Development of a post-synthetic method for tuning the Al content of OSDA-free Beta as a catalyst for conversion of methanol to olefins

Otomo, Ryoichi; Müller, Ulrich; Feyen, Mathias; Yilmaz, Bilge; Meng, Xiangju; Xiao, Feng‐Shou; Gies, Hermann; Bao, Xinhe; Zhang, Weiping; Vos, Dirk De; Yokoi, Toshiyuki

doi:10.1039/c5cy00944h

Cited by 37 publications

(17 citation statements)

References 55 publications

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“…Both the aromatics and olefin cycles were revealed to function in the reaction 19d,84. Otomo et al prepared a series of dealuminated high‐silica Beta via high‐temperature calcination and acid treatment . They found that the propylene selectivity could achieve 37.4–49.7% over the material with a Si/Al ratio of 112.…”

Section: Toward Enhanced Ethylene or Propylene Selectivitymentioning

confidence: 99%

Recent Progress in Methanol‐to‐Olefins (MTO) Catalysts

et al. 2019

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Among the 8-MR molecular sieves, silicoaluminophosphate SAPO-34 with 3D channels and moderate acid strength represents the most interesting one, the light olefins selectivity of which could reach up to 90% or even higher. [7] The excellent MTO performance of SAPO-34 was first reported by Dalian Institute of Chemical Physics (DICP) in 1990. [8] The researchers also demonstrated the good regeneration stability and high-temperature steam stability of Inspired by these pioneering discoveries, extensive research efforts have been devoted to SAPO-34 focusing on the elucidation of its crystallization mechanism, synthesis optimization, and the relevant catalytic studies, which greatly promote the technological development of the MTO process. Although SAPO-34 exhibits high catalytic activity and high selectivity toward light olefins, it suffers a rapid deactivation due to the coke deposition. Moreover, the MTO reaction on SAPO-34 catalyst is highly exothermal. These features determine that the industrial MTO process based on SAPO-34 catalyst has to adopt fluidized bed reactor, which allows efficient heat transfer and enables the continuous regeneration of the catalyst. In 2010, the world's first commercial MTO unit was successfully commissioned in Baotou, China by DICP (named DMTO technology). [5,10] The production capacity of ethylene and propylene is 0.6 Mt a −1 . To supply commercial catalysts for the DMTO unit, a 2000 t a −1 catalyst manufacturing plant was started up in Dalian in 2008. Afterward, DICP developed the DMTO-II technology, in which the byproducts of C 4 + are separated and introduced into a fluidized-bed cracking reactor to improve the yields of ethylene and propylene. Both the cracking unit and the MTO unit share one regenerator and use the same catalyst. By the end of 2018, thirteen DMTO units have been put into operation with a total production capacity of 7.16 Mt a −1 . Moreover, DICP launched the new generation of DMTO catalyst and completed the pilot test of the DMTO-III technology in 2018, both of which aim to further improve the olefins yield of DMTO units. The catalyst and technology development of the DMTO process are summarized in Figure 1.Based on SAPO-34 catalyst, UOP and Norsk Hydro also developed an MTO process with a low-pressure fast fluidizedbed reactor. [11] In 2013, a commercialized MTO plant (0.3 Mt a −1 olefins) was commissioned in Nanjing, China, which combines the UOP/Hydro MTO process and the total/UOP olefin cracking process to enhance the yield of ethylene and propylene. In addition, Shanghai Research Institute of Petrochemical Technology Methanol conversion to olefins, as an important reaction in C1 chemistry, provides an alternative platform for producing basic chemicals from nonpetroleum resources such as natural gas and coal. Methanol-to-olefin (MTO) catalysis is one of the critical constraints for the process development, determining the reactor design, and the profitability of the process. After the construction and commissioning of the world's first MTO plant by Dalian I...

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Section: Toward Enhanced Ethylene or Propylene Selectivitymentioning

confidence: 99%

Recent Progress in Methanol‐to‐Olefins (MTO) Catalysts

et al. 2019

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“…The peak at −53 ppm in the 27 Al MAS NMR demonstrates the formation of tetrahedral coordination environment Al(OSi) 4 − , meanwhile, the absence of the bond at 0 ppm suggests that there is not octahedral coordination aluminum in the V‐Si‐Al gel. Furthermore, the band at 561 cm −1 of FTIR spectra of the aged V‐Si‐Al gel ascribes to vibration of double 5‐members ring (Figure b), which demonstrates the formation of secondary structure units of ZSM‐5 through the further condensation of TO 4 (T=Si or Al)in the V‐Si‐Al gel ,…”

Section: Resultsmentioning

confidence: 94%

Template‐Free Synthesis of High‐Content Vanadium‐Doped ZSM‐5 with Enhanced Catalytic Performance

et al. 2017

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The high cost of preparation of transition metal doped ZSM‐5 zeolite is limited to the use of organic template such as tetrapropylammonium hydroxide or tetrapropylammonium bromide. In this work, vanadium atom was successfully incorporated into the framework of ZSM‐5 zeolite without using any organic template. Moreover, the method not only decreases the preparation cost of vanadium doped ZSM‐5, but also greatly enhances the utilization ratio of vanadium atom. Vanadium atom mainly exists as tetrahedral coordination in the framework of ZSM‐5 which was demonstrated by the ultraviolet visible and X‐ray photoelectron spectrum. Furthermore, vanadium doped ZSM‐5 performs high and stability catalytic activity in the oxidation of styrene compared to that of the catalyst prepared by the traditional organic template method ascribe to the greatly increase of tetrahedral vanadium species.

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“…Structural modification after synthesis is commonly used to achieve a better hierarchical structure. Acid or alkaline treatment can help the dealumination process and generate mesopores . A fluoride ion treatment helps the reconstruction of crystal structures.…”

Section: Improving Transport Efficiency By the Application Of Discretmentioning

confidence: 99%

Transport Phenomena in Zeolites in View of Graph Theory and Pseudo‐Phase Transition

Cai

Xiong

Zhang

2019

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hierarchical zeolites to enhance diffusion. A parallel phenomenon, coking, which is the primary cause of the deactivation of zeolite catalysts, leads to pore blockage in the zeolite and adversely affects diffusion rates, and also wastes feedstock and lowers atom efficiency. The suppression of coke formation is also a central topic in catalysis.Traditional kinetic studies regard catalyst pellets as isotropic and describe diffusion with a lumped diffusion coefficient, although in Monte Carlo studies, the zeolite topology is used, and models based on zeolite topology and network are built and the strong coupling of diffusion and deactivation is analyzed. As a complement to these, it is expected that in modern transport research, more use will be made of discrete models. Some exciting new findings from these include pseudophase transition phenomena noted in the deactivation process and the fast transport in nanosized channels and hierarchical catalyst structure. In this review, we seek to provide insights on zeolite diffusion studies from the traditional view to modern discrete models. Transport in Zeolites www.advancedsciencenews.com

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Development of a post-synthetic method for tuning the Al content of OSDA-free Beta as a catalyst for conversion of methanol to olefins

Cited by 37 publications

References 55 publications

Recent Progress in Methanol‐to‐Olefins (MTO) Catalysts

Recent Progress in Methanol‐to‐Olefins (MTO) Catalysts

Template‐Free Synthesis of High‐Content Vanadium‐Doped ZSM‐5 with Enhanced Catalytic Performance

Transport Phenomena in Zeolites in View of Graph Theory and Pseudo‐Phase Transition

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