Development of Heterogeneous Catalysts for the Conversion of Levulinic Acid to γ‐Valerolactone

Wright, William R.; Palkovits, Regina

doi:10.1002/cssc.201200111

Cited by 488 publications

(402 citation statements)

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“…-Angelica lactone (AnL) is used for food flavouring and as aromas in the tobacco industry [24], pheromones [25] and fuel additives [14,26], while GVL is used as solvent for biomassrelated reactions [27,28], chemical intermediates [16][17][18][29][30][31][32][33] and fuels [16,17,34,35].…”

Section: Introductionmentioning

confidence: 99%

One-pot conversion of furfural to useful bio-products in the presence of a Sn,Al-containing zeolite beta catalyst prepared via post-synthesis routes

Antunes

Lima

Neves

et al. 2015

Journal of Catalysis

137

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Aiming at the valorisation of furfural (Fur) via sustainable routes based on process intensification and heterogeneous catalysis, the one-pot conversion of this renewable platform chemical to useful bio-products, namely furfuryl alkyl ethers (FEs), levulinate esters (LEs), levulinic acid (LA), angelica lactones (AnLs) and -valerolactone (GVL), was investigated using a single heterogeneous catalyst, in 2-butanol, at 120 ºC. Various chemical 2 reactions are involved in this process, which requires catalysts with active sites for acid and reduction chemistry. For this purpose, it was explored for the first time the catalytic potentialities of modified versions of zeolite beta containing Al and Sn sites prepared from commercially available nanocrystaline zeolite beta via post-synthesis partial dealumination followed by solid-state ion-exchange. The post-synthesis conditions influenced considerably the catalytic performances of these types of materials. The best-performing catalyst was (Sn) SSIE -beta1 with Si/(Al+Sn)=19 (Sn/Al=27.6), which led to total yield of bio-products of 83% at 86% Fur conversion, and exhibited steady catalytic performance for six consecutive runs. A systematic catalytic study using the prepared catalysts with different bio-products as substrates, together with the molecular level and microstructural characterisation of the materials, helped understand the effects of different material properties on the specific reaction pathways in the overall system. These studies led to mechanistic insights into the reaction network of Fur to the bio-products in alcohol media, upon which a kinetic model was developed for the first time. The superior performance of (Sn) SSIE -beta1 in various steps was related to the dealumination degree, dispersion and amount of Sn-sites, and acid properties.

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Section: Introductionmentioning

confidence: 99%

One-pot conversion of furfural to useful bio-products in the presence of a Sn,Al-containing zeolite beta catalyst prepared via post-synthesis routes

Antunes

Lima

Neves

et al. 2015

Journal of Catalysis

137

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“…It is produced easily and economically from biomass, [10][11][12][13][14][15] and can be converted into many valuable chemicals. These include γ-valerolactone (GVL, 2), 1,4-pentanediol, methyltetrahydrofuran, and valeric acid and esters [16,17].…”

Section: Introductionmentioning

confidence: 99%

“…These include γ-valerolactone (GVL, 2), 1,4-pentanediol, methyltetrahydrofuran, and valeric acid and esters [16,17]. Of these, the stable and non-toxic GVL has already several applications: it can be used directly as a fuel additive or as a precursor for fuels and chemicals and as a renewable solvent [10,[18][19][20][21]. Various companies such as Green Future SRL, DuPont, Segetis and Biofine have developed processes for the manufacturing of levulinic acid through bio-based routes.…”

Section: Introductionmentioning

confidence: 99%

“…The separation costs are often the deciding factor, because any remaining catalyst will often react further with the product and by-products. Supported ruthenium catalysts are known to perform well in LA hydrogenation [10,19,[25][26][27][28][29]. The problem is that small changes in any number of parameters often cause large variance in catalyst performance.…”

Section: Introductionmentioning

confidence: 99%

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Highly Selective Hydrogenation of Levulinic Acid to γ-Valerolactone Over Ru/ZrO2 Catalysts

et al. 2017

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We studied the catalytic hydrogenation of levulinic acid over zirconia supported ruthenium catalysts. Four different Ru/ZrO 2 catalysts were prepared by different pre-treatments and using different zirconium supports (ZrO x (OH) 4−2x and ZrO 2 ). Although the final compositions of the catalysts are the same, the pre-treatments strongly affect catalytic activity. Remarkably, one of the catalysts gave >99% yield of γ-valerolactone under mild conditions. This catalyst was also robust, and could be recycled at least four times without any loss in activity or selectivity. The activity is attributed to the presence of small ruthenium particles together with acidic sites on the catalyst.Graphical Abstract Pre-treatment changes the performance for ruthenium nanoparticles on zirconia supports, giving TONs over 3500 in the hydrogenation of levulinic acid to γ-valerolactone with over 99% yield. Electronic supplementary materialThe online version of this article

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“…Levulinic acid has been commonly used as an additive in medicine, food, agriculture, and cosmetics ( Van de Vyver et al 2011;Galletti et al 2012;Yan et al 2015). Furthermore, -valerolactone (GVL), a hydrogenation derivative of levulinic acid, is also an important biomass-derived platform chemical (Wright and Palkovits 2012;Alonso et al 2013a;Ding et al 2014). GVL is frequently used as an additive for food and drug applications, gasoline, or as a solvent, and it is also the precursor for a series of high-value chemicals, such as isomers of butenes, methyl-tetrahydrofuran, 2-MeTHF, etc.…”

Section: Introductionmentioning

confidence: 99%

A Two-Step Conversion of Corn Stover into Furfural and Levulinic Acid in a Water/Gamma-Valerolactone System

Li¹,

Li²,

Liu³

et al. 2016

BioResources

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A two-step hydrolysis method was evaluated as a potential means of obtaining high yields of furfural and levulinic acid from corn stover using sulfuric acid as catalyst in a water/gamma-valerolactone (GVL) system. The corn stover underwent a high-temperature hydrolysis process to produce levulinic acid, followed by a low-temperature hydrolysis process to produce furfural. A series of experiments were conducted to explore the relationship between the different reaction parameters and the final yields of furfural and levulinic acid. Scanning electron microscopy (SEM) pictures together with X-ray diffraction (XRD) analysis were used to further elaborate on the hydrolysis results. Molar yields of about 70.65% furfural and 57.7% levulinic acid were obtained by applying this method with a low temperature of 140 °C and a high temperature of 190 °C, together with 0.2 M of sulfuric acid used as the catalyst. These results indicated that this was an effective way to obtain satisfactory yields of furfural and levulinic acid from corn stover.

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Development of Heterogeneous Catalysts for the Conversion of Levulinic Acid to γ‐Valerolactone

Cited by 488 publications

References 82 publications

One-pot conversion of furfural to useful bio-products in the presence of a Sn,Al-containing zeolite beta catalyst prepared via post-synthesis routes

One-pot conversion of furfural to useful bio-products in the presence of a Sn,Al-containing zeolite beta catalyst prepared via post-synthesis routes

Highly Selective Hydrogenation of Levulinic Acid to γ-Valerolactone Over Ru/ZrO2 Catalysts

A Two-Step Conversion of Corn Stover into Furfural and Levulinic Acid in a Water/Gamma-Valerolactone System

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