Dehydration of Biomass-Derived Butanediols over Rare Earth Zirconate Catalysts
Dehydration of Biomass-Derived Butanediols over Rare Earth Zirconate Catalysts
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DOI：
10.3390/catal10121392
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发表时间：
2020-11
期刊：
影响因子：
3.9
通讯作者：
Asami Matsuda;Y. Matsumura;Kazuki Nakazono;F. Sato;Ryōji Takahashi;Yasuhiro Yamada;S. Sato
中科院分区：
文献类型：
--
作者：
Asami Matsuda;Y. Matsumura;Kazuki Nakazono;F. Sato;Ryōji Takahashi;Yasuhiro Yamada;S. Sato
这项工作的目的是开发一种有效的催化剂，将从生物质中衍生的丁二醇转化为有价值的化学品，如不饱和醇。在气相流反应器中，采用16种稀土锆酸盐催化剂，在325℃下对1,4-、1,3-和2,3-丁二醇脱水生成3-丁醇-1醇、2-丁醇和3-丁醇-2-醇等不饱和醇进行了研究。采用水热法制备了高结晶度、高比表面积的稀土锆酸盐。含重稀土的锆酸盐，特别是含氧缺陷萤石结构的Y2Zr2O7，对1,4-丁二醇选择性脱水生成3-丁烯-1-醇和1,3-丁二醇选择性脱水生成3-丁烯-2-醇和2-丁烯-1-醇具有较高的催化性能，而锆酸盐催化剂对2,3-丁二醇的脱水活性较低。Y2Zr2O7的煅烧对1,4-丁二醇脱水的催化活性有显著影响：900℃以上的Y2Zr2O7煅烧温度对选择性生成不饱和醇具有较好的催化活性。高结晶度的Y2Zr2O7在325℃时，1,4-丁二醇生成3-丁-1-醇的产率最高。
The aim of this work is to develop an effective catalyst for the conversion of butanediols, which is derivable from biomass, to valuable chemicals such as unsaturated alcohols. The dehydration of 1,4-, 1,3-, and 2,3-butanediol to form unsaturated alcohols such as 3-buten-1-ol, 2-buten-1-ol, and 3-buten-2-ol was studied in a vapor-phase flow reactor over sixteen rare earth zirconate catalysts at 325 °C. Rare earth zirconates with high crystallinity and high specific surface area were prepared in a hydrothermal treatment of co-precipitated hydroxide. Zirconates with heavy rare earth metals, especially Y2Zr2O7 with an oxygen-defected fluorite structure, showed high catalytic performance of selective dehydration of 1,4-butanediol to 3-buten-1-ol and also of 1,3-butanediol to form 3-buten-2-ol and 2-buten-1-ol, while the zirconate catalysts were less active in the dehydration of 2,3-butanediol. The calcination of Y2Zr2O7 significantly affected the catalytic activity of the dehydration of 1,4-butanediol: a calcination temperature of Y2Zr2O7 at 900 °C or higher was efficient for selective formation of unsaturated alcohols. Y2Zr2O7 with high crystallinity exhibits the highest productivity of 3-buten-1-ol from 1,4-butanediol at 325 °C.