Synthesis of 3-buten-1-ol from 1,4-butanediol over ZrO2 catalyst
Synthesis of 3-buten-1-ol from 1,4-butanediol over ZrO2 catalyst
复制标题
DOI：
10.1016/j.molcata.2005.08.017
复制
发表时间：
2006-01
影响因子：
--
通讯作者：
Naoki Yamamoto;S. Sato;Ryōji Takahashi;Kanichiro Inui
中科院分区：
文献类型：
--
作者：
Naoki Yamamoto;S. Sato;Ryōji Takahashi;Kanichiro Inui
在325~375℃温度范围内，研究了1，4-丁二醇在氧化锆催化剂上的脱水反应。用少量氢氧化钠对氧化锆进行改性，大大提高了3-丁烯-1-醇的选择性。吸附的NH3和CO2的程序升温脱附分别表征了催化剂的酸性和碱性。随着Na含量的增加，催化剂表面的酸性中心数量减少，当Na含量为1.0mol%时，酸性中心数量消失，而碱性中心数量增加。在Na含量与产物选择性的关系中，对四氢呋喃和γ-丁内酯的选择性分别随着酸性中心和碱性中心数目的增加而增加。但在适当的钠含量下，3-丁烯-1-醇的选择性最高。3-丁烷-1-醇可能是由1，4-丁二醇脱水反应中单斜晶型氧化锆的酸碱协同催化作用形成的。
Dehydration of 1,4-butanediol was investigated over ZrO2at temperatures of 325–375°C. Modification of ZrO2with a small amount of sodium hydroxide greatly enhanced the selectivity to 3-buten-1-ol. Temperature-programmed desorption of adsorbed NH3and CO2elucidated acidity and basicity of the catalysts, respectively. The number of acidic sites on the ZrO2decreased with increasing Na content, and disappeared at Na content of 1.0mol%, whereas the number of basic sites increased with increasing Na content. In the relationship between Na content and the selectivity to products, selectivities to tetrahydrofuran and γ-butyrolactone simply increased with the number of acidic and basic sites, respectively. However, the selectivity to 3-buten-1-ol was maximized at an appropriate Na content. 3-Butan-1-ol is possibly formed by acid–base-concerted catalysis of monoclinic ZrO2in the dehydration of 1,4-butanediol.