Article

Kinetic analysis of aqueous-phase cyclodehydration of 1,4-butanediol and erythritol over a layered niobium molybdate solid acid

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Abstract

Aqueous-phase reactions are desirable for the transformation of biomass-derived species because the use of water is inherently environmentally friendly. Cyclodehydration of C4 diols in aqueous solution was examined using a variety of water-tolerant solid acids including H-type zeolites (H-ZSM5, H-mordenite, H-beta), Amberlyst-15 ion-exchange resin, niobic acid and layered HNbMoO6. Cyclodehydration of 1,4-butanediol (HO-CH2CH2CH2CH2-OH) and erythritol (HO-CH2CH-OHCH-OHCH2-OH) proceeded on three of the Brønsted solid acids, HNbMoO6, H-ZSM5 and Amberlyst-15. Although HNbMoO6 showed moderate activity for 1,4-butanediol dehydration, it exhibited the highest activity for erythritol dehydration. Kinetic analysis indicated that 1,4-butanediol and erythritol dehydration over HNbMoO6 followed a Tamaru-type mechanism with two successive irreversible steps. A statistical mechanics analysis of the pre-exponential factor gave good agreement with experimental results, in which the pre-exponential factor for erythritol dehydration was much larger than that for 1,4-butanediol dehydration. Both erythritol and 1,4-butanediol could be intercalated in the interlayer spaces of the oxide. The expansion of the interlayer spaces for erythritol was, however, much larger than that for 1,4-butanediol. This improvement of accessibility is considered to be responsible for the higher reactivity of erythritol.

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... Protonated layered niobium molybdate and tantalum molybdate, HNbMoO6 and HTaMoO6, function as solid acid catalysts, whereas other layered metal oxides such as HTiNbO5 and HNbWO6 do not work because reactants cannot enter the interlayers [12][13][14][15][16][17][18][19][20]. The characteristics of layered HNbMoO6 and HTaMoO6 as solid acid catalysts are their unique ability of intercalation of reactants within the interlayers with strong Brønsted acid sites and high tolerance against water. ...
... Moreover, 1,4-butanediol was converted into tetrahydrofuran (THF) via the same 1,4-cyclodehydration. The HNbMoO6 catalyst exhibited moderate activity for 1,4-butanediol cyclodehydration, while it showed high activity for erythritol cyclodehydration [19]. Kinetic study on these cyclodehydration reactions over HNbMoO6 indicated that the difference of the activity between two C4 diols could be ascribed to different mobility of the activated complex based on the transition state theory. ...
Article
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Aqueous-phase acid-catalyzed reactions are essential for the conversion of cellulose-based biomass into chemicals. Brønsted acid and Lewis acid play important roles for these reactions, including hydrolysis of saccharides, isomerization and epimerization of aldoses, conversion of d-glucose into 5-hydroxymethylfurfural, cyclodehydration of sugar alcohols and conversion of trioses into lactic acid. A variety of metal oxide solid acids has been developed and applied for the conversion of sugars so far. The catalytic activity is mainly dependent on the structures and types of solid acids. Amorphous metal oxides possess coordinatively unsaturated metal sites that function as Lewis acid sites while some crystal metal oxides have strong Brønsted acid sites. This review introduces several types of metal oxide solid acids, such as layered metal oxides, metal oxide nanosheet aggregates, mesoporous metal oxides, amorphous metal oxides and supported metal oxides for sugar conversions.
... octane ring system. The cyclo-dehydration of 1,4-butanediol and meso-erythritol are known in acid catalyzed reactions [40]. In a recent study Takagaki has compared the cyclo-dehydration of erythritol using three Brønsted solid acids: HNbMoO 6 , H-ZSM5 and Amberlyst-15. ...
... In a recent study Takagaki has compared the cyclo-dehydration of erythritol using three Brønsted solid acids: HNbMoO 6 , H-ZSM5 and Amberlyst-15. In this study HNbMoO 6 showed the highest activity for erythritol dehydration to 1,4-anhydroerythritol [40]. The only aldehyde used in our work, formaldehyde (2a) gave a mixtures of bis-acetal (3a) and cis-2,4,7-trioxa [3.3.0] ...
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Brønsted acid catalyzed condensations of meso-erythritol with aldehyde/ketones were studied using meso-erythritol:aldehyde/ketone 1:3 ratio in a Dean–Stark apparatus. The selectivity among bis-ketal and 1,3-dioxolane-ether formation can be achieved by choosing between homogeneous and heterogeneous catalysts. The catalysts could be reused without appreciable loss in activity.
... 1,4-butanediol (BDO) containing two hydroxyl groups is an important platform chemical and has been widely applied in the production of tetrahydrofuran (THF), γ-butyrolactone (GBL), polybutylene terephthalate (PBT), polyurethane (PU), and so on [1][2][3][4]. Recently, BDO has been found to be converted to 3-butene-1-ol (BTO) through selective dehydration over metal oxide catalysts such as CeO 2 [5] and ZrO 2 [6][7][8]. ...
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Ca–Zr–Sn composite oxides catalysts for 1,4-butanediol (BDO) selective dehydration to 3-butene-1-ol (BTO) are synthesized by impregnation and co-precipitation in the present work. The results show that Ca–Zr–Sn catalysts prepared from co-precipitation by using NaOH-Na2CO3 mixing alkali solution as precipitant exhibit an excellent catalytic property for BDO dehydration to BTO. For instance, Ca–Zr–Sn oxide with Ca/Zr and Sn/Zr molar ratio of 0.68 and 0.28 calcined at 650 °C gives a BDO conversion and BTO selectivity of about 97% and 82%, respectively, and exhibits no deactivation during 1000 h scale-up experimental testing. X-ray diffraction results indicate that catalytic active centers for BDO dehydration to BTO are from Ca0.15Zr0.85O crystal phase. NH3- and CO2-temperature programmed desorption prove that the surface of obtained catalysts can provide a large amount of acid and base sites simultaneously. FT-IR spectra of pyridine-adsorbed samples show that acid sites on the surface of Ca–Zr–Sn oxide catalyst mainly exist in a state of Lewis acid, which activates terminal -OH groups of BDO molecule through complexing. The activated -OH interacts with β-H activated on base sites O2− anions relative to Ca species, thereby the CH2=CH- bonds are produced through dehydration to form BTO.
... Although conventional catalysts are very effective, they produce highly corrosive media and chemically reactive waste streams [11]. However, using heteropoly acids (HPAs) for the general operation of large chemical processes is ecofriendly and safe [12][13][14]. ...
Article
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Heteropoly acids were used as catalysts for cyclodehydration of various 1,n-diols. Cyclodehydration of butane-1,4-diol, pentane-1,5-diol and hexane-1,6-diol catalysed by H3PW12O40 gave tetrahydrofuran, tetrahydropyran and oxepane, respectively. Cyclodehydration of diethylene glycol, triethylene glycol, diethylene glycol monomethyl ether and polyethylene glycol 200 catalysed by H3PW12O40 gave 1,4-dioxane. In particular, cyclodehydration of hexane-1,6-diol gave an excellent yield of oxepane (80%). The selectivity exhibited by the H3PW12O40 catalyst was even better than that exhibited by other reported catalyst systems for similar cyclodehydration reactions.
... However, glucose yield from cellobiose was still only about 41%. The results proved that the hydrolysis is strongly influenced by the interaction of Lewis acid and Bronsted base sites (Takagaki, 2016). ...
Chapter
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... However, glucose yield from cellobiose was still only about 41%. The results proved that the hydrolysis is strongly influenced by the interaction of Lewis acid and Bronsted base sites (Takagaki, 2016). ...
Chapter
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