Commun 6:8633. https://doi.org/10.1038/ncomms9633
Na K, Choi M, Ryoo R (2013) Recent Advances in the Synthesis of Hierarchically Nanoporous Zeolites. Micropor Mesopor Mater 166:3–19. https://doi.org/10.1016/j.micromeso.2012.03.054
Nordvang EC, Borodina E, Ruiz-Martínez J, Fehrmann R, Weckhuysen BM (2015) Effects of coke deposits on the catalytic performance of large zeolite H-ZSM-5 crystals during alcohol-to-hydrocarbon reactions as investigated by a combination of optical spectroscopy and microscopy. Chemistry 21(48):17324–17335. https://doi.org/10.1002/chem.201503136
Patrylak LK (1999) Chemisorption of Lewis bases on zeolites—a new interpretation of the results. Adsorpt Sci Technol 17(2):115–123. https://doi.org/10.1177/026361749901700205
Patrylak L, Likhnyovskyi R, Vypyraylenko V, Leboda R, Skubiszewska-Zięba J, Patrylak K (2001a) Adsorption properties of zeolite-containing microspheres and FCC catalysts based on Ukrainian Kaolin. Adsorpt Sci Technol 19(7):525–540. https://doi.org/10.1260/0263617011494376
Patrylak KI, Bobonych FM, Voloshyna YuG, Levchuk MM, Solomakha VM, Patrylak LK, Manza IA, Taranookha OM (2001b) Linear hexane isomerization over the natural zeolite based catalysts depending on the zeolite phase composition. Catal Today 65:129–135. https://doi.org/10.1016/S0920-5861(00)00573-3
Patrylak LK, Manza IA, Vypirailenko VYo, Korovitsyna AS, Likhniovskyi RV, (2003) Study of the mechanism of hexane isomerization under micropulse conditions. Theor Experim Chem 39:263–267. https://doi.org/10.1023/A:1025729530977
Patrylak LK, Pertko OP (2018) Peculiarities of activity renovation of zeolite catalysts coked in hexane cracking. Chem Chem Technol 12(4):538–554. https://doi.org/10.23939/chcht12.04.538
Patrylak LK, Krylova MM, Pertko OP, Voloshyna YuG (2019a) Linear hexane isomerization over Ni-containing pentasils. J Porous Mater 26(3):861–868. https://doi.org/10.1007/s10934-018-0685-1
Patrylak LK, Pertko OP, Povazshnyi VA, Melnychuk OV (2019b) Influence of modification by Zr and La on the porous characteristics and catalytic activity of in situ synthesized microspherical cracking catalysts. Voprosy Khimii i Khimicheskoi Tekhnologii 6:157–163. https://doi.org/10.32434/0321-4095-2019-127-6-157-163
Patrylak L, Krylova M, Pertko O, Voloshyna Yu, Yakovenko A (2020) n-Hexane isomerization over nickel-contaning mordenite zeolites. Chem Chem Technol 14(2):234–238. https://doi.org/10.23939/chcht14.02.234
Phung TK, Busca G (2015) On the Lewis acidity of protonic zeolites. Appl Catal A: Gen 504:151–157. https://doi.org/10.1016/j.apcata.2014.11.031
Rouqerol F, Rouqerol J, Sing K (1999) Adsorption by powders & porous solids: principles. Methodology and applications. Academic Press, San Diego
Ruíz-Baltazar A, Esparza R, Gonzalez M, Rosas G, Pérez R (2015) Preparation and Characterization of Natural Zeolite Modified with Iron Nanoparticles. J Nanomaterials 5:2–8. https://doi.org/10.1155/2015/364763
Wojciechowska KM, Król M, Bajda T, Mozgawa W (2019) Sorption of heavy metal cations on mesoporous ZSM-5 and mordenite zeolites. Materials 12:3271. https://doi.org/10.3390/ma12193271
Sánchez-López P, Antúnez-García J, Fuentes-Moyado S, Galván DH, Petranovskii V, Chávez-Rivas F (2019) Analysis of theoretical and experimental X-ray diffraction patterns for distinct mordenite frameworks. J Mater Sci 54:7745–7757. https://doi.org/10.1007/s10853-019-03407-w
Selvam T, Schwieger W, Dathe W (2018) Histamine-binding capacities of different natural zeolites: a comparative study. Environ Geochem Health 40(6):2657–2665. https://doi.org/10.1007/s10653-018-0129-5
Serrano DP, Pizarro P (2013) Synthesis Strategies in the Search for Hierarchical Zeolites. Chem Soc Rev 42:4004–4035. https://doi.org/10.1039/C2CS35330J
Treacy MMJ, Higgins JB (eds) (2001) Collection of Simulated XRD powder patterns for zeolites. Elsevier, Amsterdam
Weissenberger T, Reiprich B, Machoke AGF, Klühspies K, Bauer J, Dotzel R, Casci JL, Schwieger W (2019) Hierarchical MFI type zeolites with intracrystalline macropores: the effect of the macropore size on the deactivation behaviour in the MTO reactio. Catal Sci Technol 9:3259. https://doi.org/10.1039/C9CY00368A
Yoshioka CMN, Garetto T, Cardoso D (2005) n-Hexane isomerization on Ni-Pt catalysts/supported on HUSY zeolite: The influence from a metal content. Catal Today 107–108:693–698. https://doi.org/10.1016/j.cattod.2005.07.056
Acknowledgements
The authors acknowledge the assistance and support of M.G. Kholodny Institute of Botany of National Academy of Sciences in conducting the electron transmission microscopy experiments. The publication contains the results of studies conducted by President’s of Ukraine grant for competitive projects F84/147-2019 and by grant of National Research Fundation of Ukraine project 2020.01/0042.
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Conflict of interest
On behalf of all authors, the corresponding author states that there is no conflict of interest.
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Rights and permissions
About this article
Cite this article
Patrylak, L.K., Pertko, O.P., Yakovenko, A.V. et al. Isomerization of linear hexane over acid-modified nanosized nickel-containing natural Ukrainian zeolites. Appl Nanosci 12, 411–425 (2022). https://doi.org/10.1007/s13204-021-01682-1
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s13204-021-01682-1