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

Abstract

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.

Synthesis of 1,3-Butadiene and Its 2-Substituted Monomers for Synthetic Rubbers

“…Duan et al have reviewed the dehydration of BDOs to UOLs in connection with their further dehydration to BD [17]. Not long ago, Duan et al [62] investigated the dehydration of 2,3-BDO to 3B2OL over modified monoclinic ZrO2 catalysts, suggesting that BaO/ZrO2, SrO/ZrO2, and CaO/ZrO2 have good catalytic capacities. The optimized data were observed over BaO-0.0452-800 with a 2,3-BDO conversion of 72.4% and a 3B2OL selectivity of 74.4% during the early stage of 5 h at 350 °C.…”

“…Not long ago, Duan et al [62] investigated the dehydration of 2,3-BDO to 3B2OL over modified monoclinic ZrO 2 catalysts, suggesting that BaO/ZrO 2 , SrO/ZrO 2 , and CaO/ZrO 2 have good catalytic capacities. The optimized data were observed over BaO-0.0452-800 with a 2,3-BDO conversion of 72.4% and a 3B2OL selectivity of 74.4% during the early stage of 5 h at 350 • C. Unfortunately, a decrease in catalytic activity occurred over a long-term operation of 25 h. This is due to the formation of Perovskite compounds, such as BaZrO 3 , which are inactive for the reaction.…”

“…Synthesis of BD from butanediols (BDOs) or C4 unsaturated alcohols (UOLs)[17,[62][63][64][65]. Evolution from reagents and intermediates to the target BD is labeled by arrows, and the by-products are produced during Dehydration 1.…”

Bio-Based Solvents and Gasoline Components from Renewable 2,3-Butanediol and 1,2-Propanediol: Synthesis and Characterization

“…Hence, the noted compounds are of particular interest as renewable feedstocks for the production of chemicals. The majority of studies on 2,3-BD conversion are dedicated to its dehydrative conversion that yields methyl ethyl ketone (MEK) and isobutyraldehyde [9][10][11][12], 3-butene-2-ol [10,[13][14][15], butenes [16][17][18] and 1,3-butadiene [19][20][21]. Some 2,3-BD derivatives have been previously considered as potential motor fuel components and organic solvents.…”

MOF derived mesoporous K-ZrO2 with enhanced basic catalytic performance for Knoevenagel condensations

“…K 2 O). 8 Considering that zirconia derived from precipitation method usually possess low surface areas, new efforts have been focused on the immobilization of K + /ZrO 2 (KZ) on mesoporous silica and inducing mesopores into zirconia with the aid of block copolymers as porogens. 9,10 Well-dispersed basic catalytic sites can be produced with enhanced surface areas, which improve the diffusion rate of reactants and products, as well as catalytic performance of the solid base.…”