Liquid-phase glycerol hydrogenolysis by formic acid over Ni–Cu/Al2O3 catalysts

Gandarias, Iñaki; Requies, J.; Arias, P.L.; Armbruster, Udo; Martin, Andreas

doi:10.1016/j.jcat.2012.03.004

Cited by 168 publications

(135 citation statements)

References 44 publications

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“…In particular, bimetallic Ni-Cu systems can present advantages with respect to monometallic Ni catalysts. Gandarias et al [26] used Ni-Cu/Al 2 O 3 in the glycerol hydrogenolysis to 1,2-PDO under N 2 pressure and formic acid as hydrogen donor molecule. These authors observed that the Ni/Cu atomic ratio and acid sites affected the yield to 1,2-PDO.…”

Section: Introductionmentioning

confidence: 99%

Influence of copper on nickel-based catalysts in the conversion of glycerol

Miranda

Chimentão

Szanyi

et al. 2015

Applied Catalysis B: Environmental

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The catalytic transformation of glycerol to value-added compounds was investigated over bimetallic Ni-Cu/y-Al2 O3 catalysts with Ni/Cu atomic ratios of 8/1, 4/1, 2/1, 1/1, 1/2, 1/4, and 1/8. XPS analysis revealed that the surface composition of the catalyst exhibited progressive enrichment of Cu as its content in the catalyst increased. H2 -chemisorption indicated that the total number of exposed Ni atoms decreased as the Cu content increased. As a result, deep hydrogenolysis to produce CH4 was inhibited by the addition of Cu to the Ni catalyst, yielding higher selectivity toward the dehydration products of glycerol such as hydroxyacetone.FTIR spectra of adsorbed CO reveal that Cu asserts both geometric and electronic effects on the adsorption properties of Ni. The geometrical effect is visualized by the progressive disappearance of the bridge-bound adsorbed CO on metallic Ni by the incorporation of Cu. This suggests that the deep hydrogenolysis of glycerol to CH4 formation requires an ensemble of adjacent active Ni atoms. The electronic effect of Cu on Ni is indicated by the red shift of the IR peak of adsorbed CO as the Cu content increases. The electronic interaction between Cu and Ni species was also substantiated by XANES results. HTREM revealed metal particles very well distributed on the support with particle size of 1.5 to 5 nm. The Ni-Cu samples were not a total intermetallic alloys..

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Section: Introductionmentioning

confidence: 99%

Influence of copper on nickel-based catalysts in the conversion of glycerol

Miranda

Chimentão

Szanyi

et al. 2015

Applied Catalysis B: Environmental

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“…A Cu:Zn:Al catalyst prepared by the oxalate gel technique was found to exhibit the best performance with a 45% yield to the target product at 220 °C 3.5 MPa N2 and 4 h. These results correspond to productivity values (g1,2-PDO . gcat −1 ·h −1 ) up to five-times higher compared with previous reports [24,27]. Experiments with labeled 13 CH3OH over this catalyst allowed us to quantify the H2 formation origin (methanol and/or glycerol APR) and showed that ~70% of the total H2 is indeed produced from the reformation of methanol.…”

Section: Introductionmentioning

confidence: 63%

“…At 210 °C, 3.0 MPa N2 and 10 h, glycerol was converted by 95% with 92% selectivity to 1,2-propanediol. Gandarias et al [26][27][28] have significantly contributed to the field of CTH hydrogenation reactions, focusing mainly on 2-propanol and formic acid as hydrogen donor molecules. Formic acid was proven to be an effective donor over Ni-Cu/Al2O3 catalyst.…”

Section: Introductionmentioning

confidence: 99%

Catalytic Glycerol Hydrodeoxygenation under Inert Atmosphere: Ethanol as a Hydrogen Donor

Vasiliadou

Lemonidou

2014

Catalysts

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Glycerol hydrodeoxygenation to 1,2-propanediol (1,2-PDO) is a reaction of high interest. However, the need for hydrogen supply is a main drawback of the process. According to the concept investigated here, 1,2-propanediol is efficiently formed using bio-glycerol feedstock with H2 formed in situ via ethanol aqueous phase reforming. Ethanol is thought to be a promising H2 source, as it is alcohol that can be used instead of methanol for transesterification of oils and fats. The H2 generated is consumed in the tandem reaction of glycerol hydrodeoxygenation. The reaction cycle proceeds in liquid phase at 220-250 °C and 1.5-3.5 MPa initial N2 pressure for a 2 and 4-h reaction time. Pt-, Ni-and Cu-based catalysts have been synthesized, characterized and evaluated in the reaction. Among the materials tested, Pt/Fe2O3-Al2O3 exhibited the most promising performance in terms of 1,2-propanediol productivity, while reusability tests showed a stable behavior. Structural integrity and no formation of carbonaceous deposits were verified via Temperature Programmed Desorption of hydrogen (TPD-H2) and thermogravimetric analysis of the fresh and used Pt/FeAl catalyst. A study on the effect of various operating conditions (reaction time, temperature and pressure) indicated that in order to maximize 1,2-propanediol productivity and yield, milder reaction conditions should be applied. The highest 1,2-propanediol yield, 53% (1.1 g1,2-PDO gcat −1 ·h −1 ), was achieved at a lower reaction temperature of 220 °C. OPEN ACCESSCatalysts 2014, 4 398

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“…Furthermore, a close correlation between the ability of catalysts towards the dehydrogenation of 2-propanol and the ability to perform CTH reactions was found [46]. On the other hand, by changing the hydrogen donor molecule, it is possible to improve the performance of the CTH of glycerol on using the bimetallic Ni-Cu/Al 2 O 3 catalyst [49]. Gandarias et al performed a study on the effect of the hydrogen donor molecule, by comparing methanol (MeOH), formic acid (FA) and 2-propanol [48].…”

Section: Glycerol and Other Polyolsmentioning

confidence: 91%

“…Gandarias et al have deeply studied the reactivity of bimetallic catalysts Ni-Cu/Al 2 O 3 , prepared through the sol-gel technique, giving the best performances when pretreated at 450 • C [47][48][49]. At the beginning, the hydrogenolysis of glycerol was studied either in presence of molecular hydrogen or in conditions in which the hydrogen is produced in situ, through the aqueous phase reforming (APR) or through the catalytic transfer hydrogenolysis (CTH) by means of 2-propanol [47].…”

Section: Glycerol and Other Polyolsmentioning

confidence: 99%

Catalytic Transfer Hydrogenolysis as an Effective Tool for the Reductive Upgrading of Cellulose, Hemicellulose, Lignin, and Their Derived Molecules

et al. 2018

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Lignocellulosic biomasses have a tremendous potential to cover the future demand of bio-based chemicals and materials, breaking down our historical dependence on petroleum resources. The development of green chemical technologies, together with the appropriate eco-politics, can make a decisive contribution to a cheap and effective conversion of lignocellulosic feedstocks into sustainable and renewable chemical building blocks. In this regard, the use of an indirect H-source for reducing the oxygen content in lignocellulosic biomasses and in their derived platform molecules is receiving increasing attention. In this contribution we highlight recent advances in the transfer hydrogenolysis of cellulose, hemicellulose, lignin, and of their derived model molecules promoted by heterogeneous catalysts for the sustainable production of biofuels and biochemicals.

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Liquid-phase glycerol hydrogenolysis by formic acid over Ni–Cu/Al2O3 catalysts

Cited by 168 publications

References 44 publications

Influence of copper on nickel-based catalysts in the conversion of glycerol

Influence of copper on nickel-based catalysts in the conversion of glycerol

Catalytic Glycerol Hydrodeoxygenation under Inert Atmosphere: Ethanol as a Hydrogen Donor

Catalytic Transfer Hydrogenolysis as an Effective Tool for the Reductive Upgrading of Cellulose, Hemicellulose, Lignin, and Their Derived Molecules

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