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      Opening up ZSM-5 Hierarchical Zeolite’s Porosity through Sequential Treatments for Improved Low-Density Polyethylene Cracking †

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          Abstract

          An adequately tuned acid wash of hierarchical ZSM-5 zeolites offers a levelling up in the catalytic cracking of low-density polyethylene. Identification of crucial and limiting factors governing the activity of the zeolite was extended with studies about the accessibility of acid sites, nature of the realuminated layer and role of Lewis acid sites. The sequential treatment of a ZSM-5 zeolite offered enhanced activity in low-density polyethylene (LDPE) cracking at low and high conversions, as confirmed by a decrease in the temperatures needed to reach 20% and 80% conversion (T 20 and T 80, respectively). A linear dependence of the T 80 on the coupled IHF (indexed hierarchy factor) and AF B (accessibility factor) highlighted the importance of the textural and acidic parameters in the catalytic cracking of LDPE. Operando FT-IR-GC studies confirmed a higher fraction of short-chain hydrocarbons (C 3–C 5) in the product distribution of hierarchical catalysts resulting from the effective polymer cracking in easily accessible pores.

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          Design of hierarchical zeolite catalysts by desilication

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            Catalysis with hierarchical zeolites

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              Mechanism of hierarchical porosity development in MFI zeolites by desilication: the role of aluminium as a pore-directing agent.

              The role of the concentration and the nature of aluminium in the creation of hierarchical porosity in both commercial and synthesized MFI zeolites have been investigated through controlled mesoporosity development by desilication in alkaline medium. Framework aluminium controls the process of framework silicon extraction and makes desilication selective towards intracrystalline mesopore formation. An optimal molar Si/Al ratio in the range 25-50 has been identified; this leads to an optimal mesoporosity centred around 10 nm and mesopore surface areas of up to 235 m(2) g(-1) while preserving the intrinsic crystalline and acidic properties. At lower framework Si/Al ratios the relatively high Al content inhibits Si extraction and hardly any mesopores are created, while in highly siliceous ZSM-5 unselective extraction of framework Si induces formation of large pores. The existence of framework Al sites in different T positions that are more or less susceptible to the alkaline treatment, and the occurrence of re-alumination, are tentative explanations for the remarkable behaviour of Al in the desilication process. The presence of substantial extra framework Al, obtained by steam treatment, inhibits Si extraction and related mesopore formation; this is attributed to re-alumination of the extraframework Al species during the alkaline treatment. Removal of extraframework Al species by mild oxalic acid treatment restores susceptibility to desilication, which is accompanied by formation of larger mesopores due to the enhanced Si/Al ratio in the acid-treated zeolite.
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                Author and article information

                Contributors
                Role: Academic Editor
                Role: Academic Editor
                Role: Academic Editor
                Journal
                Molecules
                Molecules
                molecules
                Molecules
                MDPI
                1420-3049
                22 June 2020
                June 2020
                : 25
                : 12
                : 2878
                Affiliations
                Faculty of Chemistry, Jagiellonian University in Kraków, 2 Gronostajowa St., 30–87 Kraków, Poland; kamila.pyra@ 123456doctoral.uj.edu.pl (K.P.); kinga.gora-marek@ 123456uj.edu.pl (K.G.-M.)
                Author notes
                [†]

                Dedicated to Professor Jerzy Datka in appreciation of his outstanding contribution to zeolite science.

                Author information
                https://orcid.org/0000-0003-0133-4363
                https://orcid.org/0000-0002-2510-1559
                https://orcid.org/0000-0002-1296-9244
                Article
                molecules-25-02878
                10.3390/molecules25122878
                7356772
                32580524
                4d0aa492-e878-43e7-a27a-eadee96db261
                © 2020 by the authors.

                Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license ( http://creativecommons.org/licenses/by/4.0/).

                History
                : 07 May 2020
                : 18 June 2020
                Categories
                Article

                hierarchical zeolites,acid-wash,lewis acid sites,operando spectroscopy,ldpe cracking,realumination

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