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Synthesis of 1,3-Propanediol by Cross Aldol Reaction and Hydrogenation of Formaldehyde with Acetaldehyde
ACS Sustainable Chemistry & Engineering ( IF 7.1 ) Pub Date : 2022-02-10 , DOI: 10.1021/acssuschemeng.1c06393
Shifeng Jiang 1 , Zheng Li 1, 2 , Lingling Zhao 1, 2 , Mengqing Sun 1 , Xu Zhang 3 , Dongyuan Yang 4, 5 , Guoqiang Xu 1
Affiliation  

3-Hydroxypropanal (3-HPA) is formed by the cross-aldol reaction of formaldehyde (HCHO) with acetaldehyde (CH3CHO), which further converts to 1,3-propanediol (1,3-PDO). Mg/SiO2 and X-5Mg/SiO2 (X = Mn, Fe, Co, Ni) catalysts were prepared using the sol–gel method and characterized with XRD, BET, TEM, and NH3- and CO2-TPD methods. The 5Mg/SiO2 showed higher activity in terms of the yield and selectivity due to its suitable basic and acidic density. The addition of Mn to the 5Mg/SiO2 catalyst caused dispelling of weak basic sites but maintained strong basic sites, and the high CH3CHO conversion was maintained. The increase of weak acidic sites contributed to the increase of 3-HPA selectivity for the 1Mn-5Mg/SiO2 catalyst. The cross-aldol reaction of HCHO with CH3CHO to produce 3-HPA more easily proceeded than the self-aldol reaction of CH3CHO according to the reaction kinetic analysis. Furthermore, Raney nickel was successfully applied to the hydrogenation process of 3-HPA to 1,3-PDO with over 90% HPA conversion and 1,3-PDO selectivity.

中文翻译:

交叉羟醛反应和甲醛与乙醛加氢合成1,3-丙二醇

3-羟基丙醛 (3-HPA) 由甲醛 (HCHO) 与乙醛 (CH 3 CHO) 的交叉羟醛反应形成,乙醛进一步转化为 1,3-丙二醇 (1,3-PDO)。采用溶胶-凝胶法制备了Mg/SiO 2和 X-5Mg/SiO 2 (X = Mn, Fe, Co, Ni) 催化剂,并通过 XRD、BET、TEM 和 NH 3 - 和 CO 2 -TPD 方法对其进行了表征. 5Mg/SiO 2由于其合适的碱性和酸性密度,在产率和选择性方面表现出更高的活性。在 5Mg/SiO 2催化剂中添加 Mn 导致弱碱性位点的消除,但保持强碱性位点,高 CH 3维持CHO转化。弱酸性位点的增加有助于提高 3-HPA 对 1Mn-5Mg/SiO 2催化剂的选择性。根据反应动力学分析,HCHO与CH 3 CHO的交叉醛醇反应生成3-HPA比CH 3 CHO的自身醛醇反应更容易进行此外,雷尼镍成功应用于3-HPA加氢制1,3-PDO,HPA转化率超过90%,1,3-PDO选择性高。
更新日期:2022-02-10
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