Ethanol to distillate-range molecules using Cu/MgxAlOy catalysts with low Cu loadings

Cuello-Penaloza, Paolo A.; Dastidar, Raka G; Wang, Shao‐Chun; Du, Yi; Lanci, Michael P.; Wooler, Bradley; Kliewer, Chris E.; Hermans, Ive; Dumesic, James A.; Huber, George W.

doi:10.1016/j.apcatb.2021.120984

Cited by 24 publications

(35 citation statements)

References 40 publications

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“…Our recent work showed that Cu/BN could effectively catalyze ethanol dehydrogenation to acetaldehyde . The Cu/BN and pure HAP powders that were directly mixed showed similar activity and selectivity to the Cu-HAP (0.5 wt %) catalyst, demonstrating that the atomic distance between copper species and HAP is not considered critical . Then, we mixed the granules of Cu/BN and HAP together in order to further increase the distance of two components (Figure c).…”

Section: Resultsmentioning

confidence: 94%

“…The highly dispersed copper nanoparticles and migration of hydrogen on the HAP surface may contribute to the development of such a hydrogen-rich surface. The increase in surface hydrogen concentration promotes the hydrogenation process, thus enhancing the higher alcohol selectivity. , These results indicate that the “synergistic effect” occurred between copper and HAP and the addition of hydrogen changes the reaction route of ethanol.…”

Section: Resultsmentioning

confidence: 99%

“…2110 and 2127 cm –1 , respectively. The former is assigned to CO adsorbed on the interfacial Cu nanoparticles with small sizes, ,, and the latter probably corresponds to CO linear adsorption on Cu + species. , Note that only a strong chemical interaction between the metal and support could result in these distinctive metal structures. Thus, these highly dispersed Cu nanoparticles presented on the reduced 0.5Cu-HAP catalyst surface allow it to catalyze the ethanol dehydrogenation and aldehyde hydrogenation reactions.…”

Section: Resultsmentioning

confidence: 99%

“…Considering both perspectives, tailoring the acid–base catalysts by introducing transition metal species (such as Co, Ni, Cu, , Zn, and Pd) as dehydrogenation sites might improve the performance toward higher alcohols. Cu has been frequently chosen as a dehydrogenation catalyst for ethanol conversion. , Recently, Ramasamy and co-workers reported that Cu/Mg x Al y O achieved 75% 1-butanol and higher alcohol selectivity at 59% ethanol conversion . They found that at a low Cu loading, the Cu 1+ species is the active site for ethanol dehydrogenation.…”

Section: Introductionmentioning

confidence: 99%

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Enhancing Ethanol Coupling to Produce Higher Alcohols by Tuning H₂ Partial Pressure over a Copper-Hydroxyapatite Catalyst

Zhou

et al. 2022

ACS Catal.

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Catalytic upgrading of ethanol, as a platform molecule from biomass to higher alcohols (C4–12), is a low-carbon route for value-added chemical production. However, the products are generally obtained in low selectivity due to the uncontrollable reactivity of intermediates that cause a complex reaction network. In this study, we show that unsaturated intermediates of aldehydes can be rapidly hydrogenated by surface hydrogen species during the ethanol upgrading process, thereby greatly inhibiting the cyclization reaction of aldehydes. Specifically, the product distributions on the Cu-hydroxyapatite (Cu-HAP) catalyst shift stepwise to higher alcohols from aromatic oxygenates with the partial pressure of hydrogen increasing from 0 to 95 kPa. Kinetic measurements and in situ ethanol infrared results indicated that the intermediates during this process are acetaldehyde and 2-butenal. Combined with physical structure and chemical state analysis of the catalyst, we found that Cu sites catalyze the hydrogenation of the CC bond of 2-butenal under a hydrogen atmosphere. The C–C coupling of ethanol to higher alcohols over Cu-HAP follows the Guerbet mechanism. In comparison, on bare HAP, n-butanol is formed as a primary product even though little amount of acetaldehyde was detected, indicating that ethanol proceeds mainly in a direct coupling process to yield higher alcohols. This study introduces an efficient ethanol valorization approach that is enabled by subtle control of the intermediate conversion over the Cu-HAP catalyst by the hydrogen partial pressure.

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Section: Resultsmentioning

confidence: 94%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Enhancing Ethanol Coupling to Produce Higher Alcohols by Tuning H₂ Partial Pressure over a Copper-Hydroxyapatite Catalyst

Zhou

et al. 2022

ACS Catal.

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“…This can be attributed to adsorption competition between water and organic molecules at the active site. Paolo et al 14 deemed that low (0.1−0.6 wt %) Cu loading catalysts supported on Mg x AlO y promote coupling of ethanol to higher predominately linear alcohols and aldehydes with high selectivity regardless of how the Cu is added to the catalyst. Petrolini et al 12 considered that the Guerbet reaction can be accelerated by the addition of transition metals such as Cu or Ni which facilitate H-transfer to accelerate alcohol−aldehyde interconversion.…”

Section: Introductionmentioning

confidence: 99%

Improvement of Ethanol Guerbet Condensation by Acetal Hydrolysis

Cui

et al. 2022

Ind. Eng. Chem. Res.

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The Guerbet condensation of bio-ethanol is a green route to the synthesis of n-butanol. However, this route suffers from its by-product water which not only affects adversely the condensation reaction performance, but also causes the deactivation of the catalyst. Hence, the water by-product should be removed. This goal is achieved by integrating the Guerbet condensation of ethanol with acetal hydrolysis in this work. First, the Guerbet condensation of ethanol and the integrated reaction of ethanol Guerbet condensation with acetal hydrolysis were thermodynamically analyzed. The results showed that acetal hydrolysis can promote the Guerbet condensation of ethanol. Then the performance of the two reaction systems was compared experimentally using Ni−Cu/TiO 2 catalyst. The selectivity of n-butanol reached 44.4% at an ethanol conversion of 47.9% in ethanol Guerbet condensation while the selectivity of n-butanol increased to 50.4% at an ethanol conversion of 50.2% in the integrated reaction with an ethanol/acetal molar ratio of 20. Finally, the two reaction systems were kinetically analyzed, and the results showed that acetal hydrolysis can lower the activation energy of the ethanol dehydrogenation step and acetaldehyde aldol self-condensation step, thus effectively promoting the Guerbet condensation of ethanol.

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High Performing and Stable Cu/NiAlO_x Catalysts for the Continuous Catalytic Conversion of Ethanol into Butanol

Lin

Tan

et al. 2022

ChemCatChem

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The catalytic conversion of ethanol into butanol is one of crucial reactions in biorefinery for the production of renewable fuels and chemicals. The development of highly durable non-noble metal-based catalysts is of great significance but poses big challenges. Herein, we prepared a series of NiAl-hydrotalcite derived Cu/NiAlO x catalysts via the hydrothermal precipitation method. Cu addition to the system shows an enhanced reactivity in the continuous catalytic conversion of ethanol into butanol. The 0.75 %Cu/NiAlO x catalyst afford a sustained ethanol conversion of ~35 % and butanol selectivity of ~45 % within 1000 h at 250 °C, 3 MPa N 2 . Complementary characterization studies reveal that Cu addition into the catalysts could not only provide redox sites for facilitating the dehydrogenation/hydrogenation processes, but also modulate the base/ acid property for suppressing the side reactions. The excellent stability might stem from the enhanced interaction between Cu and Ni species, as evidenced by EDX-mapping and H 2 -TPR. We believe this work will help to rational design and develop of high-performing and durable non-noble metal catalysts for ethanol coupling to higher alcohols.

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Ethanol to distillate-range molecules using Cu/MgxAlOy catalysts with low Cu loadings

Cited by 24 publications

References 40 publications

Enhancing Ethanol Coupling to Produce Higher Alcohols by Tuning H₂ Partial Pressure over a Copper-Hydroxyapatite Catalyst

Enhancing Ethanol Coupling to Produce Higher Alcohols by Tuning H₂ Partial Pressure over a Copper-Hydroxyapatite Catalyst

Improvement of Ethanol Guerbet Condensation by Acetal Hydrolysis

High Performing and Stable Cu/NiAlO_x Catalysts for the Continuous Catalytic Conversion of Ethanol into Butanol

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Ethanol to distillate-range molecules using Cu/MgxAlOy catalysts with low Cu loadings

Cited by 24 publications

References 40 publications

Enhancing Ethanol Coupling to Produce Higher Alcohols by Tuning H2 Partial Pressure over a Copper-Hydroxyapatite Catalyst

Enhancing Ethanol Coupling to Produce Higher Alcohols by Tuning H2 Partial Pressure over a Copper-Hydroxyapatite Catalyst

Improvement of Ethanol Guerbet Condensation by Acetal Hydrolysis

High Performing and Stable Cu/NiAlOx Catalysts for the Continuous Catalytic Conversion of Ethanol into Butanol

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Enhancing Ethanol Coupling to Produce Higher Alcohols by Tuning H₂ Partial Pressure over a Copper-Hydroxyapatite Catalyst

Enhancing Ethanol Coupling to Produce Higher Alcohols by Tuning H₂ Partial Pressure over a Copper-Hydroxyapatite Catalyst

High Performing and Stable Cu/NiAlO_x Catalysts for the Continuous Catalytic Conversion of Ethanol into Butanol