Esterification of levulinic acid with ethanol over sulfated Si-doped ZrO2 solid acid catalyst: Study of the structure–activity relationships

Kuwahara, Yasutaka; Kaburagi, Wako; Nemoto, Koji; Fujitani, Tadahiro

doi:10.1016/j.apcata.2014.02.032

Cited by 113 publications

(66 citation statements)

References 47 publications

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“…For example, Yuwahara et al [55] showed that in the absence of catalyst levulinic acid can be esterified with ethanol at 70 ºC (1.8% in 10 h). Before attempting detailed catalytic work, a noncatalytic reaction using 2-furoic acid, and n-butanol was examined and it was observed that, under the same above mentioned experimental conditions, only a conversion of 10 % was detected at 24 h (Fig 5), indicating that from a practical point of view the reaction is not taking place in an important extent in the absence of a catalyst.…”

Section: (Figure 5) (Table 2)mentioning

confidence: 98%

Biomass valorization derivatives: Clean esterification of 2-furoic acid using tungstophosphoric acid/zirconia composites as recyclable catalyst

Escobar

Sathicq

Pizzio

et al. 2015

Process Safety and Environmental Protection

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Section: (Figure 5) (Table 2)mentioning

confidence: 98%

Biomass valorization derivatives: Clean esterification of 2-furoic acid using tungstophosphoric acid/zirconia composites as recyclable catalyst

Escobar

Sathicq

Pizzio

et al. 2015

Process Safety and Environmental Protection

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“…The obtained results by EDX for the spent catalysts are in good agreement with the data from XRD, TG analysis and N2 physisorption data. Table 5 [4,13,15,16,20,23]. The higher catalytic activity which is observed for SO 4 2-/Si-ZrO2, Keggin HPA and Wells-Dowson HPA is due to the higher amount of applied catalyst in the catalytic reaction (Table 5).…”

Section: Catalytic Activity For La Esterification With Ethanol and Bumentioning

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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“…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].…”

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%

“…The improvement of acid catalyst stability was achieved by incorporation of a moderate amount of Si (up to 30 mol% Si per Zr) into sulfated ZrO2. 15 The method of the preparation of sulphated zirconia plays a crucial role. The physico-chemical properties of the obtained sulfated zirconia depend on the ZrO2 synthesis conditions and method for sulfation.…”

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 with ethanol over sulfated Si-doped ZrO2 solid acid catalyst: Study of the structure–activity relationships

Cited by 113 publications

References 47 publications

Biomass valorization derivatives: Clean esterification of 2-furoic acid using tungstophosphoric acid/zirconia composites as recyclable catalyst

Biomass valorization derivatives: Clean esterification of 2-furoic acid using tungstophosphoric acid/zirconia composites as recyclable catalyst

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

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

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