Zeolite Catalysis Research Articles

The Paradoxical Influence of Hydrothermally Treated Zeolites on the Hydrocarbon Pool Mechanism.

Understanding the mechanistic intricacies of hydrothermally treated zeolite is crucial for valorizing any oxygen-containing renewable feedstocks (e.g., methanol, carbon dioxide, biomass). Additionally, the regeneration of deactivated zeolite catalysts under oxidative conditions, akin to hydrothermal treatment, is essential in industrial processes. While research in this area has predominantly focused on characterizing steaming-induced physicochemical changes in zeolite, their ultimate impact on the organic reaction mechanism governed by the hydrocarbon pool dual-cycle mechanism remains unclear. To bridge this knowledge gap, this study investigates the effect of steamed zeolite on the organic reaction mechanism during the industrially significant methanol-to-hydrocarbons process. We achieved this objective by strategically integrating catalytic and control experiments over the pristine and steamed zeolites and their advanced characterization, including under operando conditions, XRD structural refinement, and using "mobility-dependent" solid-state NMR spectroscopy. This multimodal characterization approach was instrumental in elucidating elusive mechanistic information in the dual-cycle mechanism, shedding light on phenomena such as the unchanged ethylene selectivity despite decreasing aromatics selectivity, while ethylene could solely be derived from arene-based reaction intermediates. This study could improve the process efficiency in zeolite catalysis by connecting steaming-induced changes in the organic reaction mechanisms with inorganic material aspects.

The Paradoxical Influence of Hydrothermally Treated Zeolites on the Hydrocarbon Pool Mechanism

Understanding the mechanistic intricacies of hydrothermally treated zeolite is crucial for valorizing any oxygen‐containing renewable feedstocks (e.g., methanol, carbon dioxide, biomass). Additionally, the regeneration of deactivated zeolite catalysts under oxidative conditions, akin to hydrothermal treatment, is essential in industrial processes. While research in this area has predominantly focused on characterizing steaming‐induced physicochemical changes in zeolite, their ultimate impact on the organic reaction mechanism governed by the hydrocarbon pool dual‐cycle mechanism remains unclear. To bridge this knowledge gap, this study investigates the effect of steamed zeolite on the organic reaction mechanism during the industrially significant methanol‐to‐hydrocarbons process. We achieved this objective by strategically integrating catalytic and control experiments over the pristine and steamed zeolites and their advanced characterization, including under operando conditions, XRD structural refinement, and using “mobility‐dependent” solid‐state NMR spectroscopy. This multimodal characterization approach was instrumental in elucidating elusive mechanistic information in the dual‐cycle mechanism, shedding light on phenomena such as the unchanged ethylene selectivity despite decreasing aromatics selectivity, while ethylene could solely be derived from arene‐based reaction intermediates. This study could improve the process efficiency in zeolite catalysis by connecting steaming‐induced changes in the organic reaction mechanisms with inorganic material aspects.

Synergistic enhancement of poly(lactide) melt strength via copolymerization and multi-arm branching strategy

The lower melt strength of poly(lactide) (PLA) limits its broader applications. Here, a strategy combining copolymerization with multi-arm branching was propose to enhance the melt strength of PLA. Initially, stereoisomeric cyclic ester monomers (CEM) synthesized via zeolite catalysis were copolymerized into PLA chains. Subsequently, rheological testing revealed that the zero-shear viscosity (η0) of linear PLA increased by 467 % with only 1 mol% of CEM units. Our study further systematically explored the relationship between the side group structure and chirality of the comonomers and the rheological properties of the copolymers. CEMs with long-chain branched structures and opposite chirality had the best enhancement effect. In order to further enhance the melt strength, we successfully achieved alterations in polymer topology by employing trimethylolpropane as an initiator, corresponding three-arm copolymers achieve up to a 67-fold increase in η0 (1.0 kPa∙s to 68.1 kPa∙s). Tensile tests indicated that the mechanical properties of the copolymers were comparable to those of PLA, with a tensile strength of approximately 65 MPa. Additionally, due to the high melt strength, we successfully produced closed-cell PLA-based foam materials with uniform pore sizes. In summary, this study furnishes a feasible method for designing polymer materials possessing the desired melt strength.

Pyrolytic Depolymerization of Polyolefins Catalysed by Zirconium‐based UiO‐66 Metal–Organic Frameworks

AbstractPolyolefins such as polyethylenes and polypropylenes are the most‐produced plastic waste globally, yet are difficult to convert into useful products due to their unreactivity. Pyrolysis is a practical method for large‐scale treatment of mixed, contaminated plastic, allowing for their conversion into industrially‐relevant petrochemicals. Metal–organic frameworks (MOFs), despite their tremendous utility in heterogeneous catalysis, have been overlooked for polyolefin depolymerization due to their perceived thermal instabilities and inability of polyethylenes and polypropylenes to penetrate their pores. Herein, we demonstrate the viability of UiO‐66 MOFs containing coordinatively‐unsaturated zirconium nodes, as effective catalysts for pyrolysis that significantly enhances the yields of valuable liquid and gas hydrocarbons, whilst halving the amounts of residual solids produced. Reactions occur on the Lewis‐acidic UiO‐66 nodes, without the need for noble metals, and yield aliphatic product distributions distinctly different from the aromatic‐rich hydrocarbons that can be obtained from zeolite catalysis. We also demonstrate the first unambiguous characterization of polyolefin penetration into UiO‐66 pores at pyrolytic temperatures, allowing access to the abundant Zr‐oxo nodes within the MOF interior for efficient C−C cleavage. Our work highlights the potential of MOFs as highly‐designable heterogeneous catalysts for depolymerisation of plastics, which can complement conventional catalysts in reactivity.

Pyrolytic Depolymerization of Polyolefins Catalysed by Zirconium-based UiO-66 Metal-Organic Frameworks.

Polyolefins such as polyethylenes and polypropylenes are the most-produced plastic waste globally, yet are difficult to convert into useful products due to their unreactivity. Pyrolysis is a practical method for large-scale treatment of mixed, contaminated plastic, allowing for their conversion into industrially-relevant petrochemicals. Metal-organic frameworks (MOFs), despite their tremendous utility in heterogeneous catalysis, have been overlooked for polyolefin depolymerization due to their perceived thermal instabilities and inability of polyethylenes and polypropylenes to penetrate their pores. Herein, we demonstrate the viability of UiO-66 MOFs containing coordinatively-unsaturated zirconium nodes, as effective catalysts for pyrolysis that significantly enhances the yields of valuable liquid and gas hydrocarbons, whilst halving the amounts of residual solids produced. Reactions occur on the Lewis-acidic UiO-66 nodes, without the need for noble metals, and yield aliphatic product distributions distinctly different from the aromatic-rich hydrocarbons that can be obtained from zeolite catalysis. We also demonstrate the first unambiguous characterization of polyolefin penetration into UiO-66 pores at pyrolytic temperatures, allowing access to the abundant Zr-oxo nodes within the MOF interior for efficient C-C cleavage. Our work highlights the potential of MOFs as highly-designable heterogeneous catalysts for depolymerisation of plastics, which can complement conventional catalysts in reactivity.

Recent Trends in Tailoring External Acidity in Zeolites for Catalysis.

Zeolites are crystalline aluminosilicates with well-defined microporous structures that have found several applications in catalysis. In recent years, great effort has been devoted to defining strategies aimed at tuning structural and acidity properties to improve the catalytic performance of zeolites. Depending on the zeolitic structure, the acid sites located inside the crystals catalyze reactions by exploiting the internal channel shape-selectivity. In contrast, strong acid sites located on the external surface do not offer the possibility to control the size of molecules involved in the reactions. This aspect generally leads to a loss of selectivity toward desired products and to the uncontrolled production of coke. Passivating surface acidity is a promising way to overcome deactivation issues and to enhance the catalytic performance of zeolites. This Mini-Review aims to provide, for the first time, a complete overview of the techniques employed in recent years to neutralize strong external acid sites. Both chemical and liquid vapor deposition of silicates have been widely employed to passivate the external surface acidity of zeolites. In recent years, the epitaxial growth of layers of aluminum-free zeolite, e.g., silicalite-1, over the surface of the acidic zeolite has been proposed as a new approach to neutralize strong external acid sites controlling diffusional phenomena. NH3-TPD, FT-IR, SEM-EDX, and other techniques have been used to provide information about the level of control of the external strong acidity of passivated zeolites. In this Mini-Review, both passivation treatments and characterization techniques are compared and advantages and disadvantages deeply discussed to elucidate the effect of passivation procedures on physical features and especially the catalytic behavior.

Enhancing the catalytic performance of H-ZSM-5 in bio n-butanol dehydration by zeolite crystal engineering

NH4F etching is used as an unbiased chemical etching technique to hierarchize commercially available nano-sized ZSM-5 crystals. A structure-function relationship is reported, describing how the introduction of mesoporosity in a microporous ZSM-5 zeolite significantly increases its catalytic performance in (aqueous) n-butanol dehydration. Three parent samples are etched under two severity modes: mild (5 minutes of etching) and harsh (40 minutes of etching). Intrinsic features of the parent ZSM-5’s, such as their silanol populations, influence the outcome of the etching procedure. For all materials, crystallinity is unaffected, total pore volume increases while micropore volume is almost constant, and active site accessibility increases. For all materials, etching increases the catalytic activity for n-butanol dehydration. Cofeeding water to n-butanol further increases the stability of all catalysts. Microkinetic modeling reveals that the increased activity is related to a decreased stability of dibutyl ether (DBE), the most abundant surface intermediate. A decreased DBE adsorption energy, due to the increased accessibility of the acid sites, facilitates its desorption. NH4F etching, a flexible and easy technique to engineer zeolites' textural properties, does not affect the intrinsic nature and quantity of their active sites, leading to superior catalytic performances. Our results highlight the possibility to further increase the efficiency of zeolite catalysis in biomass conversion processes.

Modulation of Al Distribution in High-Silica ZSM-5 Zeolites for Enhancing Catalytic Performance.

The spatial distribution of framework Al (AlF) has been one of the important factors that affect the catalytic properties of zeolites in diverse chemical reactions; however, the synthesis of high-silica zeolites with special AlF distribution remains a challenge. In this study, we successfully synthesized high-silica ZSM-5 zeolites with a unique AlF distribution by employing pentaerythritol (PET) as an additive in the presence of a few tetrapropylammonium hydroxide (TPAOH). The results demonstrated that the introduction of PET led to a higher proportion of Al atoms located at the sinusoidal and/or straight channels. It was observed that the addition of PET prevented the interaction between TPA+ and tetrahedral [AlO4]- during the crystallization process, resulting in enhanced availability of TPA species in the form of ion-paired TPA+. This effect leads to AlF atoms dominantly distributed away from the intersection and located in narrow channels, where acidic sites more effectively inhibit hydrogen transfer and coke formation. In the reaction of dimethyl ether (DME) to olefins, the catalyst with a unique Al distribution exhibited a significant prolonged catalytic lifetime, surpassing traditional TPA-ZSM-5 by more than 2-fold and maintaining DME conversion above 90% for a maximum of 148 h. The results of multiple pulse experiments also showed that these PET-assisted ZSM-5 zeolites significantly enhanced the selectivity of propene and butene. This approach provides an effective strategy to regulate AlF distribution in high-silica ZSM-5 catalysts with the assistance of neutral alcohol. It holds great potential for application in the synthesis of other high-silica zeolites, thereby enriching the diversity of zeolite catalysis.

Low Palladium‐Loading HY Zeolite Catalyzed Hydrolysis of Hydrosilanes to Silanols and Alkoxysilanes

AbstractA low palladium‐loading heterogeneous catalyst has been developed for the hydrolysis of hydrosilanes to silanols and alkoxysilanes under mild and neutral reaction conditions with broad substrate scope. After five recycling runs, this low palladium‐loading catalyst keeps good activity for this transformation.

The effect of hierarchical pore structure SAPO-34 catalyst on the diffusion and reaction behavior in MTO reaction

Establishing the hierarchical pore structure is considered as a feasible approach for enhancing diffusion and improve catalytic efficiency of SAPO-34 zeolite in the methanol-to-olefin process. Nevertheless, under reaction conditions, the correlation among the diffusion behavior in the crystal, coke deposition behavior and catalytic performance of SAPO-34 catalysts with varying pore structures remains to be clarified. Herein, we revealed the structure–activity relationship between the hierarchical pore structure, the catalytic performance and the anti-coke deposition performance of the catalyst in the MTO reaction via the synergy of reaction–diffusion experiments and molecular simulation, then the mechanism of the hierarchical pore SAPO-34 catalyst to eliminate the diffusion limit and improve the accessibility of acid sites was clarified. The results demonstrated that the establishment of a hierarchical pore structure strengthened the diffusion of reactant methanol in the pores, leading to the diffusion resistance being reduced by 5 times and the diffusion coefficient being improved by two orders of magnitude. The key reaction rate-determining step shifted from micropores diffusion to the adsorption of acid sites in hierarchical pores, and the catalytic efficiency of the catalyst was increased by 3 times. Furthermore, with the establishing hierarchical pore technique, the expansion of the accommodation space for coke deposition led to a reduction in the blocking of pores due to coke deposition, particularly around the orifices. Moreover, the accessibility of the reactant molecules to the acid sites within the pores was enhanced, resulting in a balanced ratio between pore blockage and acid site coverage, thereby improving the anti-coke deposition performance of the SAPO-34 catalyst. This work can provide important foundational data and theoretical guidance for the study of reaction–diffusion synergistic interaction in zeolite catalysis reactions.

Influence of intracrystalline diffusion constraints enhanced by channel fluctuation on zeolite catalyst performance in isomerization and aromatization

In the realm of zeolite catalysis, understanding the role of intracrystalline diffusion constraints is of paramount significance, especially in the context of isomerization and aromatization reactions. This study delves deep into the structure-performance relationships, shedding light on the profound impact of channel fluctuation on isomerization and aromatization performance. Through meticulous analysis, we scrutinized the intracrystalline diffusion constraints of olefin intermediates integral to these reactions. ZSM-5, ZSM-22, Beta, and ZSM-12 zeolites, while possessing similar crystallinity, Si/Al ratio, acidity, and diffusion path length, display distinct channel fluctuations. Insightful in situ infrared desorption experiments coupled with molecular dynamic simulations underscore that these channel fluctuations intensify the intracrystalline diffusion constraints of olefin intermediates via an entropic trapping effect. Consequently, the isomers selectivity in n-octane isomerization adopts the sequence of Pt/Al2O3-ZSM-5 < Pt/Al2O3-ZSM-22 < Pt/Al2O3-Beta < Pt/Al2O3-ZSM-12, inversely correlating with channel fluctuation. This arises from the acceleration of undesired β-scission of olefin intermediates by intracrystalline diffusion constraints accentuated by channel fluctuation, leading to cracking by-products. Contrarily, the aromatic selectivity in 1-octene aromatization mirrors the opposite trend: ZSM-5 > ZSM-22 > Beta > ZSM-12, directly associating with channel fluctuation. This owes to the augmented intracrystalline diffusion constraints fostering the cyclization and hydrogen transfer of olefin intermediates, culminating in aromatic products. This study presents an in-depth investigation into how the diffusion constraints related to channel fluctuation influence product selectivity across different zeolite catalysts, offering valuable insights for future research and application in heterogeneous catalysis.

Advances and challenges in designing active site environments in zeolites for Brønsted acid catalysis.

Zeolites contain proton active sites in diverse void environments that stabilize the reactive intermediates and transition states formed in converting hydrocarbons and oxygenates to chemicals and energy carriers. The catalytic diversity that exists among active sites in voids of varying sizes and shapes, even within a given zeolite topology, has motivated research efforts to position and quantify active sites within distinct voids (synthesis-structure) and to link active site environment to catalytic behavior (structure-reactivity). This Feature Article describes advances and challenges in controlling the position of framework Al centers and associated protons within distinct voids during zeolite synthesis or post-synthetic modification, in identifying and quantifying distinct active site environments using characterization techniques, and in determining the influence of active site environments on catalysis. During zeolite synthesis, organic structure directing agents (SDAs) influence Al substitution at distinct lattice positions via intermolecular interactions (e.g., electrostatics, hydrogen bonding) that depend on the size, structure, and charge distribution of organic SDAs and their mobility when confined within zeolitic voids. Complementary post-synthetic strategies to alter intrapore active site distributions include the selective removal of protons by differently-sized titrants or unreactive organic residues and the selective exchange of framework heteroatoms of different reactivities, but remain limited to certain zeolite frameworks. The ability to identify and quantify active sites within distinct intrapore environments depends on the resolution with which a given characterization technique can distinguish Al T-site positions or proton environments in a given zeolite framework. For proton sites in external unconfined environments, various (post-)synthetic strategies exist to control their amounts, with quantitative methods to distinguish them from internal sites that largely depend on using stoichiometric or catalytic probes that only interact with external sites. Protons in different environments influence reactivity by preferentially stabilizing larger transition states over smaller precursor states and influence selectivity by preferentially stabilizing or destabilizing competing transition states of varying sizes that share a common precursor state. We highlight opportunities to address challenges encountered in the design of active site environments in zeolites by closely integrating precise (post-)synthetic methods, validated characterization techniques, well-defined kinetic probes, and properly calibrated theoretical models. Further advances in understanding the molecular details that underlie synthesis-structure-reactivity relationships for active site environments in zeolite catalysis can accelerate the predictive design of tailored zeolites for desired catalytic transformations.

Water structures on acidic zeolites and their roles in catalysis.

The local reaction environment of catalytic active sites can be manipulated to modify the kinetics and thermodynamic properties of heterogeneous catalysis. Because of the unique physical-chemical nature of water, heterogeneously catalyzed reactions involving specific interactions between water molecules and active sites on catalysts exhibit distinct outcomes that are different from those performed in the absence of water. Zeolitic materials are being applied with the presence of water for heterogeneous catalytic reactions in the chemical industry and our transition to sustainable energy. Mechanistic investigation and in-depth understanding about the behaviors and the roles of water are essentially required for zeolite chemistry and catalysis. In this review, we focus on the discussions of the nature and structures of water adsorbed/stabilized on Brønsted and Lewis acidic zeolites based on experimental observations as well as theoretical calculation results. The unveiled functions of water structures in determining the catalytic efficacy of zeolite-catalyzed reactions have been overviewed and the strategies frequently developed for enhancing the stabilization of zeolite catalysts are highlighted. Recent advancement will contribute to the development of innovative catalytic reactions and the rationalization of catalytic performances in terms of activity, selectivity and stability with the presence of water vapor or in condensed aqueous phase.

Post‐Synthetic Ensembling Design of Hierarchically Ordered FAU‐type Zeolite Frameworks for Vacuum Gas Oil Hydrocracking

AbstractZeolites hold importance as catalysts and membranes across numerous industrial processes that produce most of the world's fuels and chemicals. In zeolite catalysis, the rate of molecular diffusion inside the micropore channels defines the catalyst's longevity and selectivity, thereby influencing the catalytic efficiency. Decreasing the diffusion pathlengths of zeolites to the nanoscopic level by fabricating well‐organized hierarchically porous architecture can efficiently overcome their intrinsic mass‐transfer limitations without losing hydrothermal stability. We report a rational post‐synthetic design for synthesizing hierarchically ordered FAU‐type zeolites exhibiting 2D‐hexagonal (P6mm) and 3D‐cubic (Ia d) mesopore channels. The synthesis involves methodical incision of the parent zeolite into unit‐cell level zeolitic fragments by in situ generated base and bulky surfactants. The micellar ensembles formed by these surfactant‐zeolite interactions are subsequently reorganized into various ordered mesophases by tuning the micellar curvature with ion‐specific interactions (Hofmeister effect). Unlike conventional crystallization, which offers poor control over mesophase formation due to kinetic constraints, crystalline mesostructures can be developed under dilute, mild alkaline conditions by controlled reassembly. The prepared zeolites with nanometric diffusion pathlengths have demonstrated excellent yields of naphtha and middle‐distillates in vacuum gas oil hydrocracking with decreased coke deposition.

Post-Synthetic Ensembling Design of Hierarchically Ordered FAU-type Zeolite Frameworks for Vacuum Gas Oil Hydrocracking.

Zeolites hold importance as catalysts and membranes across numerous industrial processes that produce most of the world's fuels and chemicals. In zeolite catalysis, the rate of molecular diffusion inside the micropore channels defines the catalyst's longevity and selectivity, thereby influencing the catalytic efficiency. Decreasing the diffusion pathlengths of zeolites to the nanoscopic level by fabricating well-organized hierarchically porous architecture can efficiently overcome their intrinsic mass-transfer limitations without losing hydrothermal stability. We report a rational post-synthetic design for synthesizing hierarchically ordered FAU-type zeolites exhibiting 2D-hexagonal (P6mm) and 3D-cubic (Ia d) mesopore channels. The synthesis involves methodical incision of the parent zeolite into unit-cell level zeolitic fragments by in situ generated base and bulky surfactants. The micellar ensembles formed by these surfactant-zeolite interactions are subsequently reorganized into various ordered mesophases by tuning the micellar curvature with ion-specific interactions (Hofmeister effect). Unlike conventional crystallization, which offers poor control over mesophase formation due to kinetic constraints, crystalline mesostructures can be developed under dilute, mild alkaline conditions by controlled reassembly. The prepared zeolites with nanometric diffusion pathlengths have demonstrated excellent yields of naphtha and middle-distillates in vacuum gas oil hydrocracking with decreased coke deposition.

Accelerated Synthesis of Nanolayered MWW Zeolite by Interzeolite Transformation.

Hierarchical zeolites can offer substantial benefits over bulk zeolites in catalysis. A drawback towards practical implementation is their lengthy synthesis, often requiring complex organic templates. This work describes an accelerated synthesis of nanolayered MWW zeolite based on the combination of interzeolite transformation (IZT) with a dual-templating strategy. FAU zeolite, hexamethyleneimine (HMI), and cetyltrimethylammonium bromide (CTAB) were respectively employed as Al source and primary zeolite, structure directing agent, and exfoliating agent. This approach allowed to reduce the synthesis of nanolayered MWW to 48 h, which is a considerable advance over the state of the art. Tracking structural, textural, morphological, and chemical properties during crystallization showed that 4-membered-ring (4MR) units derived from the FAU precursor are involved in the faster formation of MWW in comparison to a synthesis procedure from amorphous precursor. CTAB restricts the growth of the zeolite in the c-direction, resulting in nanolayered MWW. Moreover, we show that this approach can speed up the synthesis of nanolayered FER. The merits of nanolayered MWW zeolites are demonstrated in terms of improved catalytic performance in the Diels-Alder cycloaddition of 2,5-dimethylfuran and ethylene to p-xylene compared to bulk reference MWW sample.

Simulated 13C chemical shifts used to investigate zeolite catalysis

Zeolites have been successfully applied on a wide range of reaction processes (Methanol to Hydrocarbons, Fluid Catalytic Cracking, etc) and continue to attract academic and industrial investigations. Understanding of the reaction mechanisms involved in zeolite catalysis has been a long standing issue due to the wide range of intermediates and products involved, which has hindered the industrial implementation of these materials. Thus, in order to determine and discriminate between each type of compound involved in the complex reaction mixture, computational simulations have been applied to analyse the 13C chemical shifts of a wide range of known or proposed intermediates and products. The first part of this study focuses on calculating the 13C chemical shifts of C1-C3 compounds commonly part of the reactant feed, comparing the results of mobile versus immobile states and determining which compounds could have their 13C chemical shifts superimposed over others. The second part focuses on C4-C6 olefins, analysing the differences stemming from: position of double bond, ramified structure, mobile and chemical state. Finally, the third part translates the same approach from the olefins study on aromatic derivatives.

Intergrowth Zeolites, Synthesis, Characterization, and Catalysis.

Microporous zeolites that can act as heterogeneous catalysts have continued to attract a great deal of academic and industrial interest, but current progress in their synthesis and application is restricted to single-phase zeolites, severely underestimating the potential of intergrowth frameworks. Compared with single-phase zeolites, intergrowth zeolites possess unique properties, such as different diffusion pathways and molecular confinement, or special crystalline pore environments for binding metal active sites. This review first focuses on the structural features and synthetic details of all the intergrowth zeolites, especially providing some insightful discussion of several potential frameworks. Subsequently, characterization methods for intergrowth zeolites are introduced, and highlighting fundamental features of these crystals. Then, the applications of intergrowth zeolites in several of the most active areas of catalysis are presented, including selective catalytic reduction of NOx by ammonia (NH3-SCR), methanol to olefins (MTO), petrochemicals and refining, fine chemicals production, and biomass conversion on Beta, and the relationship between structure and catalytic activity was profiled from the perspective of intergrowth grain boundary structure. Finally, the synthesis, characterization, and catalysis of intergrowth zeolites are summarized in a comprehensive discussion, and a brief outlook on the current challenges and future directions of intergrowth zeolites is indicated.

Synthetic methods to vary crystallite properties of TON zeolites and their consequences for Brønsted-acid catalyzed propene oligomerization

Brønsted acid zeolites catalyze light alkene oligomerization to higher molecular weight alkenes. Rates and selectivities of propene oligomerization in MFI zeolites are regulated by intrazeolite diffusional constraints imposed by heavier alkene products that become occluded within zeolitic micropores during reaction, and by active site properties that influence kinetic rate constants. Propene oligomerization rates and selectivity are also reported to vary with zeolite topology; however, evaluating the relative influences of kinetic and diffusional factors on oligomerization rate and selectivity and their dependence on zeolite framework topology is challenged by a dearth of synthesis methods to crystallize zeolite topologies with independently varied active site and crystallite properties. Herein, we use combinations of different structure directing agents to crystallize TON zeolites, which comprise medium-pore unidirectional straight channels, with varied crystallite sizes (0.9–5.4 μm) at similar H+-site density (∼0.3 H+/unit cell (u.c.)). Propene dimerization rates (per H+, 503 K) decrease systematically with increasing TON crystallite size over a wide range of propene pressures (16–607 kPa C3H6), reflecting the strong influence of intrazeolite diffusion limitations. The effective diffusivity of propene, estimated through the effectiveness factor formalism, systematically decreases (by ∼5×) with increasing propene pressure, indicating that the higher concentrations of heavier alkene products formed at higher propene pressures inhibit intrazeolite diffusion; however, this decrease is less severe compared to that for MFI samples of similar H+-site density. An analysis of product selectivity on zeolite topologies of independently varied pore size and dimensionality (TON, MFI, MOR) reveals that the smaller pore size of TON (∼5 Å diam.) leads to higher rate constants for propene dimerization, but also restricts the growth of larger oligomer products (e.g., ≥ C9), resulting in a lighter composition of occluded products that is also more weakly influenced by changes in propene pressure compared to those present in MFI (∼5–7 Å diam.). Together, these findings reveal the distinct roles of zeolite pore size and interconnectivity in governing kinetic factors and the composition of occluded products that regulate intrazeolite diffusion during propene oligomerization catalysis in medium-pore zeolites, and thereby rate and selectivity.

Effects of Surface, Interface, and Defect on Zeolite Catalysis Probed by a 3D Anisotropic Model

Zeolite catalysts are characterized by complex surface, interface, and defect structures, which are tightly related to diffusion and subsequent reaction in these catalysts. Herein, we develop a three-dimensional anisotropic model to describe anisotropic diffusion, surface/interface barriers, and reactions in zeolites with rich defects. Benzene alkylation with ethylene catalyzed by ZSM-5 zeolite is taken as the model reaction system. The results show that diffusion anisotropy largely affects the apparent reaction rate of a zeolite catalyst, indicating that diffusion anisotropy should be accounted for. Surface and interface diffusion barriers play an important role when diffusion limitation is strong in zeolites, and it is necessary to regulate surface and interface structures in these cases. Introducing defects into zeolites is favorable. The optimal size, volume, and spatial distribution of defects are obtained to balance diffusion and reaction. This work provides a powerful model and some useful guidance for the optimal design of zeolite catalysts.