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Sulfated Zirconia with Different Crystal Phases for the Production of Ethyl Levulinate and 5‐Hydroxymethylfurfural
Energy Technology ( IF 3.6 ) Pub Date : 2019-11-20 , DOI: 10.1002/ente.201900951 Yuewen Shao 1 , Yue Li 1 , Kai Sun 1 , Zhanming Zhang 1 , Hongli Tian 1 , Guoming Gao 1 , Qingyin Li 1 , Qianhe Liu 1 , Qing Liu 2 , Xun Hu 1
Energy Technology ( IF 3.6 ) Pub Date : 2019-11-20 , DOI: 10.1002/ente.201900951 Yuewen Shao 1 , Yue Li 1 , Kai Sun 1 , Zhanming Zhang 1 , Hongli Tian 1 , Guoming Gao 1 , Qingyin Li 1 , Qianhe Liu 1 , Qing Liu 2 , Xun Hu 1
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Distinct crystal phases of an oxide affect the configuration of surface atoms, which might further affect coordination with sulfate during sulfonation for the preparation of SO42−/MxOy type of acid catalyst. Herein, such an effect is investigated with zirconia of the tetragonal or monoclinic phase as the model catalysts. The results show that sulfonation inhibits the transformation of zirconia from the tetragonal phase to the monoclinic phase, whereas the varied phase of zirconia also affects the bonding patterns of sulfate species with zirconia in sulfonation. The sulfated zirconia of monoclinic phase contains more abundant acidic sites and more Brønsted acid sites than that of sulfated zirconia of tetragonal phase. Consequently, the sulfated zirconia of monoclinic phase is more active than the sulfated zirconia of tetragonal phase for the conversion of furfuryl alcohol in ethanol and conversion of fructose in dimethyl sulfoxide, achieving the yield of ethyl levulinate of 96.4% and a high yield of 5‐hydroxymethylfurfural. The sulfated zirconia is not stable in protic solvent due to the leaching of sulfur species and the change in configurations of the sulfate species and the zirconium species, but in the aprotic solvent, they show good stability and recyclability.
中文翻译：
硫酸法合成不同晶相的氧化锆生产乙酰丙酸乙酯和5-羟甲基糠醛
氧化物的不同晶相会影响表面原子的构型，这可能会进一步影响磺化过程中与硫酸盐的配位以制备SO 4 2- / M x O y酸催化剂的类型。在此，以四方相或单斜晶相的氧化锆作为模型催化剂来研究这种效果。结果表明，磺化作用抑制了氧化锆从四方相向单斜晶相的转变，而氧化锆的变化相也影响了磺化过程中硫酸盐与氧化锆的键合方式。单斜晶相的硫酸盐氧化锆比四方相的硫酸盐氧化锆具有更多的酸性位点和更多的布朗斯台德酸位点。因此，单斜晶相的硫酸化氧化锆比四方相的硫酸化氧化锆对乙醇中的糠醇转化和二甲基亚砜中的果糖转化具有更高的活性，乙酰丙酮酸乙酯的收率达96.4％，高收率5-羟甲基糠醛。
更新日期：2019-11-20
中文翻译：
硫酸法合成不同晶相的氧化锆生产乙酰丙酸乙酯和5-羟甲基糠醛
氧化物的不同晶相会影响表面原子的构型，这可能会进一步影响磺化过程中与硫酸盐的配位以制备SO 4 2- / M x O y酸催化剂的类型。在此，以四方相或单斜晶相的氧化锆作为模型催化剂来研究这种效果。结果表明，磺化作用抑制了氧化锆从四方相向单斜晶相的转变，而氧化锆的变化相也影响了磺化过程中硫酸盐与氧化锆的键合方式。单斜晶相的硫酸盐氧化锆比四方相的硫酸盐氧化锆具有更多的酸性位点和更多的布朗斯台德酸位点。因此，单斜晶相的硫酸化氧化锆比四方相的硫酸化氧化锆对乙醇中的糠醇转化和二甲基亚砜中的果糖转化具有更高的活性，乙酰丙酮酸乙酯的收率达96.4％，高收率5-羟甲基糠醛。
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