Nano-sized H-ZSM-5 zeolite catalyzes aldol condensation reaction to prepare methyl acrylate and acrylic acid

Xie, Mingguan; Ni, Youming; Fang, Xudong; Liu, Hongchao; Chen, Zhiyang; Ding, Xiangnong; Wang, Linying; Zhu, Wenliang

doi:10.1039/d2cy00447j

Cited by 11 publications

(4 citation statements)

References 33 publications

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“…[27,28] For the production of MMA based on aldol condensation, the traditional process mainly involves four steps as show in Figure 1b, including paraformaldehyde (PFA) depolymerization or oxidative dehydrogenation of MeOH to formaldehyde (FY), aldol condensation of MAc and FY to methyl acrylate (MA), MA hydrogenation to methyl propionate (MP), and aldol condensation of MP and FY to MMA, which has aroused wide research interests in previous studies. [29][30][31][32][33][34][35] Interestingly, based on the molecular formula of MMA, it is postulated to be synthesized by the condensation of methyl acetate (MAc) and 2 molar equivalents of formaldehyde (FY), in which FY can be obtained from the dehydrogenation of methanol. Hence, the overall reaction can be designed as:…”

Section: Resultsmentioning

confidence: 99%

Leveraging the Proximity and Distribution of Cu−Cs Sites for Direct Conversion of Methanol to Esters/Aldehydes

Chen,

Zuo,

Sang

et al. 2023

Angew Chem Int Ed

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Methanol serves as a versatile building‐block for various commodity chemicals, and the development of industrially promising strategies for its conversion remains the ultimate goal in methanol chemistry. In this study, we design a dual Cu−Cs catalytic system that enables a one‐step direct conversion of methanol and methyl acetate/ethanol into high value‐added esters/aldehydes, with customized chain length and saturation by leveraging the proximity and distribution of Cu−Cs sites. Cu−Cs at a millimeter‐scale intimacy triggers methanol dehydrogenation and condensation, involving proton transfer, aldol formation, and aldol condensation, to obtain unsaturated esters and aldehydes with selectivities of 76.3 % and 31.1 %, respectively. Cu−Cs at a micrometer‐scale intimacy significantly promotes mass transfer of intermediates across catalyst interfaces and their subsequent hydrogenation to saturated esters and aldehydes with selectivities of 67.6 % and 93.1 %, respectively. Conversely, Cu−Cs at a nanometer‐scale intimacy alters reaction pathway with a similar energy barrier for the rate‐determining step, but blocks the acidic‐basic sites and diverts the reaction to byproducts. More importantly, an unprecedented quadruple tandem catalytic production of methyl methacrylate (MMA) is achieved by further tailoring Cu and Cs distribution across the reaction bed in the configuration of Cu−Cs||Cs, outperforming the existing industrial processes and saving at least 15 % of production costs.

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Section: Resultsmentioning

confidence: 99%

Leveraging the Proximity and Distribution of Cu−Cs Sites for Direct Conversion of Methanol to Esters/Aldehydes

Chen,

Zuo,

Sang

et al. 2023

Angew Chem Int Ed

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“…Hence, it is of significance to explore alternative green and efficient routes for small aliphatic ester and aldehyde production through sustainable resources. Recently, a new route of preparing MA (AA) via vapor-phase aldol condensation from methyl acetate (MeOAc) and formaldehyde (FA) shows significantly promising advantages in the academia and industry owing to the short process and the fact that the feedstock (both MeOAc and FA) could be easily produced from natural gas, biomass, and coal-based chemicals. − …”

Section: Introductionmentioning

confidence: 99%

Preparation of Methyl Acrylate through Catalytic Aldol Condensation over Cs/TS-1 Catalysts

Wang,

Gao,

Xing

et al. 2024

ACS Sustainable Chem. Eng.

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It is of great importance to design heterogeneous catalysts for aldol condensation of methyl acetate and formaldehyde to realize the green and sustainable production of methyl acrylate. Herein, Cs-based heterogeneous aldol condensation catalysts via incipient wetness impregnation were optimized through enhanced interaction between supports (amorphous SiO 2 , silicalite-1, and TS-1) and Cs sites. By various characterization techniques such as IR−OH and 133 Cs magic angle spinning NMR, it was proven that Cs/TS-1 exhibited the strongest interaction between TS-1 and Cs species with the lowest preservation of −OH groups and the largest shift toward a higher field in NMR spectra after Cs modification as well as the highly dispersed Cs sites. Correspondingly, Cs/ TS-1 shows the best catalytic performance in the gas aldol condensation of methyl acetate with formaldehyde. Importantly, it is effective to verify that the better catalytic performance is closely related to the Si/Ti−O−Cs active centers rather than that of Cs 2 O through H 2 O washing. The turnover number of Cs species of the Cs/TS-1 catalyst (468.9) was much higher than that of the silicon-supported Cs catalyst (Cs/S-1, 343.3; Cs/SiO 2 , 211.3), and the selectivity toward methyl acetate over Cs/TS-1 (81.8%) was higher than those for Cs/S-1 (73.2%) and Cs/SiO 2 (75.0%).

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“…As important intermediates in organic synthesis, acrylic acid and its derivatives, such as methyl acrylate, are widely used in producing adhesives, synthetic resins, and paint and coating additives [1,2] . Acrylic acid can be obtained through the two-step oxidation of propylene, of which the first step is propylene oxidation to acrolein, then further oxidation to acrylic acid [3] , and esterification to methyl acrylate. This process is long and complex, and there is a risk of excessive oxidation of propylene and the required products.…”

Section: Introductionmentioning

confidence: 99%

Highly selective production of renewable methyl acrylate via aldol condensation over Cu modified nitrogen-containing Beta zeolites

Wang,

Xu,

Zhang

2024

Chem Synth

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Highly selective synthesis of renewable methyl acrylate from bio-sourced formaldehyde and methyl acetate through one-step aldol condensation was successfully realized on Cu-modified nitrogen-containing Beta (NBeta) catalysts. Silicon-29 magic angle spinning nuclear magnetic resonance (29Si MAS NMR), Fourier transform infrared spectroscopy (FT-IR), temperature-programmed desorption of ammonia, temperature-programmed desorption of carbon dioxide, and element analysis indicate that nitridation weakens the acid strength, reduces the number of acidic sites and introduces basic sites through the formation of Si−N bond on Beta zeolites, thereby promoting methyl acrylate selectivity and reducing the coke formation. Adding Cu into NBeta further finely tunes the basicity and acidity balance and thus inhibits the by-product acetone. High methyl acrylate selectivity of 95% and formaldehyde conversion of 99% were achieved over Cu/NBeta catalyst under optimized conditions. The coke content decreases remarkably from 28% on H-form Beta (HBeta) zeolites to 17% on NBeta zeolites doped with Cu due to its appropriate basicity/acidity. Cu/NBeta has good regeneration capability, and the weakening of Si-N species may account for the decline of catalytic performance after successive regeneration. The catalytic performance was restored when the regenerated catalyst was nitridated again.

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Nano-sized H-ZSM-5 zeolite catalyzes aldol condensation reaction to prepare methyl acrylate and acrylic acid

Abstract: The aldol condensation reaction of formaldehyde and methyl acetate is generally considered as a green, economical, non-petroleum route for one-step production of methyl acrylate (MA) and acrylic acid (AA). However,...

Cited by 11 publications

References 33 publications

Leveraging the Proximity and Distribution of Cu−Cs Sites for Direct Conversion of Methanol to Esters/Aldehydes

Leveraging the Proximity and Distribution of Cu−Cs Sites for Direct Conversion of Methanol to Esters/Aldehydes

Preparation of Methyl Acrylate through Catalytic Aldol Condensation over Cs/TS-1 Catalysts

Highly selective production of renewable methyl acrylate via aldol condensation over Cu modified nitrogen-containing Beta zeolites

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