A methanol to olefins review: Diffusion, coke formation and deactivation on SAPO type catalysts

The kaleidoscopic applications of zeolite catalysts (zeo-catalysts) in petrochemical processes has been considered as one of the major accomplishments in recent decades. About twenty types of zeolite have been industrially applied so far, and their versatile porous architectures have contributed their most essential features to affect the catalytic efficiency. This review depicts the evolution of pore models in zeolite catalysts accompanied by the increase in industrial and environmental demands. The indispensable roles of modulating pore models are outlined for zeo-catalysts for the enhancement of their catalytic performances in various industrial processes. The zeolites and related industrial processes discussed range from the uni-modal micropore system of zeolite Y (12-ring micropore, 12-R) in fluid catalytic cracking (FCC), zeolite ZSM-5 (10-R) in xylene isomerization and SAPO-34 (8-R) in olefin production to the multi-modal micropore system of MCM-22 (10-R and 12-R pocket) in aromatic alkylation and the hierarchical pores in FCC and catalytic cracking of C4 olefins. The rational construction of pore models, especially hierarchical features, is highlighted with a careful classification from an industrial perspective accompanied by a detailed analysis of the theoretical mechanisms.

Recent advances of pore system construction in zeolite-catalyzed chemical industry processes

SAPO-34 materials with comparable Bronsted acid site density but different crystal sizes were applied as methanol-to-olefin (MTO) catalysts to elucidate the effect of the crystal size on their deactivation behaviors. 13C HPDEC MAS NMR, FTIR, and UV/vis spectroscopy were employed to monitor the formation and nature of organic deposits, and the densities of accessible Bronsted acid sites and active hydrocarbon-pool species were studied as a function of time-on-stream (TOS) by 1H MAS NMR spectroscopy. The above-mentioned spectroscopic methods gave a very complex picture of the deactivation mechanism consisting of a number of different steps. The most important of these steps is the formation of alkyl aromatics with large alkyl chains improving at first the olefin selectivity, but hindering the reactant diffusion after longer TOS. The hindered reactant diffusion leads to a surplus of retarded olefinic reaction products in the SAPO-34 pores accompanied by their oligomerization and the formation of polycyclic a...

Mechanisms of the Deactivation of SAPO-34 Materials with Different Crystal Sizes Applied as MTO Catalysts

Methanol-to-olefin (MTO) conversion has proven to be one of the most successful non-petrochemical routes for producing light olefins. Silicoaluminophosphate (SAPO) zeolite SAPO-34 is one of the best industrial catalysts for MTO conversion, but suffers from rapid deactivation due to the inherent diffusion bottleneck limited by the narrow eight-ring pore openings. To improve the MTO performance, considerable synthetic efforts have been devoted to decrease the crystal size of zeolites or introduce secondary larger pores in zeolite crystals to form hierarchical structures. This review mainly focuses on presenting the state-of-the-art synthetic strategies for nanosized and hierarchical SAPO-34 catalysts with excellent MTO performance. Furthermore, the industrialization of SAPO-34 catalysts for the MTO reaction, and some current problems and future prospects for the synthesis of SAPO-34 catalysts, are also pointed out. We expect that this review can not only shed some light on the preparation of SAPO-34 catalysts, but also stimulate the future development of high-performance SAPO-34 catalysts to meet the increasing demands of the chemical industry.

The state-of-the-art synthetic strategies for SAPO-34 zeolite catalysts in methanol-to-olefin conversion

The present investigation provides an overview of the current technology related to the green diesel, from the classification and chemistry of the available biomass feedstocks to the possible production technologies and up to the final fuel properties and their effect in modern compression ignition internal combustion engines. Various biomass feedstocks are reviewed paying attention to their specific impact on the production of green diesel. Then, the most prominent production technologies are presented such as the hydro-processing of triglycerides, the upgrading of sugars and starches into C15–C18 saturated hydrocarbons, the upgrading of bio-oil derived by the pyrolysis of lignocellulosic materials and the “Biomass-to-Liquid” (BTL) technology which combines the production of syngas (H2 and CO) from the gasification of biomass with the production of synthetic green diesel through the Fischer-Tropsch process. For each of these technologies the involved chemistry is discussed and the necessary operation conditions for the maximum production yield and the best possible fuel properties are reviewed. Also, the relevant research for appropriate catalysts and catalyst supports is briefly presented. The fuel properties of green diesel are then discussed in comparison to the European and US Standards, to petroleum diesel and Fatty Acid Methyl Esters (FAME) and, finally their effect on the compression ignition engines are analyzed. The analysis concludes that green diesel is an excellent fuel for combustion engines with remarkable properties and significantly lower emissions.

https://www.mdpi.com/1996-1073/12/5/809/pdf

Green Diesel: Biomass Feedstocks, Production Technologies, Catalytic Research, Fuel Properties and Performance in Compression Ignition Internal Combustion Engines

The synthesis of SAPO-34 with mixed template and its catalytic performance for methanol to olefins reaction

Synthesis of SAPO-34 with small and tunable crystallite size by two-step hydrothermal crystallization and its catalytic performance for MTO reaction

Rapid deactivation and short lifetime are challenges for SAPO-34 catalysts for the reaction of methanol to olefins (MTO). To overcome these drawbacks, SAPO-34 on fully calcined kaolin microspheres ...

Jie Hu

Papers

The synthesis of SAPO-34 with mixed template and its catalytic performance for methanol to olefins reaction

Synthesis of SAPO-34 with small and tunable crystallite size by two-step hydrothermal crystallization and its catalytic performance for MTO reaction

In Situ Synthesis of SAPO-34 Grown onto Fully Calcined Kaolin Microspheres and Its Catalytic Properties for the MTO Reaction