金属氧化物催化甘油与一氧化碳的直接碳酸化反应

Direct Carbonation of Glycerol with CO Catalyzed by Metal Oxides.

作者信息

Ozorio Leonardo P, Mota Claudio J A

机构信息

Universidade Federal do Rio de Janeiro, Escola de Química, Av Athos da Silveira Ramos 149, Bloco E, Rio, de Janeiro, 21941-909, Brazil.

Instituto de Química, Universidade Federal do Rio de Janeiro, Av Athos da Silveira Ramos 149, Bloco A, Rio, de Janeiro, 21941-909, Brazil.

出版信息

Chemphyschem. 2017 Nov 17;18(22):3260-3265. doi: 10.1002/cphc.201700579. Epub 2017 Oct 6.

DOI:10.1002/cphc.201700579

PMID:28796423

Abstract

Five metal oxides (ZnO, SnO , Fe O , CeO , La O ) were produced by the sol-gel method and tested in the direct carbonation of glycerol with CO . Initial tests with Fe O showed that the best reaction condition was 180 °C, 150 bar, and 12 h. The other oxides were evaluated at these conditions and were all active to the formation of glycerol carbonate. Zinc oxide was the most active catalyst, with a yield of 8.1 % in the organic carbonate. The catalytic activity decreased upon washing and drying the ZnO catalyst between the runs. Nevertheless, the activity is maintained if the ZnO is washed and calcined at 450 °C between the runs. FTIR and TGA results indicated the formation of ZnCO as the main cause of catalyst deactivation, which may be decomposed upon calcination of the material. No appreciable leaching of Zn was observed, indicating a truly heterogeneous catalysis.

摘要

通过溶胶-凝胶法制备了五种金属氧化物（ZnO、SnO 、Fe O 、CeO 、La O ），并在甘油与CO 的直接碳酸化反应中进行了测试。对Fe O 的初步测试表明，最佳反应条件为180 °C、150 bar和12 h。在这些条件下对其他氧化物进行了评估，它们对碳酸甘油酯的形成均具有活性。氧化锌是活性最高的催化剂，有机碳酸酯的产率为8.1 %。在运行之间对ZnO催化剂进行洗涤和干燥后，催化活性会降低。然而，如果在运行之间将ZnO洗涤并在450 °C下煅烧，则活性可以保持。傅里叶变换红外光谱（FTIR）和热重分析（TGA）结果表明，ZnCO 的形成是催化剂失活的主要原因，在材料煅烧时其可能会分解。未观察到明显的锌浸出，表明这是真正的多相催化。