Kinetic Insight Into Glucose Conversion To 5-Hydroxymethyl Furfural And Levulinic Acid In Licl Center Dot 3h(2)O Without Additional Catalyst

CHEMICAL ENGINEERING JOURNAL(2021)

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摘要
Conversion of glucose to 5-hydromethyl furfural (HMF) and levulinic acid (LA) was systematically investigated in LiCl center dot 3H(2)O without additional catalyst. Based on the experimental investigations by using glucose, fructose and HMF as the reaction substrate separately, corresponding reaction kinetics in LiCl center dot 3H(2)O were modelled by first-order assumption. Kinetic analysis demonstrates that high temperature favors the formation of LA, while low temperature facilitates to selectively form humins. To achieve high LA yield, at least a temperature of 140 degrees C is required. Without additional catalyst converting glucose to LA in LiCl center dot 3H(2)O, humins was predominantly derived from glucose and HMF, and glucose isomerization is the reaction rate-determining step. The activation energies of the main reactions are 160.96 kJ/mol (glucose to HMF), 139.20 kJ/mol (fructose to HMF), and 71.81-76.48 kJ/mol (HMF to LA) respectively. The activation energies for humins formation were 23.45 kJ/mol from glucose, 49.54 kJ/mol from fructose, and 42.15-65.85 kJ/mol from HMF, respectively. It is verified that LiCl center dot 3H(2)O, as compared to aqueous medium, is an excellent reaction medium for converting glucose to LA as it can provide the active centers for fructose to HMF reaction and HMF to LA reaction, but lack of highly efficient Lewis acid for glucose isomerization. With the addition of Lewis acid (such as AlCl3 and FeCl3), as high as 83.4% of LA yield can be obtained respectively when directly converting glucose, with the total selectivities of LA and HMF of 95%.
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关键词
Kinetics, Molten salt hydrate, Glucose, 5-Hydroxymethyl furfural, Levulinic acid
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