Improving 1,3-butadiene yield by Cs promotion in ethanol conversion

Patil, Pratap T.; Liu, Dapeng; Liu, Yan; Chang, Jie; Borgna, Armando

doi:10.1016/j.apcata.2017.05.025

Cited by 28 publications

(28 citation statements)

References 37 publications

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“…Considering that once acetaldehyde is formed, butadiene is immediately generated, therefore, it can be proposed that the acetaldehyde generation is the slowest step of this synthesis. This result is in line with the ones of some authors, who also proposed that the first step of the butadiene synthesis is the rate limiting step when t ‐ZrO 2 based catalysts are employed.…”

Section: Resultssupporting

confidence: 92%

“…The oxygen vacancies can be associated with strong basic sites whereas the cus species with Lewis acid sites. Both these species promote the acetaldehyde generation, i. e. the rate limiting step of the butadiene synthesis from ethanol . Thus, the Zn insertion in the ZrO 2 lattice fosters the butadiene synthesis as observed in Tables and .…”

Section: Resultsmentioning

confidence: 73%

“…Both these species promote the acetaldehyde generation, i. e. the rate limiting step of the butadiene synthesis from ethanol. [10,14,31,32] Thus, the Zn insertion in the ZrO 2 lattice fosters the butadiene synthesis as observed in Tables 1 and 2. As oxidized catalysts (see pretreatment) are employed in the catalytic tests, it can be suggested that the O of the lattice should be eliminated in order to generate the oxygen vacancies and cus sites. Indeed, replacing Zr + 4 with Zn + 2 makes the ZrO 2 surface more electrophilic.…”

Section: The Mpv Model Reactionmentioning

confidence: 71%

“…They associated the butadiene high yield with the well‐balanced basicity and Brønsted acidity of this catalyst. According to Patil et al . the interaction between ZnO−ZrO 2 generates pairs of acid and basic sites which promote the butadiene synthesis.…”

Section: Introductionmentioning

confidence: 99%

“…They associated the butadiene high yield with the well-balanced basicity and Brønsted acidity of this catalyst. According to Patil et al [14] the interaction between ZnOÀ ZrO 2 generates pairs of acid and basic sites which promote the butadiene synthesis. When adding Cs to the ZnOÀ ZrO 2 /SiO 2 catalyst they verified that the number of these sites increase, improving the catalytic behavior.…”

Section: Introductionmentioning

confidence: 99%

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The Role of the Oxygen Vacancies in the Synthesis of 1, 3‐Butadiene from Ethanol

et al. 2019

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The t‐ZrO2 doped with Zn catalyst and t‐ZrO2 as reference were employed in the butadiene synthesis from ethanol. Both catalysts were characterized by NH3‐TPD, CO2‐TPD, TPSR, the MPV model reaction, ICP, BET and EPR. Adding 0.2 wt% Zn to t‐ZrO2, the selectivity to butadiene increases three fold whereas the one to ethylene decreases. When ZrO2 is doped, the number of basic sites increases and the number of acid sites decreases. The TPSR spectra indicate that the acetaldehyde generation is the rate limiting step of the butadiene synthesis. The slowest step of the acetaldehyde generation is the H abstraction by a strong basic site. The EPR spectra show the replacement of Zr4+ by Zn2+ in the lattice of the t‐ZrO2 oxide. This phenomenon forms pairs of oxygen vacancies and coordinatively unsaturated Zr4+ ions (cus), which are strong basic sites and acid sites, respectively. Doping ZrO2 with Zn, the ethanol dehydrogenation and the butadiene synthesis are promoted not only due to the changes in the acidity and basicity of the catalyst but mainly because of the generation of oxygen vacancies and cus pairs during the reaction. These oxygen vacancies seem to behave as strong Brønsted basic sites.

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Section: Resultssupporting

confidence: 92%

Section: Resultsmentioning

confidence: 73%

Section: The Mpv Model Reactionmentioning

confidence: 71%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

The Role of the Oxygen Vacancies in the Synthesis of 1, 3‐Butadiene from Ethanol

et al. 2019

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Industrial Perspectives of Biomass Processing

Tabanelli

Cavani

2021

Biomass Valorization

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Recent Advances in Catalysts for the Conversion of Ethanol to Butadiene

Samsudin

Zhang

Jaenicke

et al. 2020

Chemistry An Asian Journal

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Butadiene is an important monomer for synthetic rubbers. Currently, the annual demand of ∼16 million tonnes is satisfied by butadiene produced as a byproduct of steam naphtha cracking where ethylene and propylene are the main products. The availability of large amounts of shale gas and condensates in the USA since about 2008 has led to a change in the cracker feed from naphtha to ethane and propane, affecting the amount of butadiene obtained. This has provided the impetus to look into direct processes for butadiene production. One option is the eco‐friendly conversion of (bio) ethanol to butadiene (ETB). This process had been developed in the 1930s in the then Soviet Union. It was operated on a large scale in USA during World War II but has since been abandoned in favour of petroleum‐based processes. The current trend, driven both by the availability of the raw material and ecological considerations, may make this process feasible again, particularly if the catalytic systems can be improved. This critical review discusses recent catalysts for the ETB process with special focus on the development since 2014, benchmarking them against earlier systems with a large database of operational experience.

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Improving 1,3-butadiene yield by Cs promotion in ethanol conversion

Cited by 28 publications

References 37 publications

The Role of the Oxygen Vacancies in the Synthesis of 1, 3‐Butadiene from Ethanol

The Role of the Oxygen Vacancies in the Synthesis of 1, 3‐Butadiene from Ethanol

Industrial Perspectives of Biomass Processing

Recent Advances in Catalysts for the Conversion of Ethanol to Butadiene

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