Methanol to aromatics: isolated zinc phosphate groups on HZSM-5 zeolite enhance BTX selectivity and catalytic stability

Qiao, Jian; Wang, Jianqiang; Frenkel, Anatoly I.; Teng, Jiawei; Chen, Xiqiang; Xiao, Jingxian; Zhang, Tiezhu; Wang, Zhendong; Yuan, Zhiqing; Yang, Weimin

doi:10.1039/c9ra09657d

Cited by 16 publications

(7 citation statements)

References 75 publications

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“…A recent study reported that isolated zinc phosphate groups directly bonded to the channels of ZSM-5 zeolites enhance the selectivity and stability in the conversion of methanol to aromatics. Analysis by 31 P MAS NMR confirmed the preferential formation of zinc phosphate groups (3 ppm) and a complementary study by EXAFS also identified a Zn–P bond visible by a peak around 3.05 Å with the actual bond length of 3.28 Å and the absence of Zn–Zn bonding …”

Section: Nonmetalsmentioning

confidence: 75%

“…Analysis by 31 P MAS NMR confirmed the preferential formation of zinc phosphate groups (3 ppm) and a complementary study by EXAFS also identified a Zn−P bond visible by a peak around 3.05 Å with the actual bond length of 3.28 Å and the absence of Zn−Zn bonding. 906 Phosphorus-doped materials, mainly mesoporous carbons and graphene with phosphorus contents up to approximately 3 at. %, have also been explored as metal-free catalysts.…”

Section: Phosphorusmentioning

confidence: 99%

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Single-Atom Catalysts across the Periodic Table

et al. 2020

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Isolated atoms featuring unique reactivity are at the heart of enzymatic and homogeneous catalysts. In contrast, although the concept has long existed, single-atom heterogeneous catalysts (SACs) have only recently gained prominence. Host materials have similar functions to ligands in homogeneous catalysts, determining the stability, local environment, and electronic properties of isolated atoms and thus providing a platform for tailoring heterogeneous catalysts for targeted applications. Within just a decade, we have witnessed many examples of SACs both disrupting diverse fields of heterogeneous catalysis with their distinctive reactivity and substantially enriching our understanding of molecular processes on surfaces. To date, the term SAC mostly refers to late transition metal-based systems, but numerous examples exist in which isolated atoms of other elements play key catalytic roles. This review provides a compositional encyclopedia of SACs, celebrating the 10th anniversary of the introduction of this term. By defining single-atom catalysis in the broadest sense, we explore the full elemental diversity, joining different areas across the whole periodic table, and discussing historical milestones and recent developments. In particular, we examine the coordination structures and associated properties accessed through distinct single-atom−host combinations and relate them to their main applications in thermo-, electro-, and photocatalysis, revealing trends in element-specific evolution, host design, and uses. Finally, we highlight frontiers in the field, including multimetallic SACs, atom proximity control, and possible applications for multistep and cascade reactions, identifying challenges, and propose directions for future development in this flourishing field.

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Section: Nonmetalsmentioning

confidence: 75%

Section: Phosphorusmentioning

confidence: 99%

Single-Atom Catalysts across the Periodic Table

et al. 2020

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“…Catalysts playing significant roles in hydrogenation in naphthalene structure and selective cracking of naphthalenic structures-which yields one-ring aromatic hydrocarbons with alkyl chains-achieve the hydrotreating (HDT) and hydrocracking (HCK) processes used in the synthesis of BTX. Another method of producing BTX is the MTA (methanol to aromatics) reaction, which has been made possible primarily by developing methanol generated from biomass, shale gas, and coal via the syngas route [68,69]. BTX synthesis from syngas can reach good selectivity using a dual bed of MnCrOx-ZSM-512-MR zeolites.…”

Section: Production Of Benzene Toluene and Xylene (Btx) Aromaticsmentioning

confidence: 99%

The Role of Zeolite (Microporous Crystalline Aluminosilicates) In Catalytic Pyrolysis of Waste High- and Low-Density Polyethylene Bags for Production of Fuel and Chemicals: A Review

Jibreel,

Bayero,

Mohamaed

et al. 2024

Ind. J. Chem. Anal.

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This review provides a state-of-the-art summary of the role which zeolite plays as a catalyst via pyrolysis as a way of recovering fuels and chemicals from waste high and or low density polyethylene bags. It also highlighted the two types of zeolite (natural or synthetic) which are used as a two-stage pyrolysis−catalysis in giving a free waxing product to pure fuel and chemicals which can be subjected to further analyzing and or upgrading. As yield of oil/wax decreased with the addition of a zeolite as catalyst from 44 and 51 wt.%, (depending on the waste high density polyethylene “HDPE” or low density polyethylene bags “LDPE” and other factors). However, the composition of the pyrolysis−catalysis oils significantly increased in aromatic hydrocarbon content accordingly. In addition, the composition of the oils shifted from high molecular weight hydrocarbons (C16+) to fuel range hydrocarbons (C5−C15), with a high content of single-ring aromatic hydrocarbons such as benzene, toluene, ethylbenzene, xylenes, and styrene. This process shows great potential for production of fuels or chemicals, and also addresses the urgent issue of waste HDPE and or LDPE disposal.

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“…By contrast, as reported in the literature, the addition of phosphorus species on HZSM-5 zeolites could effectively improve the catalyst stability and resistance to coke formation as compared with unmodified HZSM-5 zeolites. [3,33,34] In order to further improve the catalyst lifetime and BTX selectivity in the MTA reaction, nano-sized HZSM-5 zeolites modified by both ZnSiF 6 Á6H 2 O and phosphoric acid (Zn-P/HZSM-5) are prepared in this study. Moreover, nano-sized HZSM-5 zeolites modified by phosphoric acid (P/HZSM-5) with different molar concentrations are prepared as reference sample.…”

Section: Introductionmentioning

confidence: 99%

“…[ 2 ] By contrast, there is a surplus generation of methanol from coal mining. [ 3 ] In this context, the methanol to aromatics (MTA) reaction attracts the interest of industrial and academic researchers, which is considered a high‐efficiency nonpetroleum route to increase the production of BTX hydrocarbons by consuming excessive amounts of methanol.…”

Section: Introductionmentioning

confidence: 99%

Highly shape‐selective Zn‐P/HZSM‐5 zeolite catalyst for methanol conversion to light aromatics

Jia

Wang

Zhang

et al. 2020

Applied Organom Chemis

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A highly shape-selective and relatively long-lifetime HZSM-5-based catalyst (Zn-2P/HZSM-5) was prepared by chemical modification with both ZnSiF 6 Á6H 2 O and H 3 PO 4 solution. The phosphoric acid modification could effectively modulate the Brønsted acid strength of the HZSM-5 catalyst, which promotes the oligomerization, alkylation, cyclization, and hydrogen transfer reactions. The introduction of Zn-Lewis acid sites significantly improved the dehydroaromatization of higher olefins. All of these were very beneficial for the generation of BTX (i.e. benzene, toluene, and xylene) hydrocarbons in aromatization of methanol. The coke amount and the average rate of coke formation decreased over the Zn-2P/HZSM-5 catalysts, which may largely be ascribed to its lower strong acid sites and lower outer surface acidity. The catalytic performance of methanol aromatization showed that the Zn-2P/HZSM-5 catalyst exhibited the highest BTX selectivity of about 46.76% and the longest catalytic lifetime of about 498 h at T = 400 C, P = 0.1 MPa, and weight hourly space velocity = 0.7 h −1 .

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Methanol to aromatics: isolated zinc phosphate groups on HZSM-5 zeolite enhance BTX selectivity and catalytic stability

Abstract: HZSM-5 zeolite combined with unique zinc and phosphorus species, yields excellent selectivity (∼85%) to BTX (benzene, toluene, xylenes) in aromatic products.

Cited by 16 publications

References 75 publications

Single-Atom Catalysts across the Periodic Table

Single-Atom Catalysts across the Periodic Table

The Role of Zeolite (Microporous Crystalline Aluminosilicates) In Catalytic Pyrolysis of Waste High- and Low-Density Polyethylene Bags for Production of Fuel and Chemicals: A Review

Highly shape‐selective Zn‐P/HZSM‐5 zeolite catalyst for methanol conversion to light aromatics

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