Chemical Engineering Journal ( IF 13.3 ) Pub Date : 2020-07-01 , DOI: 10.1016/j.cej.2020.126143 J. Kowalska-Kuś , A. Held , K. Nowińska
A continuous flow process using heterogeneous catalysts like zeolites (BEA, MFI, FAU) was developed for the conversion of crude glycerol with acetone to solketal (2,2-dimethyl-1,3-dioxolane-4-methanol). It was found that BEA zeolite and the hierarchical zeolite of MFI structure exhibit a high catalytic activity in solketal production for 3 hr on stream. Almost 85% of glycerol conversion and 98% selectivity to solketal was achieved after 1 h of the reaction. The regeneration of spent catalysts by means of calcination with following ionic exchange restored the initial activity of the applied samples. The effect of particular impurities (alkaline cations, water, and MONG (matter organic non glycerol)) present in crude glycerol, on the deactivation process of catalysts, was also explored. Analysis of carbon balance and low-temperature nitrogen adsorption/desorption measurements, as well as FT-IR spectra of applied materials (pure and crude glycerol and spent catalysts) evidenced that the concurrent presence of MONG and alkaline cations reduce the zeolite catalysts activity.
Considering the alteration of selectivity toward five and six membered isomers with declining acidity of spent catalyst, some tentative reaction paths of both isomers formation have been proposed.
中文翻译:
在沸石催化剂上用丙酮将粗甘油缩醛化的连续流工艺
开发了使用非均相催化剂(例如沸石(BEA,MFI,FAU))的连续流工艺,用于将丙酮中的粗甘油转化为Solketal(2,2-二甲基-1,3-二氧戊环-4-甲醇)。发现BEA沸石和MFI结构的分级沸石在溶胶生产中持续运行3小时显示出高催化活性。反应1小时后,几乎达到了85%的甘油转化率和98%的对缩酮的选择性。通过煅烧和随后的离子交换,使废催化剂再生,从而恢复了所施加样品的初始活性。还研究了粗甘油中存在的特定杂质(碱性阳离子,水和MONG(有机非甘油))对催化剂失活过程的影响。
考虑到随着废催化剂的酸度下降,对五元和六元异构体的选择性变化,提出了两种异构体形成的初步反应路径。