Selective dehydration of 2,3-butanediol to 3-buten-2-ol over ZrO2 modified with CaO

Duan, Hailing; Yamada, Yoshio; Sato, Satoshi

doi:10.1016/j.apcata.2014.09.007

Cited by 36 publications

(33 citation statements)

References 34 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Since the formations of BD and 3B2OL differ in activation energy, their distribution was successfully controlled by reaction temperature. The 1,2-elimination of 2,3-BDO to produce BD and 3B2OL also occurred over the base-acid bifunctional catalysts such as ZrO 2 [19], CaO/ZrO 2 [25], SiO 2 -supported sodium phosphates [26], and SiO 2 -supported cesium dihydrogen phosphate [27]. Over the base-acid bifunctional catalysts, the 2-position hydroxyl group of 2,3-BDO was captured by an acid site and dissociated to form a carbon cation, together with the terminal hydrogen by a basic site for a carbon anion.…”

Section: Introductionmentioning

confidence: 97%

Vapor-phase catalytic dehydration of 2,3-butanediol to 3-buten-2-ol over ZrO2 modified with alkaline earth metal oxides

Duan

Yamada

Kubo

et al. 2017

Applied Catalysis A: General

Self Cite

View full text Add to dashboard Cite

Vapor-phase catalytic dehydration of 2,3-butanediol (2,3-BDO) to produce 3-buten-2-ol (3B2OL) was investigated over several monoclinic ZrO 2 (m-ZrO 2) catalysts modified with alkaline earth metal oxides (MOs), such as SrO, BaO, and MgO, to compare with the previously reported CaO/m-ZrO 2. It was found that those modifiers enhanced the 3B2OL formation to the same level as CaO did by loading an appropriate MO content. Among all the tested catalysts, the BaO/m-ZrO 2 calcined at 800 o C with a low BaO content (molar ratio of BaO/ZrO 2 = 0.0452) shows the highest 2,3-BDO conversion (72.4%) and 3B2OL selectivity (74.4%) in the initial stage of 5 h at 350 o C. In order to characterize those catalysts, their catalytic activities, crystal structures, and basic properties were studied in detail. In X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) experiment, it was elucidated that highly dispersed M-O-Zr (M= Ca, Sr, and Ba) hetero-linkages were formed on the surface by loading these MOs onto m-ZrO 2 with an appropriate content and then calcining at 800 o C. It can be concluded that the M-O-Zr hetero-linkages generate the proper base-acid balance for the efficient formation of 3B2OL from 2,3-BDO.

show abstract

Section: Introductionmentioning

confidence: 97%

Vapor-phase catalytic dehydration of 2,3-butanediol to 3-buten-2-ol over ZrO2 modified with alkaline earth metal oxides

Duan

Yamada

Kubo

et al. 2017

Applied Catalysis A: General

Self Cite

View full text Add to dashboard Cite

show abstract

“…Using two catalytic beds, with scandium oxide and alumina, selectivity to C4H6 was 94%, proving the feasibility of direct double bond dehydration of 2,3 butanediol [91]. Alternatively, two step processes, using two different catalysts (e.g., silica or alumina based) for subsequent dehydrations, have also been proposed, yielding C4H6 via the formation of unsaturated alcohols [112]. Novel chemical and biochemical technologies enable the production of C4H6 from syngas originating from the gasification of biomass or waste gases from the steel industry; butanediols can be produced from syngas via fermentation [113].…”

Section: Butadiene (C4h6)mentioning

confidence: 99%

Olefins from Biomass Intermediates: A Review

2017

View full text Add to dashboard Cite

Over the last decade, increasing demand for olefins and their valuable products has prompted research on novel processes and technologies for their selective production. As olefins are predominately dependent on fossil resources, their production is limited by the finite reserves and the associated economic and environmental concerns. The need for alternative routes for olefin production is imperative in order to meet the exceedingly high demand, worldwide. Biomass is considered a promising alternative feedstock that can be converted into the valuable olefins, among other chemicals and fuels. Through processes such as fermentation, gasification, cracking and deoxygenation, biomass derivatives can be effectively converted into C 2 -C 4 olefins. This short review focuses on the conversion of biomass-derived oxygenates into the most valuable olefins, e.g., ethylene, propylene, and butadiene.

show abstract

“…A decrease in the acid sites of monoclinic ZrO 2 is effective for the decrease in the selectivity to MEK by the modification with some basic metal oxides such as Li 2 O, La 2 O 3 , and CaO. 95 However, strong basic Li 2 O-and La 2 O 3 -modified monoclinic ZrO 2 catalysts increase the dehydrogenation product, 3H2BO. In contrast, the modification of monoclinic ZrO 2 with basic alkaline earth metal oxides such as CaO, SrO, and BaO are efficient for the production of 3B2OL.…”

mentioning

confidence: 99%

“…The site B is a basic site with medium strength newly generated by such heterolinkage of CaOZr on the alkaline earth metal oxides modified monoclinic ZrO 2 . 95 Site B eliminates the 1-position proton, followed by the elimination of the neighboring OH ¹ group coordinated to site A 1 , to produce 3B2OL, while site A 2 has a significant function for anchoring the diol molecule (Scheme 11). Monoalcohols such as 1-/2-butanols and 3B2OL are much less reactive than BDOs over the catalysts.…”

mentioning

confidence: 99%

“…New basic sites with medium strength, which belong neither to ZrO 2 nor to the alkaline earth metal oxides, are detected in the active catalysts. 95 Sc 2 O 3 catalyzes the formation of 3B2OL from 2,3-BDO (Table 3), 96 although Sc 2 O 3 is rarely used as a catalyst itself because of its high cost. After the calcination of Sc 2 O 3 at temperatures higher than 800°C, Sc 2 O 3 shows an excellent activity not only for the formation of 3B2OL from 2,3-BDO but also for the corresponding UOLs from the terminal diols, such as 1,6-hexanediol and 1,10-decanediol.…”

mentioning

confidence: 99%

See 1 more Smart Citation

Future Prospect of the Production of 1,3-Butadiene from Butanediols

Duan¹,

Yamada²,

Sato³

2016

Chem. Lett.

Self Cite

View full text Add to dashboard Cite

Global supply of 1,3-butadiene (abbreviated as BD) is faced with problems such as unstable price of petrochemicals and variation of chemical feedstock in recent years. Many research works have been conducted to produce BD from some renewable resources instead of petroleum. Among them, biomass-derived C 4 alcohols such as 1,3-butanediol (1,3-BDO), 2,3-butanediol (2,3-BDO), and 1,4-butanediol (1,4-BDO) have been considered as alternative resources to produce BD. Direct dehydration of butanediols (BDOs) into BD, however, needs high reaction temperatures while the dehydration into their corresponding unsaturated alcohols (UOLs) such as 3-buten-2-ol (3B2OL), 2-buten-1-ol (2B1OL), and 3-buten-1-ol (3B1OL) proceeds at rather low temperatures over specific catalysts. The latter step of BDO dehydration, dehydration of UOLs to BD, is readily catalyzed by solid acids even at lower temperatures than those at which BDOs are dehydrated completely. Thus, efficient formation of UOLs from BDOs would be a key process to produce BD with high selectivity. We summarize the BD production from C 4 alcohols as well as the dehydration of BDOs to UOLs, in addition to the BD production via ethanol dimerization.

show abstract

Selective dehydration of 2,3-butanediol to 3-buten-2-ol over ZrO2 modified with CaO

Cited by 36 publications

References 34 publications

Vapor-phase catalytic dehydration of 2,3-butanediol to 3-buten-2-ol over ZrO2 modified with alkaline earth metal oxides

Vapor-phase catalytic dehydration of 2,3-butanediol to 3-buten-2-ol over ZrO2 modified with alkaline earth metal oxides

Olefins from Biomass Intermediates: A Review

Future Prospect of the Production of 1,3-Butadiene from Butanediols

Contact Info

Product

Resources

About