Catalytic glycerol conversion into 1,2-propanediol in absence of added hydrogen

Dhondt, Elisabeth; Vyver, Stijn Van de; Sels, Bert F.; Jacobs, Pierre

doi:10.1039/b812886c

Cited by 140 publications

(100 citation statements)

References 14 publications

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“…Alcohol has been employed as a hydrogen source in several studies. [61][62][63] In our study, taking methanol for example, summing up of the total methanol consumption in converting 2.0 g of birch lignin into monomeric phenolics requires about 80 mg of methanol, which is only 0.3% of added methanol in the reaction. Different catalysts with alternation of supports and active components were evaluated in the LDP reaction (Table 1, entries [13][14][15][16].…”

Section: Resultsmentioning

confidence: 99%

Lignin depolymerization (LDP) in alcohol over nickel-based catalysts via a fragmentation–hydrogenolysis process

Song

Wang

Cai

et al. 2013

Energy Environ. Sci.

816

661

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Valorization of native birch wood lignin into monomeric phenols over nickel-based catalysts has been studied. High chemoselectivity to aromatic products was achieved by using Ni-based catalysts and common alcohols as solvents. The results show that lignin can be selectively cleaved into propylguaiacol and propylsyringol with total selectivity >90% at a lignin conversion of about 50%. Alcohols, such as methanol, ethanol and ethylene glycol, are suitable solvents for lignin conversion. Analyses with MALDI-TOF and NMR show that birch lignin is first fragmented into smaller lignin species consisting of several benzene rings with a molecular weight of m/z ca. 1100 to ca. 1600 via alcoholysis reaction. The second step involves the hydrogenolysis of the fragments into phenols. The presence of gaseous H 2 has no effect on lignin conversion, indicating that alcohols provide active hydrogen species, which is further confirmed by isotopic tracing experiments. Catalysts are recycled by magnetic separation and can be reused four times without losing activity. The mechanistic insights from this work could be helpful in understanding native lignin conversion and the formation of monomeric phenolics via reductive depolymerization. Broader contextNature efficiently synthesizes aromatic structures and deposits them as lignin in plants. Incorporation of catalytic technologies into lignin conversion is a possible option for valorizing the feedstock as a renewable raw material for aromatic chemical production. Use of heterogeneous catalysts facilitates separation and recycling, and has attracted great attention. However, the detailed chemistry between solid catalysts and solid feedstocks still remains unknown because of mass transfer limitations. Herein we report the valorization of native birch wood lignin into monomeric phenols over nickel-based catalysts. High chemoselectivity to aromatic products was achieved by using Ni-based catalysts and common alcohols as solvents. The results show that lignin can be selectively cleaved into propylguaiacol and propylsyringol with total selectivity >90% at a lignin conversion of about 50%. Analysis results show that birch lignin is rst fragmented into smaller lignin species consisting of several benzene rings with a molecular weight of m/z ca. 1100 to ca. 1600 via alcoholysis reaction. The second step involves the hydrogenolysis of the fragments into phenols. This study will greatly contribute to the understanding of the lignin depolymerization reaction and will be interesting for other biomass conversion.

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Section: Resultsmentioning

confidence: 99%

Lignin depolymerization (LDP) in alcohol over nickel-based catalysts via a fragmentation–hydrogenolysis process

Song

Wang

Cai

et al. 2013

Energy Environ. Sci.

816

661

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“…The protic aqueous environment promotes the transfer of protons (during the dehydration reaction) or hydride (during the hydrogenation reaction) [32,33]. The hydrogen can be supplied externally or be produced in situ by APR: this mechanism has been identified in the case of Pt/NaY [34].…”

Section: Dehydrogenation-dehydration-hydrogenation Of An Alcohol Groupmentioning

confidence: 99%

“…Lastly, when the target products are short polyols (glycerol or glycols) obtained by retro-aldol reactions, solid bases can be used: NaY (sometimes acidified by Na + -H + exchanges) [34,53], ZnO [19], MgO [67].…”

Section: Other Supportsmentioning

confidence: 99%

Transformation of Sorbitol to Biofuels by Heterogeneous Catalysis: Chemical and Industrial Considerations

Vilcocq

Cabiac

Especel

et al. 2013

Oil Gas Sci. Technol. – Rev. IFP Energies nouvelles

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Résumé -Transformation du sorbitol en biocarburants par catalyse hétérogène : considérations chimiques et industrielles -La raréfaction du pétrole et l'augmentation conjointe de la demande en carburants ont conduit à la recherche de carburants alternatifs. Dans un premier temps, la valorisation de ressources agricoles alimentaires pour la production d'éthanol et de biodiesel a permis de développer les biocarburants de première génération. Aujourd'hui les travaux de recherche s'orientent vers l'utilisation de biomasse lignocellulosique comme source de carbone renouvelable (biocarburants de deuxième génération). Alors que la filière de l'éthanol cellulosique est en plein développement, une nouvelle voie consistant à transformer des sucres et polyols d'origine lignocellulosique en alcanes légers par catalyse hétérogène bifonctionnelle en phase aqueuse a été récemment décrite. Ce procédé s'effectue à basse température et pression modérée (T < 300 °C et P < 50 bar). Il nécessite, d'une part, la formation d'hydrogène par reformage catalytique de carbohydrates en phase aqueuse et, d'autre part, la déshydratation/hydrogénation de polyols conduisant à un alcane par ruptures sélectives des liaisons C-O. Un défi lié à cette thématique réside dans le développement de systèmes catalytiques multifonctionnels stables, actifs et sélectifs dans les conditions de la réaction de transformation. L'objectif de l'article est de présenter les réactions mises en jeu, les systèmes catalytiques décrits dans la littérature pour ce type de transformation ainsi que des exemples d'applications industrielles. Abstract

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“…Within this concept, two different approaches have been investigated: the first one involves the use of aqueous solutions of glycerol, where hydrogen is formed via aqueous phase reforming (APR) of a part of glycerol [20][21][22][23]; and the second, the addition of a hydrogen donor molecule (alcohols, formic acid), through hydrogen transfer reaction. The idea of catalytic transfer hydrogenation (CTH) was firstly realized by Musolino et al [24] for selective transfer hydrogenolysis of glycerol in the presence of palladium catalysts (Pd/Fe2O3) using ethanol and 2-propanol as H2 donor molecules.…”

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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Catalytic glycerol conversion into 1,2-propanediol in absence of added hydrogen

Abstract: Conversion of glycerol into high yields of 1,2-propanediol in absence of added hydrogen is possible with Pt impregnated NaY zeolite characterized by extra-zeolitic metal particles combined with zeolite Brønsted acidity.

Cited by 140 publications

References 14 publications

Lignin depolymerization (LDP) in alcohol over nickel-based catalysts via a fragmentation–hydrogenolysis process

Lignin depolymerization (LDP) in alcohol over nickel-based catalysts via a fragmentation–hydrogenolysis process

Transformation of Sorbitol to Biofuels by Heterogeneous Catalysis: Chemical and Industrial Considerations

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

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