Catalytic upgrading of ethanol to butanol over a binary catalytic system of FeNiO and LiOH

Pang, Jifeng; Wang, Zhinuo; Liu, Shimin; Li, Xinsheng; Li, Xianquan; Wang, Junhu; Zhang, Tao

doi:10.1016/s1872-2067(20)63541-0

Cited by 23 publications

(13 citation statements)

References 46 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The biochemical route was supplanted by cost-efficient chemical synthesis of 1-butanol from petrochemical-derived propene via hydroformylation, but the need for sustainable liquid transportation fuels has renewed interest in biochemical approaches to the synthesis of 1-butanol . New microbial strains, as well as innovation in the fermentation setup, have significantly improved the productivity of microbial 1-butanol synthesis, but isolation of low concentrations of the alcohol from aqueous solution is both costly and energy intensive. ,,, Heterogeneous catalysts for ethanol upgrading generally require reaction temperatures of 250 °C or more to achieve suitable reaction rates, but the reduced activity is offset by the low price and recyclability of the catalyst in many of these systems. − While the lack of base promoter prevents the formation of sodium acetate, other side products, such as higher alcohols, CO, alkenes, or ethyl acetate, are commonly formed alongside the desired 1-butanol product. Recently developed homogeneous ruthenium, iridium, and manganese catalysts for the Guerbet reaction of fermentation-derived ethanol can achieve high turnover numbers and high selectivity among liquid products for the formation of 1-butanol at moderate conversions. − Use of base promoters, such as NaOEt, commonly result in the formation of sodium acetate alongside the desired 1-butanol product, but high catalyst activity can be achieved at temperatures at or below 160 °C.…”

Section: Introductionmentioning

confidence: 99%

Structural Evolution of MOF-Derived RuCo, A General Catalyst for the Guerbet Reaction

Neumann

Payne

Rozeveld

et al. 2021

ACS Appl. Mater. Interfaces

View full text Add to dashboard Cite

Guerbet alcohols, a class of β-branched terminal alcohols, find widespread application because of their low melting points and excellent fluidity. Because of the limitations in the activity and selectivity of existing Guerbet catalysts, Guerbet alcohols are not currently produced via the Guerbet reaction but via hydroformylation of oil-derived alkenes followed by aldol condensation. In pursuit of a one-step synthesis of Guerbet alcohols from simple linear alcohol precursors, we show that MOF-derived RuCo alloys achieve over a million turnovers in the Guerbet reaction of 1-propanol, 1-butanol, and 1-pentanol. The active catalyst is formed in situ from ruthenium-impregnated metal–organic framework MFU-1. XPS and XAS studies indicate that the precatalyst is composed of Ru precursor trapped inside the MOF pores with no change in the oxidation state or coordination environment of Ru upon MOF incorporation. The significantly higher reactivity of Ru-impregnated MOF versus a physical mixture of Ru precursor and MOF suggests that the MOF plays an important role in templating the formation of the active catalyst and/or its stabilization. XPS reveals partial reduction of both ruthenium and MOF-derived cobalt under the Guerbet reaction conditions, and TEM/EDX imaging shows that Ru is decorated on the edges of dense nanoparticles, as well as thin nanoplates of CoO x . The use of ethanol rather than higher alcohols as a substrate results in lower turnover frequencies, and RuCo recovered from ethanol upgrading lacks nanostructures with plate-like morphology and does not exhibit Ru-enrichment on the surface and edge sites. Notably, 1H and 31P NMR studies show that through use of K3PO4 as a base promoter in the RuCo-catalyzed alcohol upgrading, the formation of carboxylate salts, a common side product in the Guerbet reaction, was effectively eliminated.

show abstract

Section: Introductionmentioning

confidence: 99%

Structural Evolution of MOF-Derived RuCo, A General Catalyst for the Guerbet Reaction

Neumann

Payne

Rozeveld

et al. 2021

ACS Appl. Mater. Interfaces

View full text Add to dashboard Cite

show abstract

“…However, bioethanol mainly derives from the fermentation of sucrose, whose hygroscopic properties will easily cause separation and storage problems of existing fuel infrastructure, as well as corrosion of current automobile engines. , In addition, with much lower energy density, ethanol is not an ideal diesel additive compared to diesel, while C4+ long-chain higher alcohols are hydrophobic and less corrosive, which means that the current pipeline network can be utilized for safe transportation without any reconfiguration. , Furthermore, due to the similar calorific value and cetane value with diesel, the blender of C4+ long-chain higher alcohols with diesel is expected to significantly relieve diesel pollutant emissions …”

Section: Introductionmentioning

confidence: 99%

Upgrading of Aqueous Bioethanol to Higher Alcohols over NiSn/MgAlO Catalyst

Cai

Zhang

et al. 2021

ACS Sustainable Chem. Eng.

View full text Add to dashboard Cite

The calorific value and cetane number of C4+ long-chain higher alcohols are similar to those of diesel, blending with which can significantly reduce pollutant emissions from diesel engines. Direct upgrading of aqueous bioethanol derived from the biomass fermentation to higher alcohols faces the challenge of efficient catalysts with excellent catalytic activity and hydrothermal stability. Herein, NiSn/MgAlO catalysts prepared by loading Ni and Sn into hydrotalcite through coprecipitation and ion exchange methods were developed. Higher alcohols with a yield of 48.4 C-mol % and selectivity of 93.8% were obtained by upgrading of aqueous ethanol under hydrothermal conditions. NiSn/MgAlO catalysts exhibited excellent stability even after four recycle runs. The experiment results and catalyst characterizations revealed that the Ni(Mg)O solid solution formed by calcination of Ni(Mg)Al hydrotalcite promotes the dispersion and stability of Ni particles. Moreover, the high-valence Sn regulates the electronic structure and coordination environment of Ni (ratio of Ni0, Ni2+, Niδ+, and Ni–Sn alloys), both of which give the synergistic effect for the formation of C4+ long chain higher alcohols by selectively regulating the ethanol coupling reaction.

show abstract

“…Conversion of ethanol to n -butanol belongs to the Guerbet reaction, which involves the steps of ethanol dehydrogenation to acetaldehyde, condensation of acetaldehyde to crotonaldehyde, and hydrogenation of crotonaldehyde to n -butanol. − To balance these reaction steps, multiple active sites should be coupled subtly for high n -butanol yields. In past decades, various homogeneous catalysts, mixed oxides, hydroxyapatites, and metal enhanced oxide catalysts have been developed for this reaction. ,− Among these, the metal enhanced oxide catalysts have demonstrated great potential due to its mild reaction conditions, controllable ethanol conversion, and relatively high n -butanol selectivity. For instance, the metals of Ni, Cu, and Ru were introduced into the mixed oxides of Al 2 O 3 and MgO that derived from the hydrotalcite precursors, and then afforded ca.…”

Section: Introductionmentioning

confidence: 99%

Conversion of Ethanol to n-Butanol over NiCeO₂ Based Catalysts: Effects of Metal Dispersion and NiCe Interactions

Wang

Pang

Song

et al. 2020

Ind. Eng. Chem. Res.

Self Cite

View full text Add to dashboard Cite

Conversion of ethanol to n-butanol is of great significance in ethanol upgrading, and multiple sites of metals and oxides are generally coupled for this cascade reaction. Herein, we dispersed Ni and CeO 2 sites on different carbon supports with the aim of getting insight into the effect of metal dispersion and interactions on the conversion of ethanol to nbutanol. Our results revealed that the dispersion of Ni and CeO 2 was crucial to ethanol conversion and n-butanol selectivity. The activated carbon (AC) had a high specific surface area and abundant surface functional groups, which benefited the dispersion of Ni and CeO 2 species and created balanced Ni 0 /Ni 2+ sites, weak acid and strong base sites for the hydrogen transfer and aldol condensation reactions. Additionally, the stability of catalyst was determined by the interaction between Ni and CeO 2 species. Over the NiCeO 2 /AC catalyst, Ni and CeO 2 species strongly interacted, which depressed the carbonation of CeO 2 and maintained its high stability.

show abstract

Catalytic upgrading of ethanol to butanol over a binary catalytic system of FeNiO and LiOH

Cited by 23 publications

References 46 publications

Structural Evolution of MOF-Derived RuCo, A General Catalyst for the Guerbet Reaction

Structural Evolution of MOF-Derived RuCo, A General Catalyst for the Guerbet Reaction

Upgrading of Aqueous Bioethanol to Higher Alcohols over NiSn/MgAlO Catalyst

Conversion of Ethanol to n-Butanol over NiCeO₂ Based Catalysts: Effects of Metal Dispersion and NiCe Interactions

Contact Info

Product

Resources

About

Catalytic upgrading of ethanol to butanol over a binary catalytic system of FeNiO and LiOH

Cited by 23 publications

References 46 publications

Structural Evolution of MOF-Derived RuCo, A General Catalyst for the Guerbet Reaction

Structural Evolution of MOF-Derived RuCo, A General Catalyst for the Guerbet Reaction

Upgrading of Aqueous Bioethanol to Higher Alcohols over NiSn/MgAlO Catalyst

Conversion of Ethanol to n-Butanol over NiCeO2 Based Catalysts: Effects of Metal Dispersion and NiCe Interactions

Contact Info

Product

Resources

About

Conversion of Ethanol to n-Butanol over NiCeO₂ Based Catalysts: Effects of Metal Dispersion and NiCe Interactions