Zeolites are crystalline metallosilicates displaying unique physicochemical properties with widespread applications in catalysis, adsorption, and separation. They are generally obtained by a multi-step process that starts with primary mixture aging, followed by hydrothermal crystallization, washing, drying, and, finally, a calcination step. However, the zeolites obtained are in the powder form and because of generating a pressure drop in industrial fixed bed reactors, not applicable for industrial purposes. To overcome such drawbacks, zeolites are shaped into appropriate geometries and desired size (a few centimeters) using extrusion, where zeolite powders are mixed with binders (e.g., mineral clays or inorganic oxides). The presence of binders provides good mechanical strength against crushing in shaped zeolites, but binders may have adverse impacts on zeolite catalytic and sorption properties, such as active site dilution and pore blockage. The latter is more pronounced when the binder has a smaller particle size, which makes the zeolite internal active sites mainly inaccessible. In addition to the shaping requirements, a hierarchical structure with different levels of porosity (micro-, meso-, and macropores) and an interconnected network are essential to decrease the diffusion limitation inside the zeolite micropores as well as to increase the mass transfer because of the presence of larger auxiliary pores. Thus, the generation of hierarchical structure and its preservation during the shaping step is of great importance. The aim of this review is to provide a comprehensive survey and detailed overview on the binder-containing extrusion technique compared to alternative shaping technologies with improved mass transfer properties. An emphasis is allocated to those techniques that have been less discussed in detail in the literature.
The study on the synthesis of zeolites, including both the development of novel techniques of synthesis and the discovery of new zeolitic frameworks, has a background of several decades. In this context, the application of organic structure-directing agents (SDAs) is one of the key factors having an important role in the formation of porous zeolitic networks as well as the crystallization process of zeolites. There are various elements that are needed to be explored for elucidating the effects of organic SDAs on the final physicochemical properties of zeolites. Although SDAs were firstly used as pore generators in the synthesis of high-silica zeolites, further studies proved their multiple roles during the synthesis of zeolites, such as their influences on the crystallization evolution of zeolite, the size of the crystal and the chemical composition, which is beyond their porogen properties. The aim of this mini review is to present and briefly summarize these features as well as the advances in the synthesis of new SDAs during the last decades.
Solid-state NMR is a nondestructive and noninvasive technique used to study the chemical structure and dynamics of starch-based materials and to bridge the gap between structure–function relationships and industrial applications. The study of crystallinity, chemical modification, product blending, molecular packing, amylose–amylopectin ratio, end chain motion, and solvent–matrix interactions is essential for tailoring starch product properties to various applications. This article aims to provide a comprehensive and critical review of research characterizing starch-based materials using solid-state NMR, and to briefly introduce the most advanced and promising NMR strategies and hardware designs used to overcome the sensitivity and resolution issues involved in structure–function relationships.
Bimetallic zeolite Beta in bead format and containing Al sites with Brønsted acid behavior and Sn, Zr or Hf sites with Lewis acid character, were prepared using a two-step synthetic route. First, zeolite Beta in the format of macroscopic beads (400 to 840 μm) with hierarchical porosity (micropores accessed through meso- and macropores in the range of 30 to 150 nm) were synthesized by hydrothermal crystallization in the presence of anion-exchange resin beads as hard template and further converted into their H-form. Next, the zeolite beads were partially dealuminated using different concentrations of HNO3 (i.e., 1.8 or 7.2 M), followed by grafting with one of the above-mentioned metals (Sn, Zr or Hf) to introduce Lewis acid sites. These bimetallic zeolites were tested as heterogeneous catalysts in the conversion of dihydroxyacetone (DHA) to methyl lactate (ML). The Sn-containing zeolite Beta beads treated by 1.8 M HNO3 and grafted with 27 mmol of SnCl4 (Sn-deAl-1.8-Beta-B) demonstrated the best catalytic activity among the prepared bimetallic zeolite beads, with 99% selectivity and 90% yield of ML after 6 h at 90 °C. This catalyst was also tested in combination with Au-Pd nanoparticles supported on functionalized carbon nanotubes (CNTs) as multifunctional catalytic system for the conversion of glycerol to ML, achieving 29% conversion of glycerol and 67% selectivity towards ML after 4.5 h at 140 °C under 30 bar air. The catalytic results were rationalized by means of a thorough characterization of the zeolitic beads with a combination of techniques (XRD, N2-physisorption, SEM, XRF, TEM, UV-vis spectroscopy and pyridine-FT-IR).
Biomethane can be isolated from biogas through selective CO2 adsorption. Faujasite-type zeolites are promising adsorbents for CO2 separation due to their high CO2 adsorption capacity. While commonly inert binder materials are used to shape zeolite powders into the desired macroscopic format for application in an adsorption column, here we report the synthesis of Faujasite beads without the use of a binder and their application as CO2-adsorbents. Three types of binderless Faujasite beads (d = 0.4–0.8 mm) were synthesized using an anion-exchange resin hard template. All the prepared beads consisted mostly of small Faujasite crystals, as demonstrated by characterization with XRD and SEM, which are interconnected through a network of meso- and macropores (10–100 nm), yielding a hierarchically porous structure, as shown by N2 physisorption and SEM. The zeolitic beads showed high CO2 adsorption capacity (up to 4.3 mmol g−1 at 1 bar and 3.7 mmol g−1 at 0.4 bar) and CO2/CH4 selectivity (up to 19 at the partial pressures mimicking biogas, i.e., 0.4 bar CO2 and 0.6 bar CH4). Additionally, the synthesized beads have a stronger interaction with CO2 than the commercial zeolite powder (enthalpy of adsorption −45 kJ mol−1 compared to −37 kJ mol−1). Therefore, they are also suitable for CO2 adsorption from gas streams in which the CO2 concentration is relatively low, such as flue gas.