Industrial applications of zeolite catalysis: production and uses of light olefins

Bellussi, Giuseppe; Pollesel, Paolo

doi:10.1016/s0167-2991(05)80466-5

Cited by 72 publications

(48 citation statements)

References 30 publications

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“…These zeotype materials are formed by tetrahedral Al and P atoms in strict alternation, connected by O atoms. Since this early achievement, many new AlPO-related materials with diverse architectures have been described (8)(9)(10)(11). The discovery of the extra-large VPI-5 AlPO molecular sieve containing 18-ring channels was a remarkable breakthrough, being the first extra-large-pore crystalline material ever synthesized (12).…”

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confidence: 99%

Synthesis of an extra-large molecular sieve using proton sponges as organic structure-directing agents

Martínez-Franco

Moliner

Yun

et al. 2013

Proc. Natl. Acad. Sci. U.S.A.

109

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The synthesis of crystalline microporous materials containing large pores is in high demand by industry, especially for the use of these materials as catalysts in chemical processes involving bulky molecules. An extra-large-pore silicoaluminophosphate with 16-ring openings, ITQ-51, has been synthesized by the use of bulky aromatic proton sponges as organic structure-directing agents. Proton sponges show exceptional properties for directing extra-large zeolites because of their unusually high basicity combined with their large size and rigidity. This extra-large-pore material is stable after calcination, being one of the very few examples of hydrothermally stable molecular sieves containing extra-large pores. The structure of ITQ-51 was solved from submicrometer-sized crystals using the rotation electron diffraction method. Finally, several hypothetical zeolites related to ITQ-51 have been proposed.aluminophosphate | extra-large microporous materials | zeolite synthesis

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confidence: 99%

Synthesis of an extra-large molecular sieve using proton sponges as organic structure-directing agents

Martínez-Franco

Moliner

Yun

et al. 2013

Proc. Natl. Acad. Sci. U.S.A.

109

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“…The combustion of fossil fuels and their derivatives, however, has been associated with a steady increase in greenhouse gas levels worldwide [1], and has been implicated in climate change [2]. A more attractive solution to the world's energy needs would draw upon multiple renewable resources and prevent greenhouse gas emissions.…”

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confidence: 99%

“…Similar to the petrochemical industry, where crude oil is fractionated and refined to produce varying types of fuels and specialty chemicals, biomass could be used in a bio-refining process to achieve similar results. However, biomass-derived molecules are small molecules that have an abundance of oxygen and therefore, any process used to produce biofuels and specialty chemicals must create C-C bonds to form longer hydrocarbon chains and reduce the oxygen/carbon ratio from the biomass-derived intermediates [1].…”

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confidence: 99%

“…1.1 References [1] Huber, G. W.; Iborra, S.; Corma, A., "Synthesis of transportation fuels from biomass:…”

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confidence: 99%

“…Enolate formation is dictated by the gas phase stability of the enolate and its stabilization on the acid sites on the catalyst surface. Using pulsed ionization high pressure mass spectroscopy, Burkell et al [1] determined the gas phase acidities of C3-C10…”

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confidence: 99%

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Mechanistic Insights into Heterogeneous Catalytic Conversion of Light Oxygenates and Olefins from Biomass Derivatives

Fitzharris¹

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The decreasing availability of fossil fuel resources has generated growing interests in chemical transformations of small oxygenates and olefin molecules derived from biomass sources into larger hydrocarbon fuel and chemical precursors. Aldol condensation of light oxygenates and alkene oligomerization of light olefins which proceed via C-C bond formation paths show potential for production of valuable chemical and fuel precursors. However, oxygenate coupling by C-O bond formation such as in the reaction of methanol to dimethoxy methane (DMM) can occur together with C-C formation processes and lead to coke formation and catalyst deactivation. First principle density functional theory (DFT) calculations were carried out to probe the C-C as well as C-O coupling pathways over metal oxide as well as zeolite catalysts. More specifically we examined the paths for aldol condensation of aldehydes and ketones over ZrO2 and ZnO and alkene oligomerization and oxygenate coupling in zeolites.These three systems show similarities in the formation and stability of charged intermediates, stabilization of transition states, and intermolecular and catalytic steric effects on the activity for these reactions. Aldol condensation of C2-C4 aldehydes and ketones over model ZrO2 and ZnO surfacesshow that the rates are controlled by the kinetics for enolate formation, with m-ZrO2 being the most active surface for aldol condensation. The rates of reaction in these systems were controlled by the stabilization of an adsorbed enolate that forms on the oxide where smaller aldehydes show higher interaction energies and thus faster rates of reaction.Alkene oligomerization of C2-C4 olefins which proceed via similar C-C bond formation steps in TON, MFI, and MOR zeolites show similar results, where the relative differences in stabilization of the reacting carbenium ion by the zeolite as well as differences in alkene adsorption largely determined the overall activity for alkene oligomerization in various zeolite structures. TON was predicted to be the most active catalyst as the narrow 1-D channel maximizes the number of potential secondary interactions with the carbenium ion at the transition state.

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Catalysis at Room Temperature: Perspectives for Future Green Chemical Processes

Lam¹,

Li²,

Chau³

et al. 2015

Advances in Bioenergy

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Industrial applications of zeolite catalysis: production and uses of light olefins

Cited by 72 publications

References 30 publications

Synthesis of an extra-large molecular sieve using proton sponges as organic structure-directing agents

Synthesis of an extra-large molecular sieve using proton sponges as organic structure-directing agents

Mechanistic Insights into Heterogeneous Catalytic Conversion of Light Oxygenates and Olefins from Biomass Derivatives

Catalysis at Room Temperature: Perspectives for Future Green Chemical Processes

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