Selective conversion of ethanol to 1,3-butadiene using germanium talc as catalyst

Akiyama, S.; Miyaji, Akimitsu; Hayashi, Yoshihiro; Hiza, Misao; Sekiguchi, Yasumasa; Koyama, Tomonori; Shiga, Akinobu; Baba, Toshihide

doi:10.1016/j.jcat.2018.01.001

Cited by 36 publications

(20 citation statements)

References 38 publications

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“…In contrast, the Ge-talc had higher BD selectivity, 71%, but a slightly lower activity than Zn-talc. [70] XPS studies on Ge-talc revealed that the binding energies of O 1s, Mg 2p and Ge 3d were all lowered, implying an increase in the surface electron density which translates into higher basicity and a more reducing character. These two properties promote the dehydrogenation and reduction steps in the lead up to BD.…”

Section: Metal/metal Oxide-promoted Sio 2 à Mgo Catalystsmentioning

confidence: 99%

“…[63] Baba's group synthesized Zn and Ge-talc, a 1 : 2 layered magnesium silicate, where one MgO octahedral sheet is sandwiched between two SiO 2 tetrahedral sheets. [69,70] Despite a modest selectivity of 48%, the productivity for Zn-talc was 1.1 g BD g cat À 1 h À 1 , which puts it amongst the most active catalysts. [69] Kinetic studies indicated that Zn promoted the rate of acetaldehyde formation but did not affect the subsequent aldol condensation step.…”

Section: Metal/metal Oxide-promoted Sio 2 à Mgo Catalystsmentioning

confidence: 99%

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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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Section: Metal/metal Oxide-promoted Sio 2 à Mgo Catalystsmentioning

confidence: 99%

Section: Metal/metal Oxide-promoted Sio 2 à Mgo Catalystsmentioning

confidence: 99%

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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“…One of the key improvements made to the original Lebedev process has been in the more effective catalysis of the complicated main reaction path. Talc, or a magnesia-silicate (MgO/SiO2) crystal, has been shown to be an effective catalytic medium for the ethanol-to-BD synthesis route [17][18][19]22]. The conversion and selectivity for the desired product, 1,3butadiene, has varied somewhat in the literature due to altered experimental conditions and the Investigation into effective catalysis of the Lebedev process is ongoing.…”

Section: Lebedev Process and Other One-step Methodsmentioning

confidence: 99%

“…American companies for their war effort [22]. The key difference between the Lebedev and Ostromislensky model was the separation of the highly important initial ethanol-to-acetaldehyde step from the subsequent reactions.…”

Section: Ostromislensky Process and Other Two-step Methodsmentioning

confidence: 99%

“…1,3-butadiene selectivity then steadily rises with conversion, until conversion reaches 60 percent or higher and butene begins to dominate the reactor effluent.Using DFT, zinc was found to aid in the initial step of acetaldehyde formation, but also weakened the basicity of the catalyst and thus hurt production of the subsequent steps of the reaction network[18]. Akiyama et al employed a germanium-talc catalyst that exhibited remarkably high selectivity for 1,3-butadiene of 71 percent, but with only a 44 percent ethanol conversion rate[22].…”

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confidence: 99%

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Review of Established and Emergent Methods for the Production of C4 Olefins

Koval¹

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Review of Established and Emergent Methods for the Production of C4 Olefins James Koval Current production of C4 olefins is dominated by naphtha cracking and butane dehydrogenation, but significant research interest is developing in alternate feedstocks due to an abundance of inexpensive natural gas and bioethanol. The current C4 olefin production methods are costly, make use of already-depleted petroleum resources, and are often hazardous to workers, which forms the impetus for investigation into alternative methods and assessment of their viability as a future means of olefin production. Methods of natural gas conversion to higher order hydrocarbons are discussed, including Fischer-Tropsch synthesis and oxidative methane coupling, each of which could form the first step in a hypothetical natural gas-to-olefins process. The historically common Lebedev, Ostromislensky, and Fripiat methods for 1,3-butadiene production from ethanol feedstocks are described and analyzed, although these processes largely fell out of favor in the decades following World War II in favor of sources derived from naphtha cracking. Another well-known process involving C4 olefins, olefin metathesis, is considered, although the reaction is more commonly used to produce propylene. Biological processes are discussed as well, including the well-known production of bioethanol from sugars and starches, and also more novel processes such as an effort to use genetically engineered microorganisms to produce specific intermediates for olefin production, and in some cases, direct olefin production from these organisms. Finally, several promising schemes are identified and analyzed, in an attempt to compare their potential viability in key areas. Two of the most promising emergent methods today identified in this review are the bio-catalyzed production of 1,4-butanediol and/or butadiene using E. coli, and a microwave radiation-assisted scheme in which methane is selectively dimerized twice to form 1-butene.

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Copper and lanthanum mixed oxides as catalysts for ethanol Guerbet coupling: The role of La³⁺ on the production of long‐chain alcohols

Perrone

Siqueira

Metzker

et al. 2020

Env Prog and Sustain Energy

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Mixed oxides derived from the calcination of modified hydrotalcites precursors with copper and lanthanum were synthetized by the co‐precipitation method and characterized and applied as catalysts for ethanol Guerbet coupling reactions. The oxides obtained were used to convert ethanol into 1‐butanol and long‐chain alcohols, mostly 1‐hexanol. The selectivity for 1‐butanol and 1‐hexanol reached 62% and 10% for Cu‐MgAl(O) at 280°C. The addition of 1 mol% of La3+ (CuLa‐MgAl(O)) increased the number of basic sites comparing to Cu‐MgAl(O) changing the selectivity for 1‐butanol and 1‐hexanol reaching 16.70 and 41.7% at 280°C. The addition of lanthanum and consequently the increase on the catalyst basicity was related to the obtainment of long‐chain alcohols due to the enolate formation during the aldol condensation of Guerbet coupling.

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Selective conversion of ethanol to 1,3-butadiene using germanium talc as catalyst

Cited by 36 publications

References 38 publications

Recent Advances in Catalysts for the Conversion of Ethanol to Butadiene

Recent Advances in Catalysts for the Conversion of Ethanol to Butadiene

Review of Established and Emergent Methods for the Production of C4 Olefins

Copper and lanthanum mixed oxides as catalysts for ethanol Guerbet coupling: The role of La³⁺ on the production of long‐chain alcohols

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Selective conversion of ethanol to 1,3-butadiene using germanium talc as catalyst

Cited by 36 publications

References 38 publications

Recent Advances in Catalysts for the Conversion of Ethanol to Butadiene

Recent Advances in Catalysts for the Conversion of Ethanol to Butadiene

Review of Established and Emergent Methods for the Production of C4 Olefins

Copper and lanthanum mixed oxides as catalysts for ethanol Guerbet coupling: The role of La3+ on the production of long‐chain alcohols

Contact Info

Product

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Copper and lanthanum mixed oxides as catalysts for ethanol Guerbet coupling: The role of La³⁺ on the production of long‐chain alcohols