The effects of methanol space velocity and inlet methanol partial pressure on lifetime and selectivity of methanol-toolefins catalysis are examined and interpreted to elucidate reaction parameters and propose intermediates and reactions relevant to catalyst deactivation. The propensity of active centers in HSSZ-13 to turn over for methanol-to-olefins catalysis increases when the methanol partial pressure local to organic co-catalysts confined within the inorganic chabazite cages is lower either by decreasing methanol space velocity or inlet methanol partial pressure. High initial methane selectivity reveals methanol disproportionation, to methane and formaldehyde, a primary reaction, and continual methane formation implicates persistent participation of methanol in bimolecular hydrogen transfer reactions throughout the catalyst lifetime. Methane selectivity correlates positively with inlet methanol partial pressure reflecting enhanced relative rates of formaldehyde formation with increasing methanol partial pressure. Subsequent alkylation reactions of olefins-and aromatics-based CC chain growth carriers by formaldehyde accelerate the relative rates of hydrogen transfer and proliferate, apparently, the precursors mediating transformation of active hydrocarbon pool participants to those inducing catalyst deactivation.

Bifunctional strategies exploiting the selective and catalytic decomposition of formaldehyde by Y 2 O 3 improve the lifetime of CHA zeotypes and zeolites for methanol-toolefins catalysis 4-fold, as quantified by total turnovers, without disrupting the inherently high selectivity to light olefins. The improvement in catalyst lifetime increases with increasing proximity between H + sites of the zeotype/zeolite and the surface of the rare earth metal oxide. This proximity effect demonstrates crucial transport of formaldehyde between and within zeotypic/zeolitic domains on catalyst lifetime. These results provide mechanistic insights revealing formaldehyde as an accelerant for the initiation and termination of chain carriers and exemplify a strategy for designing improved methanol-toolefins catalysts by optimizing (bi)functionality and reaction-transport dynamical phenomena.

Conspectus Solid catalysts deployed in industrial processes often undergo deactivation, requiring frequent replacement or regeneration to recover the loss in activity. Regeneration occurs under conditions distinct from, and typically more harsh than, the catalysis, placing strict requirements on physicochemical material properties that divert catalyst optimization toward addressing regenerability over high activity and selectivity. Deactivation arises from mechanical, structural, or chemical modifications to active sites, promoters, and their surrounding matrices, and the prevailing mechanism for deactivation varies with the reaction, the catalyst, and the reaction conditions. Methanol-to-hydrocarbons processes utilize zeolites and zeotypescrystalline, microporous oxides widely deployed as catalysts in the refining and petrochemical industriesas solid acid catalysts. Deposition and growth of highly unsaturated carbonaceous residues within the micropores congest molecular transport and block active sites, resulting in deactivation. In this Account, we describe studies probing the underlying mechanisms of deactivation in methanol-to-hydrocarbons catalysis and discuss examples of leveraging the acquired mechanistic insights to mitigate deactivation and prolong catalyst lifetime. These fundamental principles governing carbon deposition within zeolites and zeotypes provide opportunity to broaden versatility of processes for C1 valorization and to relax constraints imposed by hydrothermal catalyst stability considerations to achieve more active and more selective catalysis. Methanol-to-hydrocarbons catalysis occurs via a chain carrier mechanism. A zeolite/zeotype cavity hosts an unsaturated hydrocarbon guest to together constitute the supramolecular chain carrier that engages in a complex network of reactions for chain carrier propagation. Productive propagation reactions include olefin methylation, aromatic methylation, and aromatic dealkylation. Methanol undergoes unproductive dehydrogenation to formaldehyde via methanol disproportionation and olefin transfer hydrogenation. Subsequent alkylation reactions between formaldehyde and active olefinic/aromatic cocatalysts instigate cascades for dehydrocyclization, resulting in the formation of inactive polycyclic aromatic hydrocarbons and termination of the chain carrier. Addition of a distinct catalytic function that selectively decomposes formaldehyde mitigates chain carrier termination without disrupting the high selectivity to ethylene and propylene in methanol-to-hydrocarbons catalysis on small-pore zeolites and zeotypes. The efficacy of this bifunctional strategy to prolong catalyst lifetime increases with increasing proximity between the active sites for formaldehyde decomposition and the H+ sites of the zeolite/zeotype. Coprocessing sacrifical hydrogen donors mitigates chain carrier termination by intercepting, via saturation, intermediates along dehydrocyclization cascades. This strategy increases in efficacy with increasing concentration of the hydrogen donor a...

The concurrent propagation of the aromatics-based and olefins-based catalytic cycles at early stages of the methanol-to-olefins reaction over HSAPO-34 and the resulting consequences on light olefins selectivities are demonstrated with 13 C 3-propylene/ 12 C 2-dimethyl ether isotopic tracing studies at 623 K and sub-complete dimethyl ether conversions. Transients in effluent product selectivities were rationalized by the maturation of the entrained hydrocarbon pool where catalyst turnover number is introduced as a compendious descriptor of reaction progress. The distinct 13 C-content of ethylene from other effluent products and its agreement with the 13 C-contents of entrained polymethylbenzenes indicate that ethylene is a product of aromatics-based dealkylation events while the match between methylationpredicted and experimentally observed 13 C-contents for C 5+ olefins establishes that they are products of olefins-based methylation events. Methanol-to-olefins conversion proceeds through a dual cycle mechanism proposed earlier for methanol conversion over other solid acid catalysts where the topology of HSAPO-34 specifically engenders the prevalence of the aromatics-based cycle at >∼200 mol C mol −1 H + catalyst turnovers.

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