Esterification of levulinic acid to ethyl levulinate over bimodal micro–mesoporous H/BEA zeolite derivatives

Patil, Chetana R.; Niphadkar, Prashant S.; Bokade, Vijay V.; Joshi, P.N.

doi:10.1016/j.catcom.2013.10.006

Cited by 136 publications

(78 citation statements)

References 23 publications

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“…Various solid acids have been used for the esterification of levulinic acid with alcohols, e.g., zeolites and sulfated mixed oxides (sulfated zirconia (SO [9,[20][21][22][23]. Among them, the sulfated mixed oxides with strong acid sites are the most promising candidates providing high catalytic activity in a suitable reaction time [4].…”

Section: Methodsmentioning

confidence: 99%

Synthesis of biomass derived levulinate esters on novel sulfated Zr/KIL-2 composite catalysts

Popova

Szegedi

Lazarova

et al. 2016

Microporous and Mesoporous Materials

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Zirconia nanomaterials were prepared by impregnation of KIL-2 type silica with 4, 8, 15 and 25 wt% of ZrO2, and were modified by sulfate groups in order to vary the type, strength and density of the active sites. The samples were characterized by X-ray powder diffraction (XRD), EDX analysis, N2 physisorption, SEM, TEM, UV-Vis spectroscopy, XPS, and thermogravimetric analysis (TGA). The acidic properties were investigated by FT-IR spectroscopy of adsorbed pyridine. The catalytic properties of ZrKIL-2 catalysts and their sulfated varieties were studied in levulinic acid (LA) esterification with ethanol or n-butanol. The sulfated materials showed significantly higher activity compared to the non-sulfated ones due to their stronger Brönsted and Lewis acid sites. It was found that the silica supported sulfated samples show different activity depending on the applied alcohol. With increasing ZrO2 content up to 15 wt% increasing catalytic activity and selectivity was observed to produce levulinate esters. A further increase of the amount of zirconia leads to a decrease in catalytic activity because of the significant decrease of ZrO2 dispersion and the structure deterioration of the catalyst. For the first time insight was provided into the relation between sulfates group leaching and zirconia dispersion.

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Section: Methodsmentioning

confidence: 99%

Synthesis of biomass derived levulinate esters on novel sulfated Zr/KIL-2 composite catalysts

Popova

Szegedi

Lazarova

et al. 2016

Microporous and Mesoporous Materials

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“…As far as we know, most studies were focused on the synthesis of ethyl levulinate (EL). For this purpose, various solid acid catalysts have been developed, including supported heteropolyacid [9,10], zeolites [11,12], sulfonated metal oxides [13] and silicas [14], sulfonated carbon nanotubes [15], Starbon ® mesoporous carbon [16], and hybrid catalysts [17].…”

Section: Introductionmentioning

confidence: 99%

Efficient Production of N-Butyl Levulinate Fuel Additive from Levulinic Acid Using Amorphous Carbon Enriched with Oxygenated Groups

Yang

Zhang

et al. 2018

Catalysts

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Abstract:The aim of this study was to develop an effective carbonaceous solid acid for synthesizing green fuel additive through esterification of lignocellulose-derived levulinic acid (LA) and n-butanol. Two different sulfonated carbons were prepared from glucose-derived amorphous carbon (GC400) and commercial active carbon (AC400). They were contrastively studied by a series of characterizations (N 2 adsorption, X-ray diffraction, elemental analysis, transmission electron microscopy, Fourier transform infrared spectroscopy and NH 3 temperature programmed desorption). The results indicated that GC400 possessed stronger acidity and higher -SO 3 H density than AC400, and the amorphous structure qualified GC400 for good swelling capacity in the reaction solution. Assessment experiments showed that GC400 displayed remarkably higher catalytic efficiency than AC400 and other typical solid acids (HZSM-5, Hβ, Amberlyst-15 and Nafion-212 resin). Up to 90.5% conversion of LA and 100% selectivity of n-butyl levulinate could be obtained on GC400 under the optimal reaction conditions. The sulfonated carbon retained 92% of its original catalytic activity even after five cycles.

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“…LA can be further converted into levulinate esters, γ-valerolactone, 1,4-pentanediol and 5-nonanone (via pentanoic acid) as well as diphenolic acid as an intermediate for the synthesis of epoxy resins and poly-carbonates [16][17][18][19]. Levulinate esters are also useful compounds that can be used as fuel additives, solvents and plasticizers [19][20][21][22]. Therefore, they have the potential to reduce the consumption of petroleum-derived fossil fuels.…”

Section: Introductionmentioning

confidence: 99%

“…Therefore, substitution of homogeneous catalysts by heterogeneous analogues that are easily separable and reusable is an important task. Various solid acids have been used for esterification reactions, e.g., zeolites, Wells-Dawson heteropolyacids and sulfated oxides (SO4 2− /ZrO2, SO4 2− /Nb2O5, SO4 2− /TiO2, SO4 2− /SnO2) [4,6,13,15,19,20]. The activity of sulfated oxides can be improved by optimizing preparation conditions, which can influence the number of acid sites and the dispersion state of the sulfate species.…”

Section: Introductionmentioning

confidence: 99%

“…Levulinic acid (LA) is one of the promising platform molecules obtained from lignocellulosic biomass and used for the production of fuel additives, polymers and fine chemicals [6][7][8][9][10][11][12][13][14][15]. LA can be further converted into levulinate esters, γ-valerolactone, 1,4-pentanediol and 5-nonanone (via pentanoic acid) as well as diphenolic acid as an intermediate for the synthesis of epoxy resins and poly-carbonates [16][17][18][19]. Levulinate esters are also useful compounds that can be used as fuel additives, solvents and plasticizers [19][20][21][22].…”

Section: Introductionmentioning

confidence: 99%

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Influence of the preparation method of sulfated zirconia nanoparticles for levulinic acid esterification

Popova

Szegedi

Lazarova

et al. 2016

Reac Kinet Mech Cat

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Zirconia nanomaterials were prepared by hydrothermal synthesis with or without template and were modified by post synthesis method with sulfate groups. The materials were thoroughly characterized by X-ray powder diffraction (XRD), N2 physisorption, UV-Vis spectroscopy, TG analysis and XPS spectroscopy. The catalytic performance of nanosized mesoporous ZrO2 catalysts and their sulfated modifications was studied in levulinic acid (LA) esterification with ethanol. The sulfate group's dispersion was predetermined by the use of template during the mesoporous zirconia synthesis. A relation between sulfate groups leaching and the applied synthesis conditions (with or without template) of the zirconia nanoparticles was found. Sulfated materials showed significantly higher activity compared to non-sulfated ones. Furthermore, it has been found that the presence of

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Esterification of levulinic acid to ethyl levulinate over bimodal micro–mesoporous H/BEA zeolite derivatives

Cited by 136 publications

References 23 publications

Synthesis of biomass derived levulinate esters on novel sulfated Zr/KIL-2 composite catalysts

Synthesis of biomass derived levulinate esters on novel sulfated Zr/KIL-2 composite catalysts

Efficient Production of N-Butyl Levulinate Fuel Additive from Levulinic Acid Using Amorphous Carbon Enriched with Oxygenated Groups

Influence of the preparation method of sulfated zirconia nanoparticles for levulinic acid esterification

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